JP2002273841A - Soft polyolefinic resin laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft polyolefinic resin laminated sheet excellent in flexibility, abrasion resistance, printability, high frequency fusibility, the breaking strength of a fused part and thermal creep resistance. SOLUTION: The soft polyolefinic resin laminated sheet is constituted by forming a coating layer containing a resin blend, which contains 30-70 wt.% of a polypropylene type resin (A), 10-50 wt.% of a styrenic copolymer resin (B), and 5-40 wt.% of an ethylene/vinyl acetate and/or (meth)acrylic acid (ester) copolymer (C) (herein, a ratio of copolymerized vinyl acetate and a (meth)acrylic acid (ester) to the sum total weight of A+B+C is 3-25%), on the single surface or both surfaces of a fiber cloth-containing fibric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin laminated sheet used for industrial materials. More specifically, the present invention is obtained by laminating a specific polyolefin-based resin film on a fiber cloth as a base material, and has excellent flexibility, abrasion resistance, printability and heat creep resistance, and particularly flexible containers and oils. The present invention relates to a high-frequency fusion-bondable polyolefin resin laminated sheet suitable for applications such as fences, truck bed covers, and house tents.

[0002]

2. Description of the Related Art Conventionally, sheet materials for flexible containers and other industrial material sheets, such as oil fences, truck bed covers, house tents, cushion mats, etc., are made of fiber woven fabric and soft polychloride. A composite sheet with a vinyl resin film, a composite sheet with a fiber woven fabric and a synthetic rubber, a composite sheet with a fiber woven fabric and a polyurethane resin, a composite sheet with a fiber woven fabric and a polyolefin resin, and the like are used. Above all, flexible containers are used repeatedly in logistics means,
On the user side, we pursue materials that are more durable and economical, and on the transportation side, which handles logistics, when the flexible container returns to the shipping manufacturer with empty bags, it can be folded compactly and is lightweight. Is demanding. On the side of the manufacturer of the flexible container, sewing can be performed with a high-frequency welding machine, and the high flexibility is considered to be convenient for the sewing operation. Among these sheet materials, those made of a soft polyvinyl chloride resin are most widely used, because they are excellent in durability and economy and can be subjected to high-frequency fusion. Soft polyvinyl chloride resin sheets are most often used in other industrial material sheet materials for the same reason.

[0003] Polyvinyl chloride resin is a general-purpose resin which is flexible and tough and is widely used in many fields as a synthetic resin material excellent in transparency, workability and cost.
However, recently, suspicions that phthalate esters contained as plasticizers in flexible polyvinyl chloride resin products are phorone-disrupting substances have been discussed, and furthermore, they must be mixed into groundwater systems for landfill disposal. Is also worried. On the other hand, attention has been paid to a warning that a dioxin derivative is generated when a polyvinyl chloride resin product containing phthalate esters is incinerated. Under such environmental unrest, measures have been developed to reduce the use of polyvinyl chloride resin products as much as possible for disposable articles such as packaging materials and containers, and recently, polyethylene resin, polypropylene resin, etc. Products based on polyolefin resins have begun to spread widely.

Conventionally, polyethylene resin, ethylene-vinyl acetate copolymer resin, etc., used as raw materials for sheet materials made of polyolefin resin, have been registered with the Polyolefin Hygiene Council's self-regulation standards as part numbers, notices issued by the Ministry of Health and Welfare. No. 434, which conforms to the Food Sanitation Testing Standard, US F. D. A (Section 121, 2570) allows the obtained sheet material to be used as a highly safe flexible container suitable for transporting food raw materials by selecting from those approved in part numbers. As a flexible container made of a polyolefin resin, a sheet material made of an ethylene-vinyl acetate copolymer resin is used most frequently because it is flexible and can be sewn at a high frequency.

However, since these ethylene-vinyl acetate copolymer resins contain a large amount of a highly polar vinyl acetate component to a certain extent, they are excellent in flexibility and high-frequency weldability. There is a problem that the wear resistance is insufficient and a strong acetic acid odor is accompanied. In order to solve this problem, a polyethylene resin or an ethylene-α-olefin copolymer resin is blended with an ethylene-vinyl acetate copolymer resin to improve the resin strength and wear resistance, or a polyethylene resin and It is widely used to blend an ethylene-vinyl acetate copolymer resin containing a vinyl acetate component at a high concentration based on the ethylene-α-olefin copolymer resin. According to this method, it is possible to simultaneously improve the high-frequency weldability and the resin strength and the wear resistance of the obtained sheet material to a certain degree.
No sheet material has been obtained which fully satisfies the requirements of both of these properties. That is, if the mixing ratio of the polyethylene resin and the ethylene-α-olefin copolymer resin used in the blend is increased, the resin strength and the abrasion resistance can be certainly improved, but the high frequency weldability becomes insufficient and the high frequency sewing work is difficult. Becomes On the contrary, by increasing the mixing ratio of the ethylene-vinyl acetate copolymer resin, it is possible to certainly improve the high-frequency weldability,
As a result, the resin strength and the wear resistance become insufficient.
Further, in any of the above blends, in order to contain a highly crystalline polyethylene resin or ethylene-α-olefin copolymer resin, the texture of the obtained sheet material is made hard, and the obtained flexible container is folded. However, problems such as bulkiness and inconvenience in distribution are inevitable. Further, at this time, there is a problem such that a wrinkle mark which causes fatigue deterioration is left in the resin at the bent portion due to excessive folding. Therefore, the method using the above resin blend has a problem that its application range is too narrow for a material requiring a high degree of flexibility and durability. In addition, the sheet material obtained by the above method has poor printability, requires a special printing ink, and requires the sheet material to be subjected to corona discharge treatment as a pretreatment for printing. Poor workability has been pointed out.

Polyolefin resins such as polyethylene resin, ethylene-α-olefin copolymer resin, and ethylene-vinyl acetate copolymer resin have lower heat resistance than polyvinyl chloride resin, and the above-mentioned polyolefin resin composition A flexible container manufactured from a product and heat-sealed in a bag is inferior to a flexible container made of a soft polyvinyl chloride resin in heat creep resistance of a joint thereof. In this case, there is a problem that the resin in the sewn portion at the bottom of the container is softened to cause a bottom breakage. For the purpose of solving this problem, there is a proposal to mix high melting point resin such as high density polyethylene resin or polypropylene resin,
In order to achieve the purpose of improving the heat resistance of the flexible container, it is necessary to increase the compounding ratio of these high melting point resins, so that the texture of the obtained sheet material becomes too hard and the handleability is poor, Further ethylene-
A blend of a vinyl acetate copolymer resin and a polypropylene resin has a drawback that uniform melting and kneading and molding are difficult because the melting point temperature difference between the resins is large and the melt viscosities are greatly different. For this reason, during processing, high-temperature kneading is required so that the polypropylene resin becomes a low-viscosity melt. However, in high-temperature kneading, the ethylene-vinyl acetate copolymer resin thermally decomposes (generates acetic acid gas), There is a problem that the resin deteriorates. Also, as another means,
In a method of softening by blending a rubber component such as an ethylene-propylene rubber (EPR) or an ethylene-propylene-non-conjugated diene rubber (EPDM) with a polypropylene resin as a main component, a certain degree of flexibility and transparency are obtained. Although it is possible to obtain, in this blend system, the polypropylene resin and the rubber component are essentially incompatible with each other and cause microphase separation, so that the strength and the tear strength are insufficient.

[0007] Further, the breakage of the sewn portion of the high-frequency sewn product is also caused by the substantially low adhesiveness between the fiber woven fabric and the polyolefin resin film. Processing is required. However, many of the adhesives capable of bonding with the polyolefin resin are
Even if a sufficient effect of preventing the breakage of the sewn portion is obtained at room temperature, 6
Under an environment exceeding 0 ° C., the adhesive softens and the strength of the sewn portion is suddenly lost, so that there is a defect in heat creep resistance, and ultimately it cannot be used for heat resistant applications. In addition, in the adhesive system using a curing agent, although a certain degree of improvement in heat-resistant creep properties is recognized, the sheet material is hardened, and at the same time, the tear strength is reduced and the sheet material is easily broken. It has disadvantages and therefore cannot be used for industrial materials such as flexible containers, oil fences, truck bed covers, house tents and cushion mats.

[0008] Therefore, it can be used as a substitute for an industrial material sheet made of polyvinyl chloride resin, has durability such as soft texture and high abrasion resistance, and is easy to perform secondary processing of printing and high frequency fusion. Certain polyolefin resin sheets,
Further, a polyolefin-based resin sheet excellent in the breaking strength of the high-frequency welded portion and the heat creep resistance has not been put to practical use.

[0009]

DISCLOSURE OF THE INVENTION The present invention has a soft texture and durability such as abrasion resistance, is easy to perform secondary processing of printing and high frequency fusion, and destroys a high frequency fusion portion. An object of the present invention is to provide a polyolefin resin sheet having excellent strength and heat creep resistance and suitable for applications such as flexible containers, oil fences, truck bed sheets, house tents, and cushion mats.

[0010]

According to the present invention, there is provided a flexible polyolefin resin laminated sheet according to the present invention comprising: a base fabric including a fiber fabric; and a coating layer formed on at least one surface of the base fabric and comprising a polyolefin resin blend. Wherein the polyolefin-based resin blend layer comprises (A) a component composed of a polypropylene-based resin, (B) a component composed of a styrene-based copolymer resin, and (C) an ethylene-vinyl acetate copolymer resin, and / or The components (A), (B) and (C), which are formed from a polyolefin-based resin blend containing, a component consisting of ethylene- (meth) acrylic acid (ester) copolymer resin, and contained in the resin blend The content of the component (A) is 30 to 70% by weight, the content of the component (B) is 10 to 50% by weight, and the content of the component (C) is 5 to the total weight of 40% by weight, and the total content of copolymerized vinyl acetate and (meth) acrylate in the component (C) contained in the resin blend is 3 to 25% by weight. , Is characterized. In the flexible polyolefin-based resin sheet of the present invention, it is preferable that a contamination prevention layer is formed as an outermost layer on at least one of the polyolefin-based resin blend coating layers. In the flexible polyolefin-based resin laminated sheet of the present invention, a surface layer comprising a surface polyolefin-based resin blend (a) is formed on a surface of a base fabric including the fiber cloth, and a back-surface polyolefin-based resin blend is formed on a back surface of the base fabric. (B) wherein the back and front polyolefin resin blend layers (a) and (b) each comprise (A) a component comprising a polypropylene resin, and (B) a styrene copolymer. A polyolefin-based resin blend containing a component consisting of a combined resin and (C) a component consisting of an ethylene-vinyl acetate copolymer resin and / or an ethylene- (meth) acrylic acid (ester) copolymer resin. In the surface polyolefin resin blend layer (a), the total weight of the components (A), (B) and (C) contained therein The content of the component (A) is 30 to 70% by weight, the content of the component (B) is 10 to 50% by weight, the content of the component (C) is 5 to 40% by weight, And copolymerized vinyl acetate and (meth) acrylic acid (ester) in the component (C) contained in the resin blend (a).
Is 3 to 10% by weight, and in the back polyolefin resin blend layer (b), the component (A), (B) and (C) contain the component ( A) The content of A) is 30 to 70% by weight, the content of the component (B) is 10 to 50% by weight, and the content of the component (C) is 5 to 40% by weight. It is preferable that the total content of copolymerized vinyl acetate and (meth) acrylic acid (ester) in the component (C) is 10 to 25% by weight. In the flexible polyolefin-based resin laminated sheet of the present invention, the ratio of the thickness of the surface layer formed from the polyolefin-based resin blend (a) to the thickness of the back layer formed from the polyolefin-based resin blend (b) is 1: Preferably it is 1-3: 1. In the flexible polyolefin resin laminated sheet of the present invention, at least one of the front surface layer and the back surface layer
It is preferable that a contamination prevention layer is formed as an outermost layer on the layer. In the flexible polyolefin resin laminated sheet of the present invention, the contamination prevention layer is selected from an acrylic resin, an acrylic urethane resin, an acrylic silicone resin, an acrylic resin-containing thermoplastic resin, a fluoroolefin resin, and a polyurethane resin. Preferably, it is composed of at least one kind. In the flexible polyolefin-based resin laminated sheet of the present invention, the polypropylene resin for the component (A) may be a propylene homopolymer, an ethylene-propylene copolymer, a propylene-α-olefin copolymer, or a propylene-ethylene-propylene copolymer. It is preferably at least one selected from a polymerized elastomer and a propylene-ethylene / propylene / non-conjugated diene copolymer elastomer. In the flexible polyolefin-based resin laminated sheet of the present invention, the propylene homopolymer for the component (A), the ethylene-propylene copolymer, and the propylene-α-
The olefin copolymer is preferably a polypropylene resin having syndiotactic stereoregularity polymerized in the presence of a single-site catalyst. In the flexible polyolefin-based resin laminated sheet of the present invention, the propylene homopolymer, ethylene-propylene copolymer, and propylene-α-olefin copolymer for the component (A) are polymerized in the presence of a single-site catalyst. It is preferably a polypropylene resin having tactic stereoregularity. In the flexible polyolefin resin laminate sheet of the present invention, the styrene copolymer resin for component (B) is an ABA type styrene block copolymer resin (A represents a styrene polymer block, and B represents butadiene. Polymer block, isoprene polymer block, or vinyl isoprene polymer block), AB type styrene block copolymer resin (A and B have the same meanings as described above), styrene random copolymer resin And 1 selected from the hydrogenated resins of the styrenic copolymer resins.
Preferably, it consists of more than one species. In the flexible polyolefin resin laminated sheet of the present invention, the component (A),
It is preferable that the polyolefin-based resin blend containing (B) and (C) further contains 1 to 15% by weight of synthetic amorphous silica. In the flexible polyolefin resin laminated sheet of the present invention, it is preferable that the fiber cloth is a fiber woven fabric composed of multifilament yarn or spun short fiber yarn and having a woven structure porosity of 0 to 35%. In the flexible polyolefin resin laminated sheet of the present invention,
It is preferable that the fiber cloth is resin-coated with a treating agent containing a styrene-based copolymer resin.
In the flexible polyolefin-based resin laminated sheet of the present invention, the treating agent for a fiber fabric is a styrene-based copolymer resin solution dissolved in an organic solvent, and the styrene-based copolymer resin is AB- A-type styrene block copolymer resin (A represents a styrene polymer block, B represents a butadiene polymer block, an isoprene polymer block, or a vinyl isoprene polymer block), A-
B-type styrene block copolymer resin (A and B have the same meanings as described above), styrene random copolymer resin,
It is preferable that at least one selected from the hydrogenated resins of these styrene copolymer resins. In the flexible polyolefin-based resin laminated sheet of the present invention, it is preferable that the fiber cloth is made of polyester fiber. In the flexible polyolefin-based resin laminated sheet of the present invention, it is preferable that the fiber cloth is made of polypropylene fibers. In the flexible polyolefin-based resin laminated sheet of the present invention, the polypropylene fibers are isotactic stereoregularity polymerized in the presence of a single-site catalyst,
Alternatively, it is preferably a fiber spun from a polypropylene resin having syndiotactic stereoregularity. The method for producing a flexible polyolefin-based resin sheet having at least one soft polyolefin-based resin blend coating layer according to the present invention is characterized in that the polyolefin-based resin blend is pre-blended with the component (A) and the component (B). Then, the component (C) is blended with the pre-blend (A + B), or the component (B) and the component (C) are pre-blended and the pre-blend (B +
Prepared by blending said component (A) with C),
At this time, based on the total weight of the components (A), (B), and (C) in the polyolefin-based resin blend, the blending amount of the component (A) is set to 30 to 70% by weight. The compounding amount is 10 to 50% by weight, the compounding amount of the component (C) is 5 to 40% by weight, and vinyl acetate and (meth) acrylic which are contained as a copolymerizing component in the component (C) in the resin blend The total content of the acid (ester) is adjusted to 3 to 25% by weight. In the method for producing a flexible polyolefin-based resin laminated sheet of the present invention, it is preferable to further form a contamination prevention layer as an outermost layer on at least one of the polyolefin-based resin blend coating layers. The method for producing a soft polyolefin-based resin laminated sheet having both front and back layers of the soft polyolefin-based resin blend of the present invention comprises the above-mentioned polyolefin-based resin blend for the front layer (a) and the polyolefin-based resin blend for the back layer (b) Is pre-blended with the component (A) and the component (B), and the component (C) is blended with the pre-blend (A + B), or the component (B) and the component (B) (C)
Is prepared by blending the component (A) with the pre-blend (B + C). At this time, the components (A) and (A) in each of the polyolefin-based resin blends (a) and (b) are prepared. With respect to the total weight of (B) and (C), the compounding amount of the component (A) is 30 to 70% by weight, the compounding amount of the component (B) is 10 to 50% by weight, and the component (C) ) Is 5 to 40% by weight, and the total content of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymer component in the component (C) in the surface layer resin blend (a). Is adjusted to 3 to 10% by weight, and the total content of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymer component in the component (C) in the resin blend for a back surface layer (b) is adjusted. 10-25
% By weight, and a surface layer comprising the surface layer polyolefin resin blend (a) is formed on the surface of the fiber cloth-containing base fabric, and the back surface polyolefin resin blend is formed on the back surface of the base fabric. (B) forming a back surface layer. In the method for producing a flexible polyolefin-based resin laminated sheet according to the present invention, it is preferable that the ratio of the thickness of the front surface layer to the thickness of the back surface layer is adjusted to 1: 1 to 3: 1. In the method for producing a flexible polyolefin-based resin laminated sheet of the present invention, it is preferable to further form a contamination prevention layer as an outermost layer on at least one of the front surface layer and the back surface layer. In the method for producing a flexible polyolefin-based resin laminated sheet of the present invention, the contamination-preventing layer is formed of an acrylic resin, an acrylic urethane-based resin, an acrylic silicone-based resin, an acrylic resin-containing plastic resin, a fluoroolefin-based resin, or a polyurethane-based resin. It is preferable to form from one or more selected types.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The covering layer of the flexible polyolefin resin laminated sheet or the polyolefin resin blend for forming the surface layer and the back surface layer of the present invention comprises (A) a component comprising a polypropylene resin, and (B) a styrene copolymer. A component comprising a united resin, (C) an ethylene-vinyl acetate copolymer resin,
And / or a resin blend containing an ethylene- (meth) acrylic acid (ester) copolymer resin component. As the polypropylene resin component (A) that can be used in the polyolefin resin blend,
Propylene homopolymer, ethylene-propylene copolymer, propylene-α-olefin copolymer, propylene-ethylene-propylene-based copolymer elastomer, propylene-ethylene-propylene-non-conjugated diene-based copolymer elastomer can be mentioned, These copolymers may be either random copolymers or block copolymers. Further, two or more of these polypropylene resins may be used in combination. These polypropylene resins are homopolymers obtained by homopolymerization of propylene monomers, and ethylene-polymers obtained by copolymerizing propylene monomers and ethylene monomers.
Propylene copolymer, and propylene monomer and α-
A propylene-α-olefin copolymer resin obtained by copolymerizing an olefin monomer, and an ethylene-propylene copolymer obtained by pre-polymerization obtained by multi-stage polymerization in which a propylene monomer is continuously copolymerized with a propylene monomer. A propylene-ethylene-propylene copolymer obtained by multi-stage polymerization in which a propylene monomer is continuously copolymerized with a propylene-ethylene-propylene-based copolymer elastomer and an ethylene-propylene-non-conjugated diene copolymer obtained by preliminary polymerization. Conjugated diene copolymer elastomers are included.

In the polyolefin resin blend of the present invention, the polypropylene resin component (A) is added in an amount of 30 to 7 based on the total weight of the components (A), (B) and (C).
It is contained at a content ratio of 0% by weight, particularly preferably 40 to 60% by weight. Component (A) in resin blend
If the content is less than 30% by weight, the resulting polyolefin resin laminated sheet will have insufficient wear resistance and heat creep resistance, and if the content exceeds 70% by weight, it will be obtained. The feeling of the polyolefin resin laminated sheet is excessively hard, which is not preferable.

The preferred α-olefin for producing the propylene-α-olefin copolymer resin is an α-olefin having 4 to 10 carbon atoms, for example, butene-1, pentene-1, hexene-1, octene-1. , Heptene
1,3-methyl-butene-1,4-methyl-pentene-
1,4-methyl-hexene-1, 4,4-dimethyl-pentene-1 and the like. In addition, a propylene-α-olefin copolymer resin obtained by copolymerizing one or more of these α-olefins with a propylene monomer can also be used. Specific examples thereof include a propylene-butene-1 copolymer, an ethylene-propylene-butene-1 copolymer, and an ethylene-propylene-butadiene copolymer. These propylene-based copolymers may be random copolymers, or may be any copolymers of block copolymers, the content of α-olefins contained in these copolymers It is preferably from 1 to 35% by weight. If the content of the α-olefin in the copolymer exceeds 35% by weight, the obtained polyolefin resin laminated sheet tends to cause blocking, and the low molecular weight adhesive component bleeds, which hinders practical use. If the propylene unit component is less than 65% by weight, the resulting polyolefin resin laminated sheet may have insufficient abrasion resistance, which is not preferable.

Specific examples of the propylene-ethylene-propylene-based copolymer elastomer and the propylene-ethylene-propylene-non-conjugated diene-based elastomer include those produced by the following continuous multi-stage polymerization method. First, as a first step, in the presence of a titanium compound catalyst and an aluminum compound catalyst, polymerization is carried out using a propylene monomer and, if necessary, an α-olefin monomer other than the propylene monomer.
To obtain a propylene-based polyolefin. The polyolefin includes a propylene homopolymer, a propylene-ethylene copolymer, a propylene-α-olefin copolymer and the like. As a second step, the titanium compound catalyst;
While containing the aluminum compound catalyst, the following olefin monomer (eg, ethylene, propylene, non-conjugated diene, etc.) is copolymerized.

As a method for producing the propylene-based copolymer elastomer, for example, JP-A-4-224809, JP-A-4-96912, and JP-A-4-969.
No. 07 publication, etc., and this method has the advantage that a plurality of propylene-based polyolefin resins can be continuously produced by a multi-stage polymerization process during the polymerization. There is a merit that manufacturing equipment can be used as it is. Further, in the conventional block polypropylene copolymer resin, a block component copolymerized with propylene, for example, propylene-ethylene copolymer, propylene-α-
Due to the production process, the content of the amorphous component composed of the olefin copolymer is about 50% with respect to the propylene component.
Although the upper limit is the amount by weight, the above-mentioned multi-stage polymerization makes it possible to contain the amorphous component in an amount of 50% by weight or more (up to 80 to 95% by weight). The propylene-based copolymer elastomer obtained by this multi-stage polymerization and the ordinary elastomer obtained by polymer blending a polypropylene resin and a propylene-ethylene copolymer resin are different from each other in molecular structure.

In the flexible polyolefin resin laminate sheet of the present invention, the propylene copolymer elastomer suitable for the polypropylene resin component (A) used in the polyolefin resin blend is a propylene homopolymer component or a propylene copolymer component in the first step. It is preferable to contain 10 to 45% by weight of an ethylene copolymer component, an ethylene-propylene-non-conjugated diene copolymer component, or a propylene-α-olefin copolymer component.
After the step, 55 to 55 ethylene-propylene copolymer components
It is preferred to contain 90% by weight. In the first step, the content of the propylene homopolymer component, the propylene-ethylene copolymer component, the ethylene-propylene-nonconjugated diene copolymer component, or the propylene-α-olefin copolymer component is 10% by weight. If the amount is less than the above range, sufficient strength cannot be obtained in the obtained propylene-based copolymer elastomer, and if the content exceeds 45% by weight, the texture of the obtained propylene-based copolymerized elastomer becomes hard, so Component (A) used in polyolefin resin blend layer of polyolefin resin laminate sheet
It may not be preferable as a polypropylene resin for use.

As a catalyst used for the polymerization of the polypropylene resin for the component (A), a Ziegler-Natta catalyst is representative. This catalyst system is based on Periodic Table IV
A transition metal compound catalyst having a metal-carbon bond composed of a compound of a transition metal of Groups I to VI and a compound of a metal of Groups I to III of the periodic table. It is configured. As the halogenated transition metal salt, for example, magnesium chloride,
As a metal alkyl compound such as aluminum trichloride, titanium trichloride, and titanium tetrachloride, for example, triethyl aluminum, triisobutyl aluminum and the like can be preferably used.

In the present invention, the polypropylene resin for the component (A) is a polypropylene resin polymerized by any of a gas phase method, a slurry liquid phase method, and a high pressure method using the Ziegler-Natta catalyst. Although a resin can be used, in particular, in the flexible polyolefin-based resin laminated sheet of the present invention, polymerization is performed by any of a gas phase method, a slurry liquid phase method, or a high pressure method in the presence of a single-site catalyst. When using a syndiotactic stereoregular polypropylene resin,
The flexibility of the obtained polyolefin-based resin laminated sheet is improved.

As a catalyst for obtaining a polypropylene resin having a syndiotactic stereoregularity, a single-site catalyst comprising a metallocene complex salt compound is exemplified.
No. 03, JP-A-2-274703, JP-A-2
And metallocene complex salt compounds described in JP-A-274704 and JP-A-4-69394. Examples of the metallocene complex salt compound include an organic transition metal compound containing a cyclopentadienyl derivative, and the transition metal of the organic transition metal compound is selected from Group IVB of the Periodic Table, such as zirconium, titanium, and hafnium. And the like. Specific examples of these include, for example, isopropylidene (cyclopentadienyl) 9-fluorenyl zirconium dichloride, cyclohexylidene (cyclopentadienyl)
9-fluorenyl zirconium dichloride, diphenylmethylene (cyclopentadienyl) 9-fluorenyl zirconium dichloride, methylphenylmethylene (cyclopentadienyl) 9-fluorenyl zirconium dichloride, isopropylidene (cyclopentadienyl) 2 , 7-Di-tert-butyl-9-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) 2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) 2, 7-di-tert-butyl-9-
Fluorenyl) zirconium dichloride, methylphenylmethylene (cyclopentadienyl) 2,7-di-t-
Butyl-9-fluorenyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride, 1-methyl-1ethylidene (cyclopentane Examples thereof include dienyl-1-fluorenyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, and dimethylsilanesilylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride.

In the present invention, the polypropylene resin for the component (A) is a polypropylene resin polymerized by any of a gas phase method, a slurry liquid phase method, and a high pressure method using the Ziegler-Natta catalyst. Although a resin can be used, in particular, in the flexible polyolefin-based resin laminated sheet of the present invention, polymerization is performed by any of a gas phase method, a slurry liquid phase method, or a high pressure method in the presence of a single-site catalyst. It is preferable to use the obtained polypropylene resin having isotactic stereoregularity because the resulting polyolefin resin laminated sheet has excellent wear resistance.

Examples of a catalyst for polymerizing a polypropylene resin having isotactic stereoregularity include a single-site catalyst comprising a metallocene complex salt compound. Examples of these catalysts include, for example, JP-A-61-13031.
4, JP-A-3-12406, JP-A-3-1
And metallocene complex salt compounds described in Japanese Patent No. 97516. Examples of the metallocene complex salt compound include an organic transition metal compound containing an indenyl derivative. As the transition metal of the organic transition metal compound, a metal selected from Group IVB of the Periodic Table, such as zirconium, titanium, and hafnium Is mentioned. Specific examples of these include, for example, ethylene bis (indenyl) zirconium dichloride, ethylene bis (tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethyl Silylene bis (dimethylindenyl) zirconium dichloride, dimethyl silylene bis (trimethylindenyl) zirconium dichloride, dimethyl silylene bis (2-
Methyl-4-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, bis (indenyl) titanium dichloride, dimethylsilylenebis (indenyl)
Hafnium dichloride can be exemplified.

In the present invention, the activity of polymerization is improved by using an alkylaluminoxane as a cocatalyst for the metallocene complex compound catalyst containing the cyclopentadienyl derivative and the indenyl derivative in the production of the polypropylene resin for the component (A). Can be improved. Examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and the like. For example, alkylaluminoxane is obtained by condensation of an organic aluminum such as trimethylaluminum and triethylaluminum with water and-(A
_{l (CH 3) -O-) n} - condensate can be used. The alkylaluminoxane preferably has a metal atom number ratio (aluminum atom / transition metal atom of the metallocene complex salt catalyst) of the metallocene complex salt catalyst of 100 to 1,000. The amount of the metallocene complex salt catalyst used in the polymerization system is 1 × with respect to 1 liter of the polymerization volume.
Preferably, it is used in an amount of from 10 ^-8 to 1 x 10 ^-3 gram atoms. If necessary, a known proton acid, Lewis acid, Lewis acidic compound or the like may be used in combination for the purpose of increasing the polymerization activity. Proton acids, Lewis acids, and Lewis acidic compounds are not particularly limited, but boron compounds can be preferably used.

M of the polypropylene resin for component (A) used in the flexible polyolefin resin laminated sheet of the present invention
FR (melt flow rate: 230 ° C, 2.16 kg load) is 0.5 to 50 g / 10 min, preferably 1 to 2
Those having 0 g / 10 min can be suitably used for the polyolefin resin blend layer. Melt flow rate is 0.5
If it is less than g / 10 min, it is not preferable because the forming process of the flexible polyolefin resin laminated sheet of the present invention becomes extremely difficult, and if it exceeds 50 g / 10 min, the heat creep resistance of the obtained polyolefin resin laminated sheet is inferior. Absent.

The styrene copolymer resin for component (B) used in the flexible polyolefin resin laminate sheet of the present invention is an ABA type styrene block copolymer resin (A is a styrene polymer block). And B represents a butadiene polymer block, an isoprene polymer block, or a vinyl isoprene polymer block.), AB
Type styrene block copolymer resins (A and B have the same meanings as described above), styrene random copolymer resins, and hydrogenated resins of these styrene copolymer resins can be used. These block copolymers are styrenic block copolymer resins having a polystyrene block as a hard segment.

Examples of the ABA type styrene block copolymer resin include styrene-butadiene-styrene block copolymer resin (SBS), styrene-isoprene-styrene block copolymer resin (SIS), and styrene. -Vinyl isoprene-styrene block copolymer resin (SVIS) is used, and as the ABA type hydrogenated styrene block copolymer resin, for example, hydrogenated resin of styrene-butadiene-styrene block copolymer resin is used. Styrene-ethylene-butene-styrene block copolymer resin (SEBS), styrene-ethylene-propylene-styrene block copolymer resin (SEPS) which is a hydrogenated resin of styrene-isoprene-styrene block copolymer resin, etc. And AB type styrene copolymer resin And is, for example, styrene - butadiene block copolymer resin (SB), and styrene - include isoprene block copolymer resin (SI), A
Examples of the B-type hydrogenated block copolymer resin include styrene-ethylene-butene block copolymer resin (SEB), which is a hydrogenated resin of styrene-butadiene block copolymer resin, and styrene-isoprene block copolymer resin. Styrene-ethylene-butene block copolymer resin (SEP), which is a hydrogenated resin of the united resin, may be used.

The resin blend used in the polyolefin resin blend layer of the present invention contains the component (B) composed of the styrene copolymer resin in a content of 10 to 50% by weight, particularly 20 to 40% by weight. It is preferable that
The proportion of the component (B) in the resin blend is 10% by weight.
When the ratio is less than 50%, the flexibility and processability of the obtained polyolefin resin laminated sheet are insufficient, and when the ratio exceeds 50% by weight, the flexibility of the obtained laminated sheet is sufficient. In addition, its wear resistance becomes insufficient, and its workability and mechanical strength become insufficient. Particularly, as the styrene copolymer resin for component (B) used in the polyolefin resin blend layer of the present invention,
In particular, those selected from a hydrogenated styrene block copolymer resin and a hydrogenated styrene random copolymer resin are preferable because of their excellent weather resistance.

The styrene polymer block A which can be used in the styrene copolymer resin for component (B) includes:
Aromatic vinyl monomers, for example, styrene, α-
Methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, -Vinylnaphthalene, 1-vinylanthracene and the like, among which styrene is most preferred. Examples of the polymer block B that can be used in these styrene copolymer resins include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-butadiene. Examples thereof include 3-hexadiene, and 1,3-butadiene and isoprene are particularly preferable. These ABA block copolymer resins and their hydrogenated resins, and AB block copolymer resins and their hydrogenated resins have a number average molecular weight of the A block polymer of 2,000 to 40,000. And the number average molecular weight of the B block polymer is 10,000 to 2
00000 is desirable. The number average molecular weight of the styrene copolymer resin is 30,000 to
Those having a range of 250,000 are preferred. Molecular weight 300
If the molecular weight is smaller than 00, the mechanical strength of the block copolymer resin cannot be obtained, and the strength of the polyolefin resin blend layer of the present invention is lowered.
If it exceeds 50,000, the melt viscosity becomes high, and (A) a polypropylene resin, and (C) an ethylene-vinyl acetate copolymer resin and / or an ethylene- (meth) acrylic acid (ester) copolymer resin It is not preferable because the melt-kneading property deteriorates and the molding processability becomes difficult.

The hydrogenation rate of the hydrogenated resin of the isoprene polymer block of the B block component or the isoprene-butadiene polymer block of the styrene block copolymer resin for component (B) is 70% or more. And more preferably 80% or more. If the hydrogenation rate is lower than 70%, heat resistance and weather resistance are undesirably reduced. Hydrogenation of these styrenic block copolymer resins is performed by a known method,
For example, the hydrogenation reaction, a hydrogenation catalyst and a known catalyst in a state in which a styrene-based block copolymer resin is dissolved in a solvent inert to the reaction, for example, Raney nickel, a Ziegler-based catalyst, and the like, the molecular It can be performed by a method of reacting hydrogen in a state. Further, as the B block component, the total amount of 3,4 vinyl bonds and 1,2 vinyl bonds in isoprene of the isoprene polymer block or isoprene-butadiene polymer block is 25 mol% or more before hydrogenation. Is preferred. When the total amount of the vinyl bonds is less than 25 mol%, the component (B) in the polyolefin resin blend layer of the present invention is used.
And the polypropylene resin component (A) and the ethylene-vinyl acetate copolymer resin and / or the ethylene- (meth) acrylic acid (ester) copolymer resin component (C) have insufficient compatibility, Further, it is not preferable because durability and strength of the obtained polyolefin resin blend layer are reduced. As the B block component of the polystyrene copolymer for the component (B), the content of 1,2-vinyl bond in butadiene of the butadiene polymer block is 20 mol%.
It is preferable that it is above. 20 total vinyl bonds
If it is less than mol%, the polyolefin resin blend layer of the present invention (A) the polypropylene resin, the component (A) and the ethylene-vinyl acetate copolymer resin, and / or the ethylene- (meth) acrylic acid (ester) It is not preferable because the compatibility with the copolymer resin component (C) becomes insufficient and the durability and strength of the polyolefin-based resin blend layer decrease.

When the content of the polystyrene block component exceeds 40% by weight in the ABA type block copolymer resin for component (B) and the hydrogenated resin thereof,
The compatibility with the polypropylene resin component (A) and the ethylene-vinyl acetate copolymer resin and / or the ethylene- (meth) acrylic acid (ester) copolymer resin component (C) becomes insufficient, and the polyolefin resin In order to reduce the durability and strength of the resin blend layer, the content is preferably 40% by weight or less. In the AB block copolymer resin for component (B) and the hydrogenated resin thereof, if the content of the polystyrene block component exceeds 40% by weight, the polypropylene resin component (A) and ethylene-vinyl acetate are used. Copolymer resin and / or ethylene- (meth)
The content is preferably 40% by weight or less, since the compatibility with the acrylic acid (ester) copolymer resin component (C) becomes insufficient and the durability and strength of the polyolefin resin blend layer are reduced. AB- for these components (B)
Commercially available products such as the A-type block copolymer resin and its hydrogenated resin and the AB-type block copolymer resin and its hydrogenated resin include, for example, Shell. Clayton G of Chemical Company, ToughTech of Asahi Kasei Industry Co., Ltd.
Kuraray's Hibler and Septon. Examples of the hydrogenated styrene random copolymer resin include a hydrogenated random copolymer resin of styrene and butadiene. A commercially available product of the hydrogenated styrene random copolymer resin is Nippon Synthetic Rubber Co., Ltd. ).

The MFR (melt flow rate: 230 ° C., 2.16 kg load) of the styrene copolymer resin for component (B) used in the flexible polyolefin resin laminate sheet of the present invention is 0.5 to 50 g / 10 min. , Preferably 1-2
Those having 0 g / 10 min can be suitably used for the polyolefin resin blend layer. Melt flow rate is 0.5
If it is less than g / 10 min, it is not preferable because the forming process of the flexible polyolefin resin laminated sheet of the present invention becomes extremely difficult, and if it exceeds 50 g / 10 min, the heat creep resistance of the obtained polyolefin resin laminated sheet is inferior. Absent.

The ethylene-vinyl acetate copolymer resin for component (C) and the ethylene- (meth) acrylic acid (ester) copolymer resin which can be used in the polyolefin resin blend for the flexible polyolefin resin laminate sheet of the present invention. An ethylene copolymer resin produced by polymerization of an ethylene monomer and a radically polymerizable monomer by a radical polymerization method can be used. Examples of the monomer capable of radical polymerization with an ethylene monomer include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and esterified products and acid anhydrides thereof. Examples of the esterified product of the unsaturated carboxylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, and glycidyl (meth) acrylate. These monomers can be used alone or in combination of two or more. More specifically, the ethylene-vinyl acetate copolymer resin is obtained by polymerization of an ethylene monomer and a vinyl acetate monomer, and the ethylene- (meth) acrylic acid (ester) copolymer resin is an ethylene monomer. And ethylene-acrylic acid copolymer resin obtained by polymerization of acrylic acid monomer, ethylene-acrylic acid ester copolymer resin obtained by polymerization of ethylene monomer and acrylic acid ester monomer, ethylene monomer and methacrylic acid monomer Ethylene-methacrylic acid copolymer resin obtained by polymerization of ethylene-methacrylic acid ester copolymer resin obtained by polymerization of ethylene monomer and methacrylic acid ester monomer, and a mixture of two or more of these. No. The resin blend used in the polyolefin-based resin blend layer of the present invention contains the ethylene-vinyl acetate copolymer resin and the ethylene- (meth) acrylic acid (ester) copolymer resin component (C) in an amount of 5 to 40% by weight. %, Preferably 10 to 30% by weight. Component (C) occupying in resin blend
If the ratio is less than 5% by weight, the obtained polyolefin-based resin laminated sheet has insufficient high-frequency fusion property, and if the ratio exceeds 40% by weight, the high-frequency fusion Although the adhesion is sufficient, its heat creep resistance becomes insufficient.

The ethylene copolymer resin which can be used as the component (C) of the polyolefin resin blend used in the flexible polyolefin resin laminate sheet of the present invention is preferably an ethylene copolymer having a vinyl acetate component content of 8 to 60% by weight. A vinyl acetate copolymer resin or an ethylene- (meth) acrylic acid (ester) copolymer resin having a (meth) acrylic acid (ester) component content of 8 to 60% by weight, or an ethylene-vinyl acetate copolymer resin; Weight ratio with (meth) acrylic acid (ester) copolymer resin: 100: 1 to 1
1: 100 blend, with a total vinyl acetate component and (meth) acrylic acid (ester) component of 8
It is preferably a polyolefin-based resin copolymer composition in an amount of from 60 to 60% by weight. The MFR (melt flow rate: 190 ° C., 2.16 kg load) of the (C) ethylene-vinyl acetate copolymer resin and / or ethylene- (meth) acrylic acid (ester) copolymer resin is 0.5 ~
50 g / 10 min, preferably 1-20 g / 10 min, can be suitably used for the polyolefin resin blend layer. If the melt flow rate is less than 0.5 g / 10 min, the forming process of the flexible polyolefin resin laminated sheet of the present invention becomes extremely difficult, which is not preferable.
When it is higher than g / 10 min, the resulting polyolefin-based resin laminated sheet is inferior in heat creep resistance, which is not preferable.

That is, the polyolefin resin blend used in the flexible polyolefin resin laminate sheet of the present invention comprises polypropylene resin components (A), (B) styrene copolymer resin components (B), and (C) ethylene- A resin blend containing a vinyl acetate copolymer resin and / or an ethylene- (meth) acrylic acid (ester) copolymer resin component, wherein the components (A) and (B) are contained in the resin blend. And (C), the content of the component (A) is 30 to 70% by weight, the content of the component (B) is 10 to 50% by weight, and the content of the component (C) The content is 5 to 40% by weight. Further, the total weight of the component (C) contained in the resin blend and vinyl acetate (meth) acrylic acid (ester) as a copolymer component is the total weight of the components (A), (B) and (C). 3 to 25% by weight, preferably 6 to 2% by weight
0% by weight, more preferably 8 to 16% by weight. Vinyl acetate component and (meth) acrylic acid (ester)
If the total content of the components is less than 3 parts by weight, the obtained high-frequency-fused property of the soft polyolefin-based resin laminated sheet becomes insufficient, which is not preferable. Although the high-frequency fusing property of the laminated sheet is sufficient, the heat-resistant creep property and the wear resistance are insufficient.

Further, the flexible polyolefin resin laminated sheet of the present invention is formed by laminating a front and back double-sided layer made of a polyolefin resin blend on both the front and back surfaces of a base cloth including a fiber cloth. The blend front surface layer and the polyolefin resin blend back surface layer may be different from each other. That is, the polypropylene-based resin component (A), styrene-based copolymer resin component (B), ethylene-vinyl acetate copolymer resin, and / or ethylene- (meth) ) Acrylic acid (ester) copolymer resin component (C) and polyolefin-based resin blend surface layers (a) and (b) composed of resin blends (a) and (b), respectively. The ratio of the component (A) contained in the surface layer resin blend (a) is 30 to 70% by weight, and the ratio of the component (B) is 10 to 50% by weight. The ratio of the component (C) is 5 to 40% by weight, and in the resin blend (a), vinyl acetate and (meth) acrylic acid (ester) contained as a copolymer component in the component (C). Total content of 3 to 10% by weight, preferably 5-8% by weight. Further, the ratio of the component (A) contained in the resin blend (b) for the backside layer is 3%.
0 to 70% by weight, and the ratio of the component (B) is 10 to 70% by weight.
50% by weight, the ratio of the component (C) is 5 to 40% by weight, and vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component in the component (C) in the resin blend (b). )) And the total content of components (A) and (B)
And (C) in an amount of 10 to 25% by weight, preferably 14 to 20% by weight. The ratio of the thickness of the front layer formed from the resin blend (a) to the thickness of the back layer formed from the resin blend (b) is 1: 1 to 1: 1.
The ratio is preferably 3: 1, more preferably 1.
The ratio is 2: 1 to 2: 1. By doing so, the wear resistance of the obtained laminated sheet can be improved.

The MFR (melt flow rate: 230) of the resin blend containing the above components (A), (B) and (C)
° C, 2.16 kg load) is 0.5 ~ 100g / 10min
And more preferably 1 to 50 g / 1.
0 min. Melt flow rate is 0.5g / 10
If it is less than 100 min / 10, it may be extremely difficult to mold the obtained flexible polyolefin resin laminated sheet. Abrasion may be insufficient. The tensile yield value (JIS K-7113) of this resin blend layer is 5
It is preferably at least 00 N / cm ² (51 kgf / cm ² ), more preferably 500 to 900 N / cm ² (9
1.8kgf / cm ²⁾ it is. Tensile yield value is 500N / cm
^If it is less than ² , the abrasion resistance of the obtained polyolefin resin laminated sheet may be insufficient, and if it exceeds 900 N / cm ² , the abrasion resistance of the obtained polyolefin resin laminated sheet is satisfactory. Even if it is obtained, handling becomes difficult because its texture becomes hard.

In the present invention, a polyolefin-based resin blend is prepared by adding an ethylene-vinyl acetate copolymer resin to a preliminary blend of a polypropylene-based resin component (A) and a styrene-based copolymer resin component (B). And / or
Ethylene- (meth) acrylic acid (ester) copolymer resin component (C) is post-blended, or styrene copolymer resin component (B) and (C) ethylene-vinyl acetate copolymer resin, and And / or the polypropylene resin component (A) is post-blended with the pre-blend with the ethylene- (meth) acrylic acid (ester) copolymer resin component (C). The melting temperature difference between the component (A) and the component (C) is large, and under molding conditions close to the melting temperature of the component (C), the compatibility between the component (A) and the component (C) is insufficient, Accordingly, the processability is deteriorated, and under the molding conditions close to the melting temperature of the component (A), the compatibility between the component (A) and the component (C) is improved, but the melt viscosity of the obtained preliminary blend is low. And the workability deteriorates. Accordingly, the collective melt-kneading of the component (A) + (B) + (C) resin blends has a disadvantage in that the processability is increased due to the fact that the melting temperatures of the components are different and the compatibility of the components is biased depending on the molding temperature conditions. Inadequate,
Further, the mechanical strength originally possessed by the resin blend may not be satisfactorily obtained. Further, for the same reason as above, a kneading system in which the component (B) is blended with the preliminary blend {(A) + (C)} is not preferable.

When the synthetic amorphous silica is contained in the resin blend of the flexible polyolefin resin laminated sheet of the present invention in an amount of 1 to 15% by weight, the high-frequency fusion property and the heat creep resistance can be improved. 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 bonding water, water bonded to a silanol group (Si-OH group) on the silica surface through hydrogen bonding and water present as a hydroxyl group contained in the silanol group itself, It is distinguished from anhydrous silica having a very low water content obtained by other dry synthesis methods or aerogel synthesis methods of silica. The average agglomerated particle size of the synthetic amorphous silica is not particularly limited, but is preferably 1 to 20 μm, more preferably 2 to 10 μm, and preferably 2 to 10 μm. Is preferably 3 to 15% by weight, more preferably 5 to 10% by weight. The amount of the synthetic amorphous silica used in the resin blending compound in 100 parts by weight is preferably 1 to 15 parts by weight. If the addition amount is less than 1% by weight, the effect of improving the heat-resistant fracture strength of the fusion-bonded article of the obtained polyolefin-based resin laminated sheet may be insufficient, and the compounding amount of the synthetic amorphous silica may be less than 15%. If the content is more than 10% by weight, the molding fluidity of the resin blend layer compound may be deteriorated and processing may be difficult. In addition, the film abrasion strength of the obtained polyolefin resin laminated sheet may be reduced, and sufficient durability may be obtained. May not be possible. The high-frequency weldability is further improved by including 1 to 15% by weight of the above-mentioned synthetic amorphous silica in the polyolefin-based resin blend layer of the flexible polyolefin-based resin laminate sheet of the present invention, and furthermore, the heat-resistant creep of the fusion bonded article. Performance can also be improved.

The polyolefin resin blend of the flexible polyolefin resin laminate sheet of the present invention may be colored with an organic pigment and / or an inorganic pigment. Conventionally known organic pigments can be used, for example,
Azo pigments, phthalocyanine pigments, dyed lake pigments, anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments,
Examples include dioxazine-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, and other examples, such as nitroso pigments, alizarin lake pigments, metal complex salt azomethine pigments, and aniline-based pigments. Examples of the inorganic pigments include zinc oxide (zinc white), titanium oxide (rutile type, anatase type), antimony trioxide, iron oxide, lead oxide, chromium oxide, zirconium oxide, and spinel type (XY ₂ O ₄ ) structure. Oxides, metal oxides such as rutile type [Ti (XY) O ₂ ] structure oxides, composites of zinc sulfide and barium sulfate (lithopone), metal sulfides such as calcium sulfide and zinc sulfide,
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; and aluminum hydroxide ( Metal hydroxides such as alumina white), a composite of aluminum hydroxide and calcium sulfate (satin white), and a composite of aluminum hydroxide and barium sulfate (gloss white);
Metal chromate salts such as lead chromate (yellow) and barium chromate, other carbon black, titanium black, acetylene black, graphite, white carbon, diatomaceous earth, talc, clay, aluminum powder, colored aluminum powder, metal deposition Examples include crushed film, silver-white mica titanium, colored mica titanium, and dichroic interference mica titanium. These pigments can be used in combination of two or more kinds, and the addition amount is not particularly limited. In addition, the polyolefin-based resin blend layers on the front and back may be in different colors.

The polyolefin-based resin blend of the flexible polyolefin-based resin laminate sheet of the present invention may optionally contain additives. In particular, it is preferable to add an ultraviolet absorber, an antioxidant, a light stabilizer, and the like for the purpose of improving the durability of the polyolefin-based resin blend layer. 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 processability and appearance during film molding.

The polyolefin resin blend layer of the flexible polyolefin resin laminate sheet of the present invention can be processed by a conventionally known molding method, for example, a T-die extrusion method, an inflation method, a calender method, or the like. The compound for the polyolefin-based resin blend layer is a known method, for example, using a Banbury mixer, a kneader, a twin-screw kneader, etc., a method of compounding by kneading and kneading, and after melt-kneading, a single-screw extruder pelletizer, It can be obtained by a method of granulating into pellets using a twin-screw extrusion pelletizer or the like. The polyolefin-based resin blend layer of the present invention is prepared by
-Can be formed by a processing technique such as a die extrusion method, an inflation method, and a calendar method.In particular, for the production of a film colored with an organic pigment, an inorganic pigment, or the like, or a processing with many color changing operations, a calender is used. When the method is used, the compound loss is reduced, and the method is simple and preferable. The polyolefin-based resin blend layer of the present invention is preferably subjected to a molding process in a temperature range of 100 to 200 ° C. by a calender method. The thickness of the polyolefin resin blend layer to be calendered is 80
５００500 μm, preferably 150-350
More preferably, it is μm. If this thickness is thinner than the above range, the molding process is difficult, and when laminating and sticking to the fiber cloth, the head of the film is cut off at the intersection of the fiber fabric, and not only the waterproof property is impaired, but also the sheet May decrease the durability. The thickness of the flexible polyolefin-based resin laminate sheet of the present invention is not limited, but may be from 80 to 500.
μm polyolefin resin blend film from 1 to 4
It is preferable to use a plurality of sheets and laminate them to a base cloth. In particular, when a polyolefin-based resin blend film layer is formed on both sides of the base fabric using two films each having a thickness of 180 to 300 μm, it is most preferable in terms of obtaining a laminated sheet having excellent durability and high-frequency fusion bonding properties. .

The ratio of the thickness of the surface resin blend layer (a) of the flexible polyolefin resin laminated sheet of the present invention to the thickness of the resin blend layer (b) formed on the back surface (a) :( b)
Is preferably from 1: 1 to 3: 1, and particularly preferably from 1.2: 1 to 2: 1. The minimum thickness of the surface resin blend layer (a) is preferably 0.1 mm. For example, specifically, the film thickness of (a) :( b) is 0.2 m
m: 0.2 mm to 0.6 mm: 0.2 mm. If the thickness of the front-surface resin blend layer (a) is smaller than that of the rear-surface resin blend layer (b) (ratio (a) :( b) is less than 1: 1), the durability of the obtained polyolefin-based resin laminated sheet will be poor. When the ratio of the thickness of the front resin blend layer (a) to the thickness of the back resin blend layer (b) exceeds 3: 1, the resulting polyolefin resin sheet becomes excessively heavy ( Thicker), which makes handling difficult.

The fiber fabric for the base fabric which can be used for the flexible polyolefin resin laminated sheet of the present invention may be any of a woven fabric, a knitted fabric and a resin-impregnated fabric. However, it is particularly preferable to use a plain woven fabric because the obtained polyolefin-based resin laminated sheet has an excellent balance between warp and weft properties.
The warp / weft yarns of the fiber cloth may be woven by any of synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers, or mixed fibers composed of two or more of these. Specifically, polypropylene fibers, Synthetic fiber yarns such as polyethylene fiber, vinylon fiber, polyester fiber, aromatic polyester fiber, nylon fiber, aromatic polyamide fiber, acrylic fiber, polyurethane fiber, and inorganic fiber such as glass fiber, silica fiber, alumina fiber, carbon fiber, etc. However, in consideration of workability and versatility, polypropylene fibers and polyester fibers can be preferably used. These fiber yarns can be used in any shape such as a multifilament yarn, a staple spun yarn, a monofilament yarn, a split yarn, and a tape yarn, but the fiber yarn used in the present invention is a multifilament yarn. Excellent in strength and dimensional stability of the sheet from which short fiber spun yarn is obtained,
Most preferred. The fiber fabric used for the flexible polyolefin-based resin laminated sheet of the present invention may be a polyester fiber, a polypropylene fiber, or a multi-filament fiber yarn composed of a mixed fiber thereof, or a plain woven fabric made of a spun short fiber yarn. preferable.

In the present invention, the polyester fiber yarn which can be used for forming a fiber cloth is polyethylene terephthalate (PET) obtained by polycondensation of terephthalic acid and ethylene glycol as a resin material.
Polybutylene terephthalate (PBT) obtained by polycondensation of terephthalic acid and butylene glycol is exemplified. Among them, polyester fibers melt-spun from polyethylene terephthalate resin can be preferably used in view of fiber strength and melt spinnability. In addition, polyethylene terephthalate may contain about 5% by weight of a copolymer monomer such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, and diethylene glycol, in addition to the above monomers.

In the present invention, the above-mentioned polypropylene fiber yarn usable for the fiber fabric includes a yarn spun from a polypropylene resin, a yarn spun from a blend of a polypropylene resin and a polyethylene resin, and a polypropylene fiber made of polyethylene. Yarns coated with a resin and spun are exemplified. As a polypropylene resin as a raw material of these polypropylene fiber yarns, an isotactic stereoregular polypropylene obtained by polymerizing a propylene monomer using a stereoregular catalyst such as a Ziegler-Natta catalyst has fiber strength and spinning. It can be preferably used in view of the properties, particularly preferably a polypropylene fiber yarn having a high isotactic stereoregularity polymerized in the presence of a single-site catalyst, or a high-molecular weight polymerized in the presence of a single-site catalyst Polypropylene fiber yarns having syndiotactic stereoregularity, and these polypropylene resin films are slit into tapes, stretched 5 to 15 times, molecularly oriented, then split into fibers by mechanical operation and twisted splits. It may include a yarn. As a single-site catalyst capable of obtaining a high degree of isotactic stereoregularity, a metallocene complex salt compound comprising an organic transition metal compound containing an indenyl derivative described in (A) Polypropylene resin of the polyolefin resin blend is mentioned. The single-site catalyst capable of obtaining a high degree of syndiotactic stereoregularity includes an organic transition containing a cyclopentadienyl derivative described in (A) Polypropylene resin of the polyolefin resin blend. A metallocene complex salt compound comprising a metal compound can be exemplified.

As a method of spinning a multifilament yarn for a fiber fabric, a thermoplastic resin such as the above polyester resin or the above polypropylene resin is heated to a temperature higher than a melting temperature (melting point) to form a fluid, viscous melt. This is passed through a spinneret having a large number of pores having a specific diameter (about 0.2 to 0.6 mmφ), extruded into an inert cooling medium such as air, nitrogen, or water, and rapidly cooled and solidified to thereby obtain a long length. A method of producing a fiber spinning yarn using a conventionally known melt spinning method and equipment is used. The unstretched long fiber spun yarn is 80-
Stretching 3.0 to 5.0 times by 100 ° C. heat drawing or cold drawing near room temperature to arrange the fiber microstructure,
The fibers can be crystallized to have strength. This stretching step may be incorporated in the spinning step,
Preferably, the drawing step and the multifilament twisting step are performed simultaneously. Further, a two-step heat treatment may be performed as necessary. These melt spinning speeds are not particularly specified because the spinning speeds vary depending on the type and equipment of the thermoplastic resin to be used, but, for example, the spinning speed when melt spinning from a polyester resin is 1000 to 10
Those spun at a speed of 000 m / min, especially 2000 to 6000 m / min, can be preferably used.

In the present invention, the filament yarn for fiber fabric is 139 dtex to 2222 dtex (125 to 20 dtex).
00 denier), especially 278 dtex to 1111 dtex
(250 to 1000 denier) multifilament yarn can be preferably used. 1 multifilament yarn
If it is less than 35 dtex (125 denier), the tear strength of the obtained sheet may be insufficient, and it may be less than 22 dtex.
If it exceeds 22 dtex (2000 denier), the breaking strength and the tearing strength are improved, but the diameter of the yarn becomes thicker and the sheet becomes thicker, and at the same time, the unevenness of the weft intersection of the fiber fabric becomes larger and the smoothness becomes poor. May be enough.
Further, the fiber fabric used for the flexible polyolefin resin laminated sheet of the present invention is preferably a plain weave through. There are no particular limitations on the number of warp yarns and weft yarns of the fiber fabric, but a multifilament yarn of 139 to 2222 dtex (125 to 2000 denier) is used for the warp / weft 25.4.
A woven fabric obtained by driving 8 to 38 pieces per mm, for example, 55
In the case of a multifilament yarn of 5 dtex (500 denier), a plain woven fabric obtained at a driving number of 14 to 24 per 25.4 mm, 1111 dtex (1000 denier)
12 per 25.4 mm for multifilament yarn
An example is a plain woven fabric obtained by driving about 22 strands.

As the short fiber spun yarn, a thermoplastic resin such as the polyester resin and the polypropylene resin described above is heated to a temperature higher than the melting temperature (melting point) to form a fluid, viscous melt, which is Specific caliber (0.2 to 0.6
extruded through an inert cooling medium such as air, nitrogen, water, etc.
0 to 10000 m / min, especially 2000 to 6000 m / min
2 to 6 cm long fiber spun bundle (tow) spun at a speed of min
The staples obtained by cutting into lengths are spread, and while doubling draft is applied, the drawn sliver is stretched at a speed of 200 to 700 m / min to make the fiber parallelism constant to obtain roving (roving). A tow-spun product obtained by applying a draft and a twist to a predetermined count is preferably used. The twisted yarn is a single twisted yarn, a single yarn or two or more single yarns twisted by S (right) twisting or Z (left) twisting by aligning a single yarn or two or more single yarns, and then performing a primary twist. A twisted yarn obtained by pulling two or more twisted yarns together and twisting them, and other strongly twisted yarns may be used. The number of twists of these twisted yarns is 500 for single twisted yarns and ordinary twisted yarns.
It is preferably from 2,000 times / m to 2,000 times / m for a strongly twisted yarn. In addition, as the range of the twist coefficient of the proportionality constant representing the relationship between the yarn count and the number of twists, the twist coefficient is 1.3 to 3.0.
Sweet twist of about, normal twist of about 3.0 to 4.5 twist coefficient,
A strong twist yarn having a twist coefficient of about 4.5 to 5.5 is cited, and a normal twist yarn having a twist coefficient of 3.0 to 4.5 is particularly preferable. These short-fiber spun yarns are used in shuttle looms, shuttle-less looms (rapier, gripper,
It can be manufactured using a conventionally known spinning method and equipment such as a water jet method and an air jet method.

The short fiber spun yarn has a thickness of 5
91dtex (10th British), 295dtex (20th), 197dtex (30th), 148dtex (40th), 97dtex (60th), especially 591
dtex (10th), 422dtex (14th), 370dt
ex (16th), 295dtex (20th), 246dtex
Short fiber spun yarn in the range of (24 count), 197 dtex (30 count) and the like can be preferably used. (The number of these yarns is not limited to a multiple of 10.) If the short fiber spun yarn is thinner than 97 dtex (60 number), the tear strength of the obtained canvas may be insufficient, and 591 dtex may be obtained.
If the thickness is larger than (10th), the breaking strength and the tearing strength are improved, but the diameter of the yarn is increased and the resulting sheet becomes thicker, and at the same time, the unevenness of the weft intersection of the fiber fabric becomes larger, resulting in poor smoothness. May be enough. These staple spun yarns may be made of single yarn, twin yarn, or three or more single yarns, or two ply yarns or two ply yarns of one inch as warp and weft. 30-16
A spun plain woven fabric obtained by driving zero fibers is preferred. Particularly preferably, 295 dtex (20 count) single yarn, or 295
A spun plain woven fabric obtained by driving yarns at a weave density of 50 to 70 warp yarns and 40 to 60 weft yarns per 25.4 mm using dtex twin yarn can be suitably used. In addition, a spun plain woven fabric obtained from a core spun yarn obtained by spinning a short fiber spun yarn around an outer layer (sheath) using a multifilament yarn as an inner layer (core) can also be used.

Further, these multifilament yarns,
Alternatively, the porosity (opening portion) of the fiber fabric made of the short fiber spun yarn is suitably 35% or less, preferably 5 to 30%. If the porosity is less than 5%, the yarn density is too high, and the inter-bridge fusion bondability between the polyolefin resin blend layers formed on the front and back surfaces of the fiber fabric is reduced,
It is not preferable because it deteriorates the dynamic durability. In particular, when the porosity is less than 5%, a thermoplastic resin composition or an adhesive layer comprising a composition of a thermoplastic resin and a curing agent or a cross-linking agent is applied to the surface of the fiber fabric to which the resin blend layer is adhered. If formed, the flexible polyolefin resin laminated sheet of the present invention can be used without lowering the dynamic durability. On the other hand, if the porosity exceeds 35%, the flexibility and dynamic durability of the sheet are improved, but the driving density of the fiber yarn included in the weft direction is reduced, and not only the strength of the obtained sheet is reduced, but also the strength is reduced. However, the dimensional stability is deteriorated and the practicability is lost, which is not preferable. The value of the porosity can be obtained as a value obtained by calculating the area occupied by the fiber yarn in a unit area of the fiber cloth as a percentage and subtracting it from 100. The method of obtaining the porosity as a unit area of 10 cm in the meridian direction × 10 cm in the weft direction is simple and preferable.

The base fabric containing the fiber fabric used for the flexible polyolefin resin laminated sheet of the present invention is preferably subjected to resin coating with a treating agent containing a styrene copolymer resin. As the treatment agent,
A styrene-based copolymer resin dissolved in an organic solvent, wherein the styrene-based copolymer resin includes A-
BA type styrene block copolymer resin (A is a styrene polymer block, B is a butadiene polymer block, an isoprene polymer block, or a vinyl isoprene polymer block.), An AB type styrene block copolymer resin (A and B have the same meanings as described above.), And at least one selected from styrene random copolymer resins and hydrogenated resins of these styrene copolymer resins. These are styrene-based copolymer resins described in (B) Styrene-based copolymer resin of the polyolefin-based resin blend.

Examples of the organic solvent for dissolving these styrene copolymer resins include alcohol solvents such as isopropanol and n-butanol, aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as hexane and heptane. Hydrogen solvents, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, ketone solvents such as methyl ethyl ketone and cyclohexanone, amide solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone, and ethyl acetate And an organic solvent selected from one or more of ester solvents such as butyl acetate, and other solvents such as tetrahydrofuran. The concentration of the styrene copolymer resin dissolved and contained in the treatment agent is preferably 1 to 30% by weight. If the content is less than 1% by weight, the resulting polyolefin resin laminated sheet may have insufficient heat creep resistance and dynamic durability, and the content may exceed 30% by weight. When it becomes large, the coating treatment or the coating treatment on the fiber cloth may become difficult due to a remarkable increase in the solution viscosity of the treatment agent. As a coating treatment, impregnation treatment, and coating treatment method for the fiber cloth, known processing methods, for example, dipping method, dip coating method, doctor knife coating method, gravure coating method, rotary screen coating method, spray coating method and the like It can be carried out by impregnating and / or applying the treating agent one or more times. At this time, the adhesion weight of the (B) styrene copolymer resin is 1 to 50 g / m2 in dry weight.
² , and when the adhesion weight is less than 1 g / m ² , the resulting polyolefin resin laminated sheet may have insufficient heat creep resistance and dynamic durability.
Also, when the adhesion weight exceeds 50 g / m ² ,
The number of coatings increases, the production becomes complicated, and the corresponding effects of improving the heat creep resistance and the joint strength cannot be obtained. Moreover, the obtained laminated sheet becomes unnecessarily heavy, and the handleability of the sheet deteriorates.

The treating agent used in the present invention may contain a silicon compound in addition to the styrenic copolymer resin. Examples of the silicon compound-containing composition include a composition comprising at least one selected from synthetic amorphous silica, colloidal silica, and a silane coupling agent.
Examples of the synthetic amorphous silica include anhydrous silica obtained by a dry method, silica obtained by an airgel method, silica obtained by a wet method, and the like, and those having an average particle diameter of about 1 to 20 μm can be used. .
The amount of silica contained in the pretreatment agent is preferably 1 to 20% by weight based on the styrene-based copolymer resin, and it is preferable to use a silane coupling agent in combination. As the colloidal silica, a colloidal silica sol (SiO ₂ ) having a BET average particle diameter of 10 to 50 nm using an organic solvent as a dispersion medium can be used. As the silane coupling agent, a compound having two or more different reactive groups in a molecule represented by the general formula: XR—Si (Y) ₃ ,
For example, X = amino group, vinyl group, epoxy group, chloro group, mercapto group and the like (R = alkyl chain), Y = methoxy group and ethoxy group. In addition, these hydrolysates, co-hydrolysis compounds with alkoxysilane compounds, and the like can also be used. The silane coupling agent is preferably used at a concentration of 1 to 5% by weight based on the styrene-based copolymer resin.

The treating agent may contain resin components other than the styrene copolymer resin. These resin components are used for dissolving the styrene copolymer resin. There is no particular limitation as long as it is soluble in the organic solvent, but preferably ionomer resin, acrylic resin, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, polyurethane resin, saturated polyester resin, polyamide Thermoplastic resins such as base resins and modified resins thereof can be used. In particular, ethylene copolymer resins modified with glycidyl methacrylate, dimethylaminoethyl methacrylate, itaconic anhydride, maleic anhydride, N-methylmaleimide, and the like, and acrylic copolymer resins are preferable. If necessary, a thermosetting resin such as a phenolic resin, a melamine resin, a urea resin, an unsaturated polyester resin, an epoxy resin, a thermosetting polyurethane resin, or an allyl phthalate resin is blended and used. You can also.
The pretreatment agent is 1) a styrene copolymer resin dissolved in an organic solvent. 2) A styrene-based copolymer resin dissolved in an organic solvent and further containing a silicon compound. 3) A resin obtained by dissolving a styrene copolymer resin with an organic solvent and further dissolving another thermoplastic resin. 4) A resin in which a styrene-based copolymer resin is dissolved in an organic solvent and another thermoplastic resin is dissolved therein and further contains a silicon compound.

In the flexible polyolefin-based resin laminated sheet of the present invention, a polyolefin-based resin blend layer is formed on at least one surface of the base fabric containing the above-mentioned fiber cloth or the base cloth containing the fiber-coated cloth resin-treated with the above-mentioned treating agent. Have been. As an example, the soft polyolefin-based resin laminated sheet of the present invention is a base resin containing the above-mentioned fiber cloth, or a surface resin blend of a polyolefin-based resin blend on both front and back surfaces of a base cloth containing a fiber cloth resin-treated with the above-mentioned treating agent. The layer (a) and the backside resin blend layer (b) are formed. As a method for laminating these resin blend layers, an adhesive layer may be provided between the polyolefin-based resin blend layer and the fiber cloth, or lamination may be performed without an adhesive. Examples of the adhesive include known adhesives, for example, polyurethane-based, polyester-based, polyamide-based, vinyl acetate-based, acrylic-based, cyanoacrylate-based, and modified products thereof. However, in the present invention,
In the case of using a base cloth obtained by resin-coating a fiber cloth with the above treatment agent, it is not generally necessary to use these adhesives. In the above laminating method, a calendar topping method of thermally laminating the polyolefin resin blend layer on each side of the fiber cloth simultaneously with the molding processing of the polyolefin resin blend layer, or T-
A die extrusion lamination topping method may be used, or a polyolefin resin blend film is formed by a calender method, a T-die extrusion method, an inflation method, etc., and then a laminator is used to form two or more polyolefin resin blends. The method of laminating a film on a fiber fabric by thermocompression bonding at one time may be used. For the production of the flexible polyolefin resin laminated sheet of the present invention, a polyolefin resin blend film molded by a calender method and a fiber A production method by thermocompression bonding with a fabric is preferred because it is efficient and economical. At this time, it is preferable that the polyolefin resin blend film on the front surface side and the back surface side be bridged by hot-melt through the void space of the fiber cloth to improve the adhesive strength, and the bending durability. It is preferable that the resin is coated with the treatment agent not only for improving the adhesive strength and the bending durability but also for improving the heat creep resistance. The resin coating of the fiber cloth with the treatment agent is a particularly effective treatment for the base cloth in which the occupied area of the void space of the fiber cloth is less than 5%. Good adhesive strength and bending durability can be sufficiently obtained without the need.

In the flexible polyolefin resin laminated sheet of the present invention, it is preferable from the viewpoint of maintaining an aesthetic appearance that a pollution prevention layer is formed as an outermost layer on at least one of the polyolefin resin blend layers. The contamination prevention layer is an acrylic resin, an acrylic urethane resin,
It is preferably formed of at least one selected from an acrylic silicone resin, an acrylic resin-containing thermoplastic resin, a fluoroolefin resin, and a polyurethane resin. As the acrylic resin, a resin obtained by radical polymerization of a (meth) acrylate monomer is preferable. For example, methyl (meth) acrylate (here, methyl (meth) acrylate means methyl acrylate and methyl methacrylate) The same notation is used hereinafter.) Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, ethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, glycidyl (meth) acrylate, polyethylene glycol (meth) acrylate,
Acrylic resins obtained by homoradical polymerization of trimethylolpropane tri (meth) acrylate or the like, or copolymerization of (meth) acrylate monomers with other radically copolymerizable monomers can also be used. Examples of the monomer capable of being radically copolymerized with the (meth) acrylate monomer include, for example, an alkyl group having 2 carbon atoms.
To 18 alkyl methacrylates, alkyl acrylates having an alkyl group of 1 to 18 carbon atoms, and unsaturated acids such as α, β-unsaturated acids such as acrylic acid and methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. Group-containing divalent carboxylic acids and their alkyl esters, aromatic vinyl compounds such as styrene, α-methylstyrene, and nuclear-substituted styrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; maleic anhydride; maleimide; N-substituted Maleimide and the like.

As the acrylic silicone resin, Si-
Obtained by reacting a modified silicone having two or more functional groups having an OH group and a Si-OMe group (for example, a methylmethylphenyl silicone resin having a silanol group or an alkoxy group) with an alcoholic hydroxyl group-containing resin in the presence of an alkyl titanate catalyst. Silicone modified products such as acryl-modified silicone resin, acryl-urethane-modified silicone resin, urethane-modified silicone resin, urethane-modified silicon-fluorine copolymer resin, moisture-curable acryl-silicon oligomer (Si- (OR) ₃ Graft-modified acrylic: R is methyl, ethyl) and the like. The acrylic urethane-based resin is a polycondensate of an acrylic polyol and a polyisocyanate. Examples of the thermoplastic resin containing an acrylic resin include a blend resin of an acrylic resin and a urethane resin, a blend resin of an acrylic resin and a silicone resin, a blend resin of an acrylic resin and a fluoroolefin resin, and an acrylic resin. An acrylic urethane-based resin such as a blended resin of a polyester-based resin and a polyester-based resin, or a blended resin of an acrylic silicone-based resin and a fluoroolefin-based resin.

Examples of the fluoroolefin resin include a vinyl ether-fluoroolefin copolymer resin having a hydroxyl value of 0 to 250 and a vinyl ester-fluoroolefin having a hydroxyl value of 0 to 250 obtained by copolymerization of a fluoroolefin and a vinyl ether or vinyl ester. A copolymer resin, a combination composition of such a fluorine resin and a polyisocyanate compound, and an amino resin (a melamine resin, a benzoguanamine resin, a urea resin), and the like are used. Examples of the fluoroolefin include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, and the like. And acid-modified products of these vinyl ether moieties, etc., and as the vinyl ester, Veova-9, Veova-10 (manufactured by Shell Chemical), vinyl acetate, vinyl crotonate and the like can be used.

As the polyurethane resin, addition polymerization of a diisocyanate compound and at least one selected from polyol compounds having two or more hydroxyl groups in the molecular structure with a compound having a functional group which reacts with the isocyanate group is used. Those obtained by the reaction can be used. As the diisocyanate, an aromatic, aliphatic, or alicyclic (including a hydrogenated product) diisocyanate compound is used. As a polyol compound having two or more hydroxyl groups, a molecular weight of 300 to 10,000, preferably,
500 to 5000, which contains an amount that reacts with the diisocyanate compound. Further, in addition to the diol, a compound having a functional group that reacts with an isocyanate group may be used as a molecular chain length regulator. To these thermoplastic polyurethane resins, if necessary, a diisocyanate or a polyisocyanate compound containing three or more isocyanate groups in a molecule, a carbodiimide compound, an oxazoline compound, an aziridine compound, and the like are added, and the film strength and Those having improved heat resistance and the like are preferable, and it is more preferable to use a non-yellowing polyurethane resin produced from an aliphatic or alicyclic (including a hydrogenated product) diisocyanate from the viewpoint of light resistance.

The anti-contamination layer of the present invention is formed by one of the above-mentioned acrylic resins, acrylic urethane resins, acrylic silicone resins, thermoplastic resins containing acrylic resins, fluoroolefin resins and polyurethane resins. The above-mentioned treating agent dissolved in an organic solvent at a solid content of 3 to 30% by weight may be used, for example, by a gravure coating method, a microgravure coating method, a comma coating method, a roll coating method, a reverse roll coating method, a bar coating method, Kiss coat method,
The coating can be performed by applying a uniform coating by a known coating method such as a flow coating method, and then drying (hot air).

The bonding of the flexible polyolefin resin laminated sheet of the present invention can be easily performed by fusion using a high frequency welder. As the high-frequency welder joining method, specifically, two or more polyolefin-based resin laminated sheets or the polyolefin-based resin laminated sheet of the present invention and a part of each of the thermoplastic resin molded products that can be heat-fused therewith Are placed between two electrodes (one of the electrodes is a weld bar), and a high frequency (1 to 20) is applied to the electrodes while pressing the weld bar on the joint.
0 MHz), pressurize with a weld bar, and apply heat fusion to these superimposed parts due to the molecular frictional heat of the thermoplastic resin generated in the applied parts.
Seal. 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 a function of a portion where high-frequency electromagnetic radiation energy absorbed by the thermoplastic resin is converted into heat, and the dielectric loss factor is at least 0.01.
It is preferable that it is above. As a high-frequency welder, a commercially available model, for example, YC manufactured by Yamamoto Binita Co., Ltd.
Such as KM-5000TA and KA-7000TE of Seidensha Electronics Co., Ltd .;
LW-4060S or the like can be used.

As another joining method of the wear-resistant polyolefin resin sheet of the present invention, ultrasonic energy (16 to 30 KHz) generated from an ultrasonic vibrator is amplified through a tip of a tool horn, and a plurality of layers are fused. Ultrasonic welder fusion method, in which fusion heat is generated at the boundary surface of the thermoplastic resin welded material by applying to the thermoplastic resin welded material, and is instantaneously fused in about 1 second, or electric control of the heater Thus, hot air set in a stepless manner at 20 to 700 ° C. is blown between the adherends through a nozzle selected in accordance with the fusion specification of the fused body to instantaneously melt the surface of the adherend, and immediately Hot-air fusion method in which the adherend is pressed and bonded, or hot plate fusion method in which the adherend is pressed and sealed using a mold (trowel) heated with a built-in heater above the melting temperature of the thermoplastic resin Which one Fusion bonding is also possible by the method,
For flexible container bags that require complicated three-dimensional sewing, it is preferable to perform sewing using a special mold by high-frequency welding.

[0062]

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the scope of these examples. In the following Examples and Comparative Examples, evaluation of workability, evaluation of flexibility, evaluation of abrasion resistance, evaluation of printability, evaluation of high-frequency welder fusing property, evaluation of heat creep resistance, etc. The test method is as follows.

(1) Evaluation of processability A polyolefin resin compound was mixed with a mixer (Laboplast Mill C type Banbury mixer B600: temperature 12).
0 ° C .: rotation speed 50 rpm: kneaded for 4 minutes at Toyo Seiki Seisakusho Co., Ltd., and the obtained kneaded material was tested on a test roll (φ6 inch two roll: roll gap 1.0) set at 150 ° C.
mm: Nishimura Koki Co., Ltd.) and kneaded for 1 minute, thickness 1.
The appearance and tear strength (JIS K-6301: B-type dumbbell method) of a sheet obtained by rolling a 0 mm sheet were evaluated. ：: good workability (good appearance and tear strength) △: slightly poor workability (poor appearance or tear strength) ×: poor workability (poor appearance and tear strength)

(2) Evaluation of the flexibility
A cylinder having a size of mm × 30 mm is produced (the glue is fixed with a cyanoacrylate instant adhesive) JIS K-6382
The compression test was performed, and the stress at 50% compression (in a state where the diameter of the cylinder was crushed to 10 mm at 20 ° C.) was obtained and compared. Testing machines for evaluating flexibility include loop stiffness
A tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used. ：: good flexibility (150 g or less) △: slightly poor flexibility (151 to 199 g) ×: poor flexibility (200 g or more)

(3) Evaluation of abrasion resistance i) The abrasion resistance of the canvas surface was evaluated by the abrasion strength test C method (the Taber method) specified in JIS L-1096. A rotary abrasion tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used as a tester for evaluating the wear strength. A wear wheel (H-18), a wear load of 0.5 kg, and a wear frequency of 100 were used.
An abrasion test was performed under the condition of 0 times, and a difference in mass (abrasion loss) of the sample before and after the test was obtained and compared. It was determined that the smaller the value, the better the abrasion resistance of the sheet. ii) Under the above conditions, the number of wears until the fiber fabric was exposed on the sheet surface was determined.

(4) Evaluation of printability Screen stencils on which 225 screen lines of "ABCD" alphabet letters were made, and screen process ink for PVC (trade name: Sericol VG-003B Gold Red: Teikoku Ink Manufacturing Co., Ltd.) "ABCD" on the sheet using
Screen printing of alphabet letters (Sericall V
G: Dedicated diluent “D-003 solvent” = 100: 15)
Then, after drying at room temperature for 6 hours, an adhesive tape (trademark: Cellotape: Nichiban Co., Ltd.) was attached to the printing section, and rubbed strongly several times from above the adhesive tape to completely adhere the adhesive tape to the printing section. Thereafter, the adhesive tape was held at a portion where one end of the adhesive tape was peeled off, the adhesive tape was peeled off from the printed portion, and the degree of the area of the printing ink transferred to the adhesive surface of the adhesive tape was evaluated according to the following criteria. A: No printing ink was transferred to the adhesive tape. (Good adhesion) ：: 1 to 9% of the printing ink is transferred to the adhesive tape. (Generally good adhesion) Δ: 10 to 19% of the printing ink is transferred to the adhesive tape. (Not so good adhesion) ×: 20% or more of the printing ink was transferred to the adhesive tape. (Poor adhesion) ××: 100% of printing ink is transferred to the adhesive tape. (No adhesion at all)

(5) Evaluation of High-Frequency Welder Fusing Property The ends of the two polyolefin resin laminated sheets were linearly overlapped with a width of 4 cm, and 4 cm × 3
0cm weld bar (tooth profile: 9 linear moldings with 4 cm width at regular intervals / 25.4 mm, convex height 0.5 mm: 9 linear moldings with 4 cm width at regular intervals / 25.4 mm with concave portions Concave depth 0.5
mm) using a high-frequency welder fusing machine (YF-7000, manufactured by Yamamoto Vinita Co., Ltd .: output 7 KW). In addition, a 3 cm wide sample including the fusion joint was sampled, and a shear test (JIS L-1) of the fusion joint was performed.
096), and the destruction state of the 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 .: fusion is possible by strengthening and lengthening the fusion conditions. * Welder welding conditions: welding time 10 seconds, cooling time 5 seconds anode current 1.2 A, weld bar temperature 40 to 60 ° C. ×: no welding even if the welding conditions are set strong and long. * Welder fusion conditions: fusion time: 10 seconds, cooling time: 5 seconds, anode current: 1.4 A, weld bar temperature: 40-60 ° C (The joint strength is sufficient.) Δ: Partial thread breakage is accompanied by breakage of the joint. (The joint strength is obtained.) X: Complete thread breakage at the joint. (Low joint strength)

(6) Evaluation of heat creep resistance In the heat creep resistance test, a test piece having a test piece width of 3 cm and a test piece length of 30 cm including a joint portion of 4 cm and a test piece length of 30 cm was taken from the welded fusion sheet of (5) and subjected to heat creep resistance. A creep tester (manufactured by Toyo Seiki Seisaku-sho, Ltd .: 100 LDR)
) Was used to evaluate a heat creep resistance test at 50 ° C. × 25 kgf load × 24 hours. ：: After 24 hours, there was no breakage of the joint, and the load of 25 kgf was endured. ×: Shear breakage of the thread was found in the joint within 24 hours.

Example 1 1) Polyolefin resin blend layer (front surface: back surface =
5: 4) i) (A-1) a polypropylene resin (M) obtained by bulk polymerization of propylene in the presence of a metallocene-based catalyst (diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and methylaminoxan)
FR 3.2g / 10min / 230 ° C: Crystal melting point 130
° C: syndiotactic pentad fraction 0.767 /
¹³ C-NMR) and 50 parts by weight of (B-1) a styrene-based copolymer resin (trade name: Hybler 7125 (HVS-
3): Styrene-hydrogenated vinyl isoprene-styrene copolymer resin: MFR 6.0 g / 10 min / 230 ° C .: 20 parts by weight of styrene content: 20 wt%: Kuraray Co., Ltd.) and a test roll set at 150 ° C. 2 rolls of φ6 inch: roll gap 1.0 mm: pre-mixed for 2 minutes with Nishimura Koki Co., Ltd. ii) (C-1) Ethylene-vinyl acetate copolymer resin (trade name: Evatate K2010: MFR 3.0) as the component (C) in the pre-kneading compound of the components (A) and (B).
g / 10 min / 190 ° C .: vinyl acetate content 25% by weight: 20 parts by weight of Sumitomo Chemical Co., Ltd. and (C-2) an ethylene-vinyl acetate copolymer resin (trade name: Ebaslen 4)
10P: MFR 1.0 g / 10 min / 190 ° C .: vinyl acetate content 60% by weight: Dainippon Ink and Chemicals, Inc.
20 parts by weight were added and kneaded with a test roll set at 150 ° C. for 2 minutes to obtain a polyolefin resin blend consisting of (A) + (B) + (C) = 100 parts by weight. iii) Synthetic amorphous silica (trade name: Nip Seal E200: Nippon Silica Kogyo Co., Ltd .: water content 6% by weight) based on 100 parts by weight of the polyolefin resin blend comprising the above components (A) + (B) + (C) : Average particle size of 3 μm), 3 parts by weight, phosphate ester lubricant (trade name: LTP-2: Kawaken Fine Chemical Co., Ltd.) 1.0 part by weight, benzotriazole ultraviolet absorber (trade name: Biosorb 510: Kyodo Yakuhin) Co., Ltd.) 0.2 parts by weight, hindered amine light stabilizer (trade name: Tinuvin 770: Ciba Specialty Co., Ltd.)
0.1 parts by weight of Chemicals Co., Ltd. and 3 parts by weight of a color pigment [(organic pigment colored pellets: trademark: HCM1)
617 Blue: 20% by weight of cyanine blue (α): 2 parts by weight of Dainichi Seika Kogyo Co., Ltd. + inorganic pigment colored pellets: Trademark: HCM2060 White: 60% by weight of titanium dioxide (R): Dainichi Seika 2 parts by weight) and kneaded uniformly with a test roll at 150 ° C. for 3 minutes, and a 0.25 mm thick resin blend containing 11% by weight of the total amount of vinyl acetate component from the kneaded composition. The film and a 0.20 mm thick resin blend film were calendered and rolled. The tensile yield value of this blend film was 747 N / cm ² .

2) Fiber cloth (multifilament base cloth)
Styrene copolymer resin (trade name: Septon 2007: MFR 2.4 g / 10 min / 230 ° C.), which is a pretreated styrene-hydrogenated isoprene-styrene copolymer resin (styrene-ethylene-propylene-styrene copolymer resin) Styrene content 30 wt%: Kuraray Co., Ltd.)
A toluene solution containing the styrene-based copolymer resin solution was prepared by dissolving the styrene-based copolymer resin solution in an amount of 100% by weight. 1 part by weight of Kogyo Kogyo Co., Ltd .: 100% by weight of an organic component) and 2 parts of synthetic amorphous silica (trade name: Nip Seal E200: Nippon Silica Kogyo Co., Ltd .: water content 6% by weight: average particle diameter 3 μm).
A part by weight was added and the mixture was stirred uniformly to obtain a lower treatment liquid. Next, 80
Using a mesh line gravure transfer roll coater, this pretreatment liquid was applied to a polyester fiber plain fabric [750 denier (833 dtex) PET multifilament (96f):
Warp density 19 yarns / 2.54 cm x weft density 20 yarns / 2.5
4 cm: porosity 18%: mass 75 g / m ² ] and dried in a hot-air drying oven at 80 ° C. for 2 minutes.
The mass of the PET fiber woven fabric prepared on both sides is 81 g /
m ² .

3) Product of polyolefin resin blend layer
The 0.25 mm thick resin blend film obtained in 1) is placed on the front side and the 0.20 mm thick resin blend film is placed on the back side of both sides of the plain polyester fiber plain fabric obtained in layer 2). And bonded by thermocompression bonding using a laminator set at a roll temperature of 160 ° C., and a resin blend layer (front) :( back) thickness ratio / 5: 4, thickness 0.56.
A polyolefin-based resin laminated sheet having a thickness of 461 g / m ² and a mass of 461 g / m ² was obtained.

Example 2 The polyester fiber plain fabric of Example 1 was replaced with a polypropylene fiber plain fabric [680 denier (755 dtex) PP multifilament (120f):
Yarn density: 24 warps / 2.54 cm x 25 wefts / 2.54
cm: porosity 16%: mass: 80g / m ^2: ※ (Co.) ground polymeric isotactic polypropylene S1
From 06LA (MFR15g / 10min / 230 ℃)
Melt spinning at 70 ° C.], and bonding a polyolefin resin blend layer having a thickness of 0.25 mm and 0.20 mm to both the front and back surfaces of the following treated polypropylene fiber plain fabric in the same manner as in Example 1 except that Blend layer (table):
(Back) thickness ratio / 5: 4, total thickness 0.56 mm, mass 4
A polyolefin resin laminated sheet of 66 g / m ² was obtained.

Example 3 Example 3 was the same as Example 1 except that the composition and layer thickness ratio of the polyolefin resin blend layer of Example 1 were changed as follows. First, (A-
2) Polypropylene resin (E-2640: MFR2.5)
g / 10min / 230 ° C: 30 parts by weight of syndiotactic polypropylene: Idemitsu Petrochemical Co., Ltd.
3) Polypropylene resin (trademark: Cataloy KS-3)
53P: EPR-PP reactor resin: MFR 0.45
g / 10min / 230 ° C, EPR60wt%, PP40wt
%: 30 parts by weight of Sun Allomer Co., Ltd. and 25 parts by weight of (B-1) a styrene-based copolymer resin were blended to give 15 parts by weight.
Test roll set at 0 ° C (φ6 inch 2 rolls:
Pre-kneading was performed for 2 minutes with a roll gap of 1.0 mm). Next, (C-) was added to the preliminary kneading compound of (A) + (B).
2) Add 15 parts by weight of ethylene-vinyl acetate copolymer resin (trade name: Ebaslen 410P), knead with a test roll set at 150 ° C for 2 minutes, and (A) + (B) + (C)
= 100 parts by weight to obtain a polyolefin resin blend. Further, the same additives as those of Example 1 (synthetic amorphous silica,
(A phosphoric ester-based lubricant, a benzotriazole-based ultraviolet absorber, a hindered amine-based light stabilizer, and a coloring pigment) were mixed in the same parts by weight as in Example 1.
The resulting kneaded composition was calendered into a 0.27 mm thick resin blend film containing 9% by weight of a vinyl acetate component and a 0.18 mm thick resin blend film. The same 0.21 mm-thick resin blend film was placed on the front side and the 0.18 mm-thick resin blended film was placed on the back side. In the same manner, the thickness ratio of the resin blend layer (front): (back) / 3:
2. A polyolefin resin laminated sheet having a total thickness of 0.56 mm and a mass of 461 g / m ² was obtained. The tensile yield value of the blend film was 633 N / cm ² .

Example 4 The polyester fiber plain fabric of Example 3 was replaced with a polypropylene fiber plain fabric [680 denier (755 dtex) PP multifilament (120f):
Yarn density: 24 warps / 2.54 cm x 25 wefts / 2.54
cm: porosity 16%: mass: 80g / m ^2: ※ (Co.) ground polymeric isotactic polypropylene S1
From 06LA (MFR15g / 10min / 230 ℃)
Melt spinning at 70 ° C.], and bonding a polyolefin resin blend film having a thickness of 0.27 mm and 0.18 mm to both sides of the above-mentioned plain polypropylene fiber plain fabric, Layer (front): (back) thickness ratio / 3: 2, total thickness 0.56m
m, and a polyolefin resin laminated sheet having a mass of 466 g / m ² was obtained.

[Example 5] (A-A) obtained by bulk polymerization of propylene in the presence of a Ziegler-Natta catalyst
1) 50 parts by weight of a polypropylene resin and (B-2) a styrene-based copolymer resin (trademark: Septon 2007: styrene-hydrogenated isoprene-styrene-based copolymer resin (styrene-ethylene-propylene-styrene-based copolymer resin)) : MFR 2.4g / 10min / 230 ° C: Styrene content 30wt%: Kuraray Co., Ltd. 20 parts by weight were blended, and a test roll (φ6 inch two rolls: roll gap 1.0mm) set at 150 ° C was used for 2 parts. Premixed for minutes. Next, the (C-2) ethylene-vinyl acetate copolymer resin (trade name:
Ebaslen 410P: MFR 1.0g / 10min / 19
0 ° C .: V-vinyl acetate content 60% by weight: 10 parts by weight of Dainippon Ink and Chemicals, Inc. and (C-3) ethylene-methyl methacrylate copolymer resin (trade name: Aclift WH206: MFR 2.0 g / 10 min / 190 ° C .: 20 wt% of methyl methacrylate content: 20 parts by weight of Sumitomo Chemical Co., Ltd., and kneading for 2 minutes with a test roll set at 150 ° C., (A) + (B) + (C) = 10
A polyolefin resin blend consisting of 0 parts by weight was obtained. Further, the same additives (synthetic amorphous silica, phosphate ester-based lubricant, benzotriazole-based UV absorber, hindered amine-based light stabilizer, and color pigment) as in Example 1 were further added to the polyolefin-based resin blend. The same weight parts as in Example 1 were mixed and uniformly kneaded with a test roll at 150 ° C. for 3 minutes, and the kneaded composition contained 10% by weight of a total amount of a vinyl acetate component and a (meth) acrylic acid (ester) component. 25mm thick resin blend film,
A 0.20 mm thick resin blend film was calendered and rolled. With the 0.25 mm thick resin blend film on the front side and the 0.20 mm thick resin blend film on the back side, the following treated polyester fiber plain woven span (short spun yarn base fabric) Example 1
Bonded in the same manner as described above, and the resin blend layer (front): (back) thickness ratio / 5: 4, total thickness 0.66 mm, mass 614 g /
Thus, a polyolefin-based resin laminated sheet of m ² was obtained. Also,
The tensile yield value of the blend layer was 643 N / cm ² .

Polyester fiber plain weave span (staple fiber spinning)
Using a gravure transfer roll coater with a pretreatment 80 mesh line,
The same pretreatment liquid as in Example 1 was applied to a plain weave span made of spun polyester (PET) short fiber yarn [yarn density: 44 warp 20th twin yarn (590dtex) 44 yarns / 2.54cm × weft 20th twin yarn (590dtex) 40 / 2.54 cm: porosity 6.
2%: mass 228 g / m ² ]
It was dried in a hot air drying oven at 80 ° C. for 2 minutes. The mass of the plain weave span of PET fiber treated on both sides is 234 g / m ^2.
Met.

Example 6 The polyester fiber plain weave span of Example 5 was replaced with a plain weave span consisting of spun polypropylene (PP) short fiber yarn [yarn density: warp 24 count double yarn (49
2dtex) 36 / 2.54cm × weft 24 count twin yarn (49
2 dtex) 36 / 2.54 cm: porosity 5.8%: mass 2
05g / m ² * Isotactic Polypropylene S106LA made by Grand Polymer Co., Ltd. (MFR15g / 1
0 min / 230 ° C.) to 270 ° C. melt spinning]. By laminating on both sides, a polyolefin resin laminated sheet having a resin blend layer (front) :( back) thickness ratio / 5: 4, a total thickness of 0.66 mm, and a mass of 590 g / m ² was obtained.

Example 7 Example 7 was the same as Example 5 except that the composition and layer thickness ratio of the polyolefin resin blend layer of Example 5 were changed as follows. First, (A-
2) 30 parts by weight of a polypropylene resin, (A-3) 30 parts by weight of a polypropylene resin, and (B-2) 25 parts by weight of a styrene-based copolymer resin, and a test roll (φ6 inch 2) set at 150 ° C. This roll was preliminarily kneaded with a roll gap of 1.0 mm for 2 minutes. Next, the above (A) +
(C-2) Ethylene-in the pre-kneading compound of (B)
Vinyl acetate copolymer resin (trademark: Ebaslen 410P:
MFR 1.0 g / 10 min / 190 ° C .: 15 parts by weight of vinyl acetate content: 60% by weight (Dainippon Ink and Chemicals, Inc.) were added, and the mixture was kneaded with a test roll set at 150 ° C. for 2 minutes, and (A) + ( A polyolefin-based resin blend consisting of B) + (C) = 100 parts by weight was obtained. Further, the same additives as in Example 1 (synthetic amorphous silica, phosphate-based lubricant,
A benzotriazole-based UV absorber, a hindered amine-based light stabilizer, and a coloring pigment) were mixed in the same parts by weight as in Example 1 and uniformly kneaded with a test roll at 150 ° C. for 3 minutes to obtain a vinyl acetate component of 9 from the kneaded composition. A 0.27 mm-thick resin blend film containing 0.1% by weight and a 0.18 mm-thick resin blend film containing the same by weight were calendered. The polyester fiber plain weave span (short spinning) treated in the same manner as in Example 5 with the 0.27 mm thick resin blend film on the front side and the 0.18 mm thick resin blend film on the back side And a resin blend layer (front): (back) thickness ratio of 3: 2, a total thickness of 0.66 mm, and a mass of 614 g / m.
^Thus, a polyolefin resin laminated sheet 2 was obtained. The tensile yield value of the blend layer was 627 N / cm ² .

Example 8 The plain weave span of the polyester fiber of Example 7 was replaced with a plain weave span made of spun polypropylene (PP) short fiber yarn [yarn density: warp 24th twin yarn (49
2dtex) 36 / 2.54cm × weft 24 count twin yarn (49
2 dtex) 36 / 2.54 cm: porosity 5.8%: mass 2
05 g / m ² : * Isotactic polypropylene S106LA (MFR 15 g /
10 min / 230 ° C.) and melt spinning at 270 ° C.], except that the thickness is 0.27 mm.
And a 0.18 mm polyolefin-based resin blend film were bonded to both the front and back surfaces of the above-mentioned plain-treated polypropylene fiber plain weave span. , mass 590 g / m ²
Was obtained.

Table 1 shows the constitutions and test results of the polyolefin resin laminated sheets of Examples 1 to 8.

[0081]

[Table 1]

[Effects of Examples 1 to 8] (A) polypropylene resin component, (B) styrene copolymer resin component, (C) ethylene-vinyl acetate copolymer resin, and / or ethylene A (meth) acrylic acid (ester) copolymer resin component comprising a resin blend, wherein the component (A), (B), (C) based on the total weight of the component (A), contained in the resin blend (C) The content of A) is 30 to 70% by weight, the content of the component (B) is 10 to 50% by weight, the content of the component (C) is 5 to 40% by weight, and To
By satisfying the condition that the total content of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymer component in the component (C) is 3 to 25% by weight, Examples 1 to 8 Each of the obtained polyolefin-based resin laminated sheets was excellent in flexibility and abrasion resistance, and was easily subjected to high-frequency fusion and secondary processing of printing. Further, the heat resistance was excellent, and particularly, the heat creep resistance of the joined portion by high frequency fusion was also good. In particular, by pretreating the fiber fabric for a base fabric with a styrene copolymer resin, the joint strength of the obtained sheet was improved, and at the same time, the heat creep resistance was further improved (Comparative Examples 1 and 2). , 5, 6). The pretreatment of the base fabric with the styrene-based copolymer resin in Examples 1 to 8 did not impair the flexibility of the sheet and did not impair the tear strength of the sheet (Comparative Example). 3, 4, 7, 8). Still more preferably, the tensile yield value of the polyolefin resin blend layer is set to 500 N /
cm ² or more, and as shown in Examples 1, 2, 5, and 6, the thickness ratio of the blend layer on the front surface and the back surface is 5: 4.
As shown in Examples 3, 4, 7, and 8, by setting the thickness ratio of the blend layer on the front surface and the back surface to 3: 2, the wear durability of the sheet can be further improved. (Comparative Examples 3, 4, 7, and 8).
In the step of processing a resin blend containing the components (A) + (B) + (C), particularly, the blending step is performed in the manner of [(A)
By performing the procedure of + (B) + (C), it was confirmed that the processability of the resin blend was extremely good.

Example 9 (1) Polyolefin-based resin blend film (a) (i) Propylene mass in the presence of a metallocene-based catalyst (diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and methylaminoxan) (A-1) polypropylene resin obtained by polymerization (MFR 3.2 g / 10 min / 230 ° C .: crystalline melting point 13)
0 ° C: syndiotactic pentad fraction 0.767
/ ¹³ C-NMR) and 60 parts by weight of (B-1) a styrene-based copolymer resin (trade name: Hybler 7125 (HVS-
3): Styrene-hydrogenated vinyl isoprene-styrene copolymer resin: MFR 6.0 g / 10 min / 230 ° C .: Styrene content 20 wt%: Kuraray Co., Ltd. 20 parts by weight were blended, and a test roll set at 150 ° C. φ6 inch two rolls: Roll gap 1.0 mm: Preliminary kneading for 2 minutes by Nishimura Koki Co., Ltd.

(Ii) Add the (C-1) ethylene-vinyl acetate copolymer resin (trade name: Evatate K2010: MFR 3.0 g) to the pre-kneading compound of the components (A) and (B).
/ 10min / 190 ° C: vinyl acetate content 25% by weight:
10 parts by weight of Sumitomo Chemical Co., Ltd. and (C-2) an ethylene-vinyl acetate copolymer resin (trade name: Ebaslen 410)
P: MFR 1.0 g / 10 min / 190 ° C .: vinyl acetate content 60% by weight: 10 parts by weight of Dainippon Ink and Chemicals, Inc. were added and kneaded with a test roll set at 150 ° C. for 2 minutes, and component (A) + (B) + (C) -containing polyolefin-based resin blend was obtained.

(Iii) The above components (A) + (B) + (C)
To 100 parts by weight of a polyolefin-based resin blend containing
Nippon Silica Industry Co., Ltd .: Water content 6% by weight: Average particle size 3
μm), a phosphate ester lubricant (trade name: LT)
P-2: Kawaken Fine Chemical Co., Ltd.) 1.0 part by weight,
0.2 parts by weight of a benzotriazole-based ultraviolet absorber (trade name: Biosorb 510: Kyodo Yakuhin Co., Ltd.) and 0.1 parts by weight of a hindered amine-based light stabilizer (trade name: Tinuvin 770: Ciba Specialty Chemicals Co., Ltd.) And 2 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.) + Inorganic pigment colored pellets: Trade name: HCM2060 White: 60% by weight of titanium dioxide (R): 2 parts by weight of Dainichi Seika Kogyo Co., Ltd.] and kneaded uniformly with a test roll at 150 ° C. for 3 minutes. A 0.25 mm thick resin blend film (a) containing 8.5% by weight of the total amount of vinyl components was calendered and rolled. The tensile yield value of this blend layer was 827 N / cm ² .

(2) Polyolefin resin blend filler
And Lum (b) (i) (A -1) Polypropylene resin 55 parts by weight,
(B-1) A test roll (φ6 inch 2) prepared by blending 15 parts by weight of a styrene copolymer resin and setting the temperature at 150 ° C.
This roll was preliminarily kneaded with a roll gap of 1.0 mm for 2 minutes. (Ii) (C-1) 10 parts by weight of ethylene-vinyl acetate copolymer resin and (C-2) ethylene-vinyl acetate copolymer resin 2 in the pre-kneading compound of (A) + (B).
0 parts by weight, and add 2 parts with a test roll set at 150 ° C.
After kneading for minutes, a polyolefin-based resin blend containing the components (A) + (B) + (C) was obtained. (Iii) Synthetic amorphous silica (trade name: Nip Seal E200: Nippon Silica Kogyo Co., Ltd .: water content 6 weight parts) based on 100 weight parts of the polyolefin resin blend containing the above components (A) + (B) + (C) %: Average particle diameter 3 μm), 3 parts by weight, phosphate ester lubricant (trade name: LTP-2: Kawaken Fine Chemical Co., Ltd.) 1.0 part by weight, benzotriazole ultraviolet absorber (trade name: Biosorb 510: joint) 0.2 parts by weight of hindered amine light stabilizer (trade name: Tinuvin 770: Ciba Specialty Co., Ltd.)
0.1 parts by weight of Chemicals Co., Ltd. and 3 parts by weight of a coloring pigment [(organic pigment colored pellets: trademark: HCM1)
617 Blue: 20% by weight of cyanine blue (α): 2 parts by weight of Dainichi Seika Kogyo Co., Ltd. + inorganic pigment colored pellets: Trademark: HCM2060 White: 60% by weight of titanium dioxide (R): Dainichi Seika 2 parts by weight], and uniformly kneaded with a test roll at 150 ° C. for 3 minutes. From this kneaded composition, a 0.20 mm thick plate containing 14.5% by weight of the total amount of vinyl acetate component was added. The resin blend film (b) was calendered and rolled. The tensile yield value of this blend layer was 657 N / cm ² .

(3) Fiber Cloth (Multifilament Based
Styrene copolymer resin (trade name: Septon 2007: MFR 2.4 g / 10 min / 230) which is a pretreated styrene-hydrogenated isoprene-styrene copolymer resin (styrene-ethylene-propylene-styrene copolymer resin) ° C: Styrene content 30 wt%: Kuraray Co., Ltd.)
A toluene solution containing the styrene-based copolymer resin solution was prepared by dissolving the styrene-based copolymer resin solution in an amount of 100% by weight, and a silane coupling agent (KBM303: β / (3,4 epoxycyclohexyl) ethyltrimethoxysilane: Industrial Co., Ltd .: 100 parts by weight of active ingredient) and 1 part by weight of synthetic amorphous silica (trade name: Nipseal E200: Nippon Silica Kogyo Co., Ltd .: water content 6% by weight: average particle diameter 3 μm)
A part by weight was added and the mixture was stirred uniformly to obtain a lower treatment liquid. Next, 80
Using a mesh roll gravure transfer roll coater, this pretreatment liquid was applied to a polyester fiber plain fabric [833 dtex (7
50 denier) PET multifilament (96f):
Warp density 19 yarns / 2.54 cm x weft density 20 yarns / 2.5
4 cm: porosity 18%: mass 75 g / m ² ] and dried in a hot-air drying oven at 80 ° C. for 2 minutes.
The mass of the PET fiber woven fabric prepared on both sides is 81 g /
m ² .

(4) Polyolefin-based resin blend filler
Lamination of the film The resin blend film (a) having a thickness of 0.25 mm and a vinyl acetate content of 8.5% by weight obtained in the step (1) is added to the plain polyester fiber woven fabric obtained in the step (3).
With a 0.20 mm thick, resinous resin blend filter (b) having a vinyl acetate component content of 14.5% by weight on the back side, using a laminator set at a roll temperature of 160 ° C. The resin blend layer (front): (back) thickness ratio: 5: 4, thickness 0.56 mm,
A polyolefin resin laminated sheet having a mass of 461 g / m ² was obtained.

Example 10 The polyester fiber plain woven fabric of Example 9 was replaced with a polypropylene fiber plain woven fabric [755 dtex].
(680 denier) PP multifilament (120
f): Yarn density: 24 warps / 2.54 cm × 25 wefts /
2.54 cm: porosity 16%: mass: 80 g / m ² *
Grand Polymer Isotactic Polypropylene S106LA (MFR15g / 10min / 230)
° C) to 270 ° C for melt spinning,
In the same manner as in Example 9, a 0.25 mm polyolefin resin blend film (a) and a 0.20 mm polyolefin resin blend film (b) were attached to both surfaces of the above-mentioned plain polypropylene fiber plain fabric, and a resin blend was prepared. Layer (front): (back) thickness ratio / 5: 4, thickness 0.56
A polyolefin-based resin laminated sheet having an mm and a mass of 466 g / m ² was obtained.

Example 11 (1) Polyolefin resin blend film (a) (A-2) Polypropylene resin (E-2640: MFR)
2.5 g / 10 min / 230 ° C .: 65 parts by weight of syndiotactic polypropylene: Idemitsu Petrochemical Co., Ltd.
(B-1) A test roll (φ6 inch 2) prepared by blending 25 parts by weight of a styrene copolymer resin and setting the temperature at 150 ° C.
This roll was preliminarily kneaded with a roll gap of 1.0 mm for 2 minutes. Next, 10 parts by weight of the ethylene-vinyl acetate copolymer resin (C-2) was added to the pre-kneading compound of the components (A) and (B), and the mixture was kneaded for 2 minutes with a test roll set at 150 ° C. A polyolefin resin blend containing (A) + (B) + (C) was obtained. Further, the above (A)
+ (B) + (C) to the polyolefin resin blend, the same additives as in Example 9 (synthetic amorphous silica, phosphate ester lubricant, benzotriazole ultraviolet absorber, hindered amine light stabilizer , A color pigment) in the same amount as in Example 9 and uniformly kneaded with a test roll at 150 ° C. for 3 minutes. The layer (a) was calendered and rolled. The tensile yield value of this blend film was 784 N / cm ² .

(2) Polyolefin-based resin blend filler
Lum (b) (A-2) 30 parts by weight of polypropylene resin, (A-3)
Polypropylene resin (trademark: Cataloy KS-353)
P: EPR-PP reactor resin: MFR 0.45 g /
10min / 230 ° C, EPR60wt%, PP40wt%:
30 parts by weight of Sun Allomer Co., Ltd. and 15 parts by weight of the styrene copolymer resin (B-1) were blended, and were mixed with a test roll (φ6 inch two rolls: roll gap 1.0 mm) set at 150 ° C. Premixed for minutes. Next, (C-
2) Add 25 parts by weight of ethylene-vinyl acetate copolymer resin and knead for 2 minutes with a test roll set at 150 ° C.
A polyolefin-based resin blend containing the components (A) + (B) + (C) was obtained. Further, the above components (A) + (B) +
The same additives as in Example 9 (synthetic amorphous silica, phosphate ester lubricant, benzotriazole ultraviolet absorber, hindered amine light stabilizer, coloring pigment) were applied to the (C) -containing polyolefin resin blend. The same parts by weight as in Example 9 were mixed and uniformly kneaded for 3 minutes with a test roll at 150 ° C., and a 0.18 mm thick resin blend film (b) containing 15% by weight of a vinyl acetate component was calendered from the kneaded composition by calender rolling. ) Was molded. The tensile yield value of this blend film was 525 N / cm ² .

(3) Fiber Cloth (Multifilament Based
Cloth) Preparation The same as in Example 9. (4) Lamination of Polyolefin Resin Blend Film A resin blend film having a thickness of 0.27 mm and a vinyl acetate component content of 6% by weight obtained in the above step (1) on the pretreated polyester fiber plain fabric of the above step (3). A laminator with a roll temperature setting of 160 ° C. was used, with (a) on the front side and a 0.18 mm thick, resinous resin blend film (b) having a vinyl acetate component content of 15% by weight on the back side. Thermocompression bonding and bonding, resin blend layer (table):
(Back) thickness ratio: 3: 2, thickness 0.56 mm, mass 461
g / m ² of a polyolefin resin laminated sheet was obtained.

Example 12 Polyester of Example 11
Fiber plain woven fabric, polypropylene fiber plain woven fabric [755 dtex
(680 denier), PP multifilament (120
f): Yarn density: 24 warps / 2.54 cm × 25 wefts /
2.54 cm: porosity 16%: mass: 80 g / m ^Two *
Grand Polymer Co., Ltd. isotactic polypro
Pyrene S106LA (MFR15g / 10min / 230
° C) to 270 ° C for melt spinning]
The same preparations as in Example 9 were performed. 0.2 same as in Example 11
7mm polyolefin resin blend film (a)
And 0.18mm polyolefin resin blend fill
(B) and the above-mentioned plain polypropylene woven fabric
Bonded to the surface in the same manner as in Example 9 and blended with resin
Layer (front): (back) thickness ratio / 3: 2, thickness 0.56 mm,
Mass 466 g / m^Two Polyolefin resin laminated sheet
I got

Example 13 (1) Polyolefin-based resin blend film (a) (A-1) 60 parts by weight of a polypropylene resin;
2) Styrene copolymer resin (trademark: Septon 200)
7: Styrene-hydrogenated isoprene-styrene copolymer resin (styrene-ethylene-propylene-styrene copolymer resin): MFR 2.4 g / 10 min / 230 ° C .: styrene content 30 wt%: Kuraray Co., Ltd.) 20 parts by weight Was preliminarily kneaded with a test roll set at 150 ° C (φ6 inch two rolls: roll gap 1.0 mm) for 2 minutes. Next, (C-2) 10 parts by weight of an ethylene-vinyl acetate copolymer resin and (C-3) an ethylene-methyl methacrylate copolymer resin (trademark) were added to the pre-kneading compound of the components (A) and (B). ： Aclift WH206 ：
MFR 2.0 g / 10 min / 190 ° C .: methyl methacrylate content 20 wt%: 10 parts by weight (Sumitomo Chemical Co., Ltd.) was added, and the mixture was kneaded with a test roll set at 150 ° C. for 2 minutes to obtain component (A) + (B) ) + (C) -containing polyolefin resin blend was obtained. Further, the same additives (synthetic amorphous silica, phosphate-based lubricant, benzotriazole-based ultraviolet absorber, hindered amine-based light stabilizer, coloring pigment) as in Example 9 were added to the polyolefin-based resin blend. The same weight parts are mixed together and uniformly kneaded with a test roll at 150 ° C. for 3 minutes. From this kneaded composition, a 0.25 mm thick resin blend containing 8% by weight of a total amount of a vinyl acetate component and a methyl methacrylate component. The film (a) was calendered and rolled. The tensile yield value of this blend layer was 766 N / cm ² .

(2) Polyolefin resin blend filler
Lum (b) (A-1) 55 parts by weight of a polypropylene resin;
2) blending 15 parts by weight of a styrene copolymer resin,
Preliminary kneading was performed for 2 minutes on a test roll (φ6 inch two rolls: roll gap 1.0 mm) set at 150 ° C.
Next, (C-2) 20 parts by weight of an ethylene-vinyl acetate copolymer resin and (C-3) 10 parts by weight of an ethylene-methyl methacrylate copolymer resin were added to the pre-kneading compound of the components (A) and (B). And kneading for 2 minutes with a test roll set at 150 ° C., and the components (A) + (B) + (C)
A polyolefin-based resin blend was obtained. Further, the same additives (synthetic amorphous silica, phosphate-based lubricant, benzotriazole-based ultraviolet absorber) as in Example 9 were added to the polyolefin-based resin blend composed of the above components (A) + (B) + (C). , A hindered amine light stabilizer and a coloring pigment) were mixed in the same parts by weight as in Example 9 and uniformly kneaded with a test roll at 150 ° C. for 3 minutes, and a total of a vinyl acetate component and a methyl methacrylate component was obtained from the kneaded composition. A 0.20 mm thick resin blend film (b) containing 14% by weight was calendered and rolled. The tensile yield value of this blend layer was 620 N / cm ² .

[0096] (3) polyester fiber plain weave span (short fiber
With a gravure transfer roll coater under processing 80 Messhi'yu line Wei spun yarn base fabric), plain weave span the same pretreatment liquid under treatment solution as in Example 9 made of polyester (PET) staple fiber spun yarns [ Yarn density: warp 20th twin yarn (590 dtex) 44 yarns / 2.54
cm × 20-count twin yarn (590 dtex) 40 yarns / 2.54
cm: porosity: 6.2%: mass: 228 g / m ² ] and dried in a hot air drying oven at 80 ° C. for 2 minutes. The mass of the PET fiber plain weave span that had been prepared on both sides was 234 g / m ² . (4) Lamination of Polyolefin Resin Blend Layer The 0.25 mm-thick vinyl acetate component and the methyl methacrylate component obtained in the step (A) having a content of 8 Weight% of the resin blend film (a) on the front side, and 0.20 mm thick,
A resin resin blend film (b) having a content of a vinyl acetate component and a methyl methacrylate component of 14% by weight is bonded to the back surface side by thermocompression bonding using a laminator set at a roll temperature of 160 ° C. Then, a thickness ratio of the resin blend layer (front) :( back) / 5: 4, a thickness of 0.66 mm, and a mass of 615 g / m ² were obtained.

Example 14 Polyester of Example 13
Fiber plain woven fabric, polypropylene fiber plain woven fabric [755 dtex
(680 denier), PP multifilament (120
f): Yarn density: 24 warps / 2.54 cm × 25 wefts /
2.54 cm: porosity 16%: mass: 80 g / m ^Two *
Grand Polymer Co., Ltd. isotactic polypro
Pyrene S106LA (MFR15g / 10min / 230
° C) to 270 ° C for melt spinning,
The same 0.25 mm polyolefin resin as in Example 13
Blend layer (a) and 0.20 mm polyolefin resin
Fat blend layer (b) and the above treated polypropylene fiber
Laminated on both sides of the plain fabric in the same manner as in Example 9,
Fat blend layer (front): thickness ratio of (back) / 5: 4, thickness
0.66mm, mass 590g / m^TwoPolyolefin tree
A fat laminated sheet was obtained.

Example 15 (1) Polyolefin-based resin blend film (a) (A-2) 65 parts by weight of a polypropylene resin;
2) blending 25 parts by weight of a styrene copolymer resin,
Preliminary kneading was performed for 2 minutes on a test roll (φ6 inch two rolls: roll gap 1.0 mm) set at 150 ° C.
Next, 10 parts by weight of the ethylene-vinyl acetate copolymer resin (C-2) was added to the pre-kneading compound of the components (A) and (B), and the mixture was kneaded for 2 minutes with a test roll set at 150 ° C. A polyolefin resin blend of (A) + (B) + (C) was obtained. Further, the above components (A) + (B)
The same additives as in Example 9 (synthetic amorphous silica, phosphate ester-based lubricant, benzotriazole-based UV absorber, hindered amine-based light stabilizer, coloring pigment) for the polyolefin-based resin blend composed of + (C) Was mixed with the same parts by weight as in Example 9, and 3
The mixture was kneaded uniformly for 1 minute, and a 0.27 mm thick resin blend film (a) containing 6% by weight of a vinyl acetate component was calendered from the kneaded composition by calender rolling. The tensile yield value of this blend layer was 696 N / cm ² .

(2) Polyolefin resin blend filler
LUM (b) (A-2) 30 parts by weight of a polypropylene resin;
3) 30 parts by weight of a polypropylene resin and 15 parts by weight of a (B-2) styrene copolymer resin are blended,
Was preliminarily kneaded with a test roll (φ6 inch two rolls: roll gap 1.0 mm) set for 2 minutes. Next, (C-
2) Add 25 parts by weight of ethylene-vinyl acetate copolymer resin and knead for 2 minutes with a test roll set at 150 ° C.
A polyolefin-based resin blend of components (A) + (B) + (C) was obtained. Further, the above components (A) + (B) + (C)
The same additives (synthetic amorphous silica, phosphate ester-based lubricant, benzotriazole-based UV absorber, hindered amine-based light stabilizer, and color pigment) as in Example 9 were added to the polyolefin-based resin blend composed of And kneading the mixture uniformly with a test roll at 150 ° C. for 3 minutes, and adding 15% by weight of a vinyl acetate component from the kneaded composition.
The contained 0.18 mm thick resin blend film (b) was calendered and rolled. The tensile yield value of this blend layer was 540 N / cm ² .

(3) Polyester fiber plain weave span (short fiber
(Processed yarn base fabric) The same as in Example 13. (4) Lamination of Polyolefin Resin Blend Layer A resin blend having a thickness of 0.27 mm and a vinyl acetate component content of 6% by weight obtained in the step (1) on the plain polyester fiber woven fabric of the step (3). The film (a) is placed on the front side, the thickness is 0.18 mm, and the content of the vinyl acetate component is 15
A laminator with a roll temperature setting of 160 ° C. so that the weight% of the resin blend film (b) is on the back side.
To obtain a polyolefin resin laminated sheet having a resin blend layer (front) :( back) thickness ratio of 3: 2, a thickness of 0.66 mm, and a mass of 615 g / m ² .

Example 16 Polyester of Example 15
Fiber plain woven fabric, polypropylene fiber plain woven fabric [680 denier
(755 dtex) PP multifilament (120
f): Yarn density: 24 warps / 2.54 cm × 25 wefts /
2.54 cm: porosity 16%: mass: 80 g / m^Two: ※
Grand Polymer Co., Ltd. isotactic polypro
Pyrene S106LA (MFR15g / 10min / 230
° C) to 270 ° C for melt spinning]. Example 15
0.27mm polyolefin resin blend
Film (a) and a 0.18 mm polyolefin resin block
Render film (b) and the above treated polypropylene fiber
Affixed to both sides of Weihei woven fabric in the same manner as in Example 9,
Thickness ratio of resin blend layer (front): (back) / 3: 2, thickness
0.66mm, mass 590g / m ^Two Polyolefin tree
A fat laminated sheet was obtained.

The results of Examples 9 to 16 are shown in Tables 2 and 3.

[0103]

[Table 2]

[0104]

[Table 3]

[Effects of Examples 9 to 16] As the resin blend layer (a) formed on the surface of the fiber woven fabric base fabric,
(A) polypropylene-based resin, (B) styrene-based copolymer resin, (C) ethylene-vinyl acetate copolymer resin, and / or ethylene- (meth) acrylic acid (ester)
A resin blend comprising the components (A) + (B) + (C) of the copolymer resin, wherein the resin blend (a) is contained in the resin blend (a) based on the total weight of the components (a), (b) and (c). The content of the component (A) is 30 to 70% by weight, the content of the component (B) is 10 to 50% by weight, the content of the component (C) is 5 to 40% by weight, and Resin blend (a)
The total content of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymer component in component (c) is 3
(A) polypropylene resin, (B) styrene copolymer resin, (C)
A resin blend comprising components (A) + (B) + (C) of an ethylene-vinyl acetate copolymer resin and / or an ethylene- (meth) acrylic acid (ester) copolymer resin, The ratio of the component (A) contained in the resin blend (a) is 30 to 70% by weight, and the ratio of the component (B) is 1 based on the total weight of the components (A), (B) and (C).
0 to 50% by weight, the ratio of the component (C) is 5 to 40% by weight, and the component (c) of the resin blend (b) is used.
The total content of the vinyl acetate component and the (meth) acrylic acid (ester) component contained in the copolymer component is 10
-25% by weight, and preferably, the thickness ratio between the resin blend layers (a) and (b) is 1: 1.
By satisfying the condition of あ る 3: 1, Examples 9 to
All of the polyolefin resin laminated sheets obtained in No. 16 were excellent in flexibility and abrasion resistance, and were easily subjected to high-frequency fusion and secondary processing of printing. Further, the heat resistance was excellent, and particularly, the heat creep resistance of the joined portion by high frequency fusion was also good.
In particular, by pretreating the fiber woven fabric with a styrene-based copolymer resin, the joint strength of the obtained sheet was improved, and the heat creep resistance was further improved (Comparative Examples 1, 2, and 2). 5, 6). Examples 9 to 16
The pretreatment of the fiber woven fabric base fabric with the styrenic copolymer resin carried out in the above step did not impair the flexibility of the sheet and did not impair the tear strength of the sheet (Comparative Example 3,
4, 7, 8). Furthermore, the tensile yield value of the polyolefin-based resin blend layer is set to 500 N / cm ² or more. The thickness ratio is 5: 4,
Alternatively, as shown in Examples 11, 12, 15, and 16, by setting the thickness ratio of the blend layer of the front surface (a) and the back surface (b) to 3: 2, the wear durability of the sheet is further improved. (Comparative Examples 3, 4, 7, and 8). In addition, component (A) + (B) +
In the step of processing the (C) -containing resin blend, the process of the resin blend is extremely excellent by performing the blending step in particular in the order of the components [Component (A) + (B)] + Component (C). Confirmed that there is.

Example 17 Polyolefin of Example 1
A treating agent having the following composition is applied to the surface of the base resin laminated sheet.
Using a gravure transfer roll coating machine for 80 mesh lines
Apply the whole surface and dry it in a hot air drying oven at 80 ° C for 2 minutes to contaminate it.
An anti-dye layer was formed. Dry coating amount is 5g / m ^Two So
Was. <Acrylic resin surface treatment agent> Trademark: Sony Bond SC-474: Sony Chemical Co., Ltd .: Acrylic copolymer resin (solid content 30 wt%) 100 parts by weight Trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: UV absorber 0.1 parts by weight

[Example 18] A treating agent having the following composition was applied to the entire surface of the polyolefin resin laminated sheet of Example 2 using a gravure transfer roll coater of 80 mesh lines, and dried with hot air at 80 ° C. After drying in an oven for 2 minutes, a contamination prevention layer was formed. The dry coating amount was 5 g / m ² . <Polyester resin surface treatment agent> Trademark: Byron 53SS: Toyobo Co., Ltd .: 100 parts by weight of saturated polyester copolymer resin (solid content 30 wt%) Trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: UV absorber 0.1 Parts by weight

[Example 19] A treating agent having the following composition was applied to the entire surface of the polyolefin resin laminated sheet of Example 5 using a gravure transfer roll coater of 80 mesh lines, and dried with hot air at 80 ° C. After drying in an oven for 2 minutes, a contamination prevention layer was formed. The dry coating amount was 5 g / m ² . <Polyurethane resin surface treatment agent> Trademark: Takerac E-350: Takeda Pharmaceutical Co., Ltd .: 100 parts by weight of polyester polyurethane (solid content: 26 wt%) Trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: UV absorber 1 part by weight

Example 20 Polyolefin of Example 6
A treating agent having the following composition is applied to the surface of the base resin laminated sheet.
Using a gravure transfer roll coating machine for 80 mesh lines
Apply the whole surface and dry it in a hot air drying oven at 80 ° C for 2 minutes to contaminate it.
An anti-dye layer was formed. Dry coating amount is 5g / m ^Two So
Was. <Fluoroolefin resin surface treatment agent> Trademark: Fluorotop 1053: Asahi Glass Co., Ltd .: 100 parts by weight of fluoroolefin vinyl ether copolymer resin (solid content: 50 wt%) Trademark: Takenate D-140N: Takeda Pharmaceutical Co., Ltd .: Isophorone isocyanate curing agent (solid content: 75 wt%) 10 parts by weight Trade mark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: UV absorber 0.2 parts by weight

With respect to the polyolefin resin laminated sheets of Examples 17 to 20, the evaluation tests (2), (3),
(4) and the following antifouling property evaluation test were performed. (7) Evaluation of antifouling property (environmental fouling test) The polyolefin-based resin laminated sheets of Examples 17 to 20 were stretched in a 30 ° direction and a vertical direction of an exposure table installed in the south direction and exposed outdoors. After 6 months of exposure, the surface of the sheet was lightly rubbed 5 times with a gauze moistened with tap water, wiped with water, washed with tap water for 10 seconds, and then naturally dried for 6 hours. Surface color difference ΔE (J
IS-Z-8729) was measured, and the antifouling property was evaluated according to the following criteria. The outdoor exposure test was carried out in Soka City, Saitama Prefecture from April to September. A: ΔE = 0 to 2.9: good without stain. Maintain the initial state. ：: ΔE = 3 to 4.9: Discoloration due to dirt is present, but not noticeable. Tables 4 and 5 show the evaluation results of Examples 17 to 20.

[0111]

[Table 4]

[0112]

[Table 5]

[Effects of Embodiments 17 to 20] Embodiments 17 to 20
The polyolefin-based resin laminate sheet obtained in step 19 is provided with a pollution-preventing layer made of an acrylic resin, a polyester-based resin, and a polyurethane-based resin, respectively. Printability improved. In particular, the polyolefin-based resin laminate sheet obtained in Example 20 was provided with a contamination-preventing layer made of a fluoroolefin-based resin, so that the adhesion and removal of environmental stains (stain resistance) was greatly improved.

Comparative Example 1 The polyolefin of Example 1
From the components (A) + (B) + (C) composition of the resin blend layer
(B) The component styrene copolymer resin is omitted, and (A-1)
Polypropylene resin (MFR 3.2g / 10min / 23
0 ° C: Crystal melting point 130 ° C: Syndiotactic penta
Head fraction 0.767 /¹³C-NMR) 80 parts by weight,
(C-1) Ethylene-vinyl acetate copolymer resin (trademark:
Evatate K2010: MFR 3.0g / 10min / 1
90 ° C: vinyl acetate content 25% by weight: Sumitomo Chemical
(A) + (C) composition consisting of 20 parts by weight
The composition was the same as in Example 1 except that
The same 0.25mm and 0.20mm thick vinyl acetate component
A resin blend layer having a content of 5% by weight was formed in the same manner as in Example 1.
Fabricated by method. Further, the same polyester fiber as in Example 1 was used.
In the first comparative example, the fiber used in the first example was used.
Preparation of the textile was omitted. Except for this, Example 1 and
Similarly, the thickness ratio of the resin blend layer (front): (back) /
5: 4, thickness 0.56mm, mass 460g / m ^Two Polio
A refined resin laminated sheet was obtained. Also, the blend layer
Tensile yield value is 984 N / cm^Two Met.

Comparative Example 2 From the composition of the polyolefin resin blend layer of Example 1 (A) + (B) + (C), (B) the styrene copolymer resin was omitted, and (A-1) polypropylene (A) + comprising 20 parts by weight of a resin and 80 parts by weight of an ethylene-vinyl acetate copolymer resin (C-1)
(C) The composition was the same as in Example 1 except that the composition was 100% by weight.
A resin blend layer having a thickness of 20 mm and a vinyl acetate content of 20% by weight was produced in the same manner as in Example 1. In addition, the same polypropylene fiber plain woven fabric as in Example 2 was used, but in Comparative Example 2, the pretreatment for the fiber woven fabric performed in Example 2 was omitted. Except for this, in the same manner as in Example 1, the thickness ratio of the resin blend layer (front): (back) / 5: 4, thickness 0.56 m
m, and a polyolefin-based resin laminated sheet having a mass of 465 g / m ² . The tensile yield value of the blend layer is 643 N
/ Cm ² .

Comparative Example 3 From the composition of the polyolefin resin blend layer of Example 1 with the components (A) + (B) + (C), (C) an ethylene-vinyl acetate copolymer resin and / or
The ethylene- (meth) acrylic acid (ester) copolymer resin was omitted, and (A-2) a polypropylene resin (E-264)
0: MFR 2.5 g / 10 min / 230 ° C .: Syndiotactic polypropylene: Idemitsu Petrochemical Co., Ltd.) 80
Parts by weight and (B-1) a styrene-based copolymer resin (trademark:
High Blur 7125 (HVS-3): Styrene-hydrogenated vinyl isoprene-styrene copolymer resin: MFR6.
0g / 10min / 230 ° C: Styrene content 20wt%:
Component (A) + consisting of 20 parts by weight of Kuraray Co., Ltd.
(B) The composition other than the composition was the same as in Example 1, and the vinyl acetate component and (meth) acrylic acid (ester) were used.
A resin blend layer having a component content of 0% by weight was produced in the same manner as in Example 1. However, the thickness of the surface forming resin blend layer was 0.12 mm, and the thickness of the back surface forming resin blend layer was 0.24 mm. In addition, the same polyester fiber plain woven fabric as in Example 1 was used, but in Comparative Example 3, the preparation of the fiber woven fabric performed in Example 1 was changed to the following composition.
Except for this, in the same manner as in Example 1, a polyolefin-based resin laminated sheet having a resin blend layer (front) :( back) thickness ratio of 1: 2, a thickness of 0.51 mm, and a mass of 412 g / m ² was obtained. . The tensile yield value of the blend layer was 743 N / cm ^2.
Met.

<Urethane-based resin pretreatment composition> Trademark: Permusen WF-41-083: Avicia Co., Ltd. Polycarbonate type polyurethane emulsion (solid content: 40% by weight) 100 parts by weight Trademark: Aquanate 110: Nippon Polyurethane Industry Co., Ltd. : Hydrophilic group-containing polyisocyanate compound (solid content 100% by weight) 6 parts by weight Diluent: distilled water 40 parts by weight
Using a polyester coater [833 dt
ex (750 denier) PET multifilament (96
f): Warp density 19 yarns / 2.54 cm × weft density 20 yarns /
2.54 cm: Porosity 18%: Mass 75 g / m^Two ] One side
And dried in a hot air drying oven at 80 ° C for 2 minutes.
I let you. The mass of the PET fiber woven fabric that has been subjected to the preparation on both sides is 9
3g / m ^Two Met.

Comparative Example 4 The composition of the polyolefin resin blend layer of Example 1 was calculated from the composition of the components (A) + (B) + (C) and (C) an ethylene-vinyl acetate copolymer resin and / or
The ethylene- (meth) acrylic acid (ester) copolymer resin is omitted, and the component (A) is composed of (A-2) 20 parts by weight of a polypropylene resin and (B-1) 80 parts by weight of a styrene-based copolymer resin. The composition was the same as in Example 1 except that the composition was + (B). It was produced in. However, the thickness of the surface forming resin blend layer was 0.12 mm, and the thickness of the back surface forming resin blend layer was 0.24 mm. Further, the same polypropylene fiber plain woven fabric as in Example 2 was used,
In Comparative Example 4, the pretreatment of the fiber fabric performed in Example 2 was changed to the following composition. Except for this, in the same manner as in Example 1, the thickness ratio of the resin blend layer (front): (back) / 1: 2,
A polyolefin resin laminated sheet having a thickness of 0.51 mm and a mass of 417 g / m ² was obtained. The tensile yield value of the blend layer was 563 N / cm ² .

<Polyester Resin Pretreatment Composition> Trademark: Vylonal MD1250: Toyobo Co., Ltd. 100% by weight of polyester resin emulsion (solid content: 30% by weight) Trademark: Aquanate 110: Nippon Polyurethane Industry Co., Ltd .: Hydrophilic 4 parts by weight of a group-containing polyisocyanate compound (solid content: 100% by weight) Diluent: 20 parts by weight of distilled water The above-mentioned pretreatment liquid was treated with an 80 mesh wire gravure transfer roll coater using a polypropylene fiber plain fabric [755].
dtex (680 denier), PP multifilament (1
20f): yarn density 24 warps / 2.54 cm × wefts 25 / 2.54 cm: porosity 16%: mass: 80 g / m ² : *
Grand Polymer Isotactic Polypropylene S106LA (MFR15g / 10min / 230)
C) to 270 ° C. and melt-spun at 270 ° C.) and dried in a hot-air drying oven at 80 ° C. for 2 minutes. The weight of the PET fiber woven fabric that had been subjected to the pretreatment on both sides was 94 g / m ² .

Comparative Example 5 The component (A) polypropylene resin was omitted from the component (A) + (B) + (C) composition of the polyolefin resin blend layer of Example 5, and (B-1) a styrene copolymer The composition was the same as that of Example 5 except that the component (B) + (C) was composed of 50 parts by weight of the combined resin and 50 parts by weight of the ethylene-vinyl acetate copolymer resin (C-1). Same thickness as in Example 5 0.25mm and 0.20mm
A thick resin blend layer having a vinyl acetate component content of 12.5% by weight was produced in the same manner as in Example 5. In addition, the same polyester fiber plain woven fabric as in Example 5 was used, but in Comparative Example 5, the pretreatment for the fiber woven fabric performed in Example 5 was omitted. Except for this, in the same manner as in Example 5, the thickness ratio of the resin blend layer (front): (back) / 5: 4, thickness 0.66 mm,
A polyolefin resin laminated sheet having a mass of 615 g / m ² was obtained. The tensile yield value of the blend layer is 533 N / cm.
^{Was 2} .

Comparative Example 6 The (A) polypropylene resin was omitted from the components (A) + (B) + (C) of the polyolefin resin blend layer of Example 6, and (B-2) a styrene copolymer Resin (trademark: Septon 2007: Styrene-
Hydrogenated isoprene-styrene copolymer resin (styrene-ethylene-propylene-styrene copolymer resin): M
FR 2.4g / 10min / 230 ° C: styrene content 3
0 wt%: Kuraray Co., Ltd.) and 50 parts by weight of (C-2) an ethylene-vinyl acetate copolymer resin (trade name: Ebaslen 41)
0P: MFR 1.0 g / 10 min / 190 ° C .: vinyl acetate content 60% by weight: Dainippon Ink and Chemicals, Inc. 5
The composition was the same as that of Example 6 except that the component (B) + (C) was composed of 0 parts by weight. 30
A resin blend layer of weight% was prepared in the same manner as in Example 6. In addition, the same polypropylene fiber plain fabric as in Example 6 was used, but in Comparative Example 6, the pretreatment for the fiber fabric performed in Example 6 was omitted. Except for this, in the same manner as in Example 6, the thickness ratio of the resin blend layer (front): (back) / 5:
4. A polyolefin resin laminated sheet having a thickness of 0.66 mm and a mass of 590 g / m ² was obtained. The tensile yield value of the blend layer was 546 N / cm ² .

Comparative Example 7 Component (A-1) of Polyolefin Resin Blend Layer of Example 5 Polypropylene Resin 8
5 parts by weight, (B-2) 5 parts by weight of styrene copolymer resin, (C-1) ethylene-vinyl acetate copolymer resin 10
The composition was the same as that of Example 5 except that the composition was changed to the components (A) + (B) + (C) consisting of parts by weight. 5
It was prepared in the same manner as described above. However, the thickness of the surface forming resin blend layer was 0.12 mm, and the thickness of the back surface forming resin blend layer was 0.24 mm. In addition, the same polyester fiber plain fabric as in Example 5 was used, but in Comparative Example 7, the composition of the pretreatment liquid for the fiber fabric performed in Example 5 was changed to the following composition. Except for this, in the same manner as in Example 5, the thickness ratio of the resin blend layer (front): (back) / 1: 2, and the thickness of 0.
A polyolefin resin laminated sheet having a size of 56 mm and a weight of 569 g / m ² was obtained. The tensile yield value of the blend layer is 86.
It was 6 N / cm ² .

<Urethane resin pretreatment composition> Trademark: Permusen WF-41-083: Avicia Co., Ltd. Polycarbonate polyurethane emulsion (solid content: 40% by weight) 100 parts by weight Trademark: Aquanate 110: Nippon Polyurethane Industry Co., Ltd. : Hydrophilic group-containing polyisocyanate compound (solid 100% by weight) 6 parts by weight Diluent: distilled water 40 parts by weight Polyester (PET) was applied to the above-mentioned undertreatment solution using an 80 mesh line gravure transfer roll coater. Plain weave span composed of short fiber spun yarn [Yarn density: 44 warp 20th twin yarn (590dtex) 44 / 2.54cm x 40th weft 20th double yarn (590dtex) 40 / 2.54cm: Porosity 6.2%:
Mass 228 g / m ² ] on the entire surface, 80 ° C.
In a hot air drying oven for 2 minutes. The weight of the PET fiber woven fabric that had been subjected to the preparation on both sides was 246 g / m ² .

Comparative Example 8 The composition of the polyolefin-based resin blend layer of Example 6 was the same as that of (A-1) 20 parts by weight of a polypropylene resin, (B-2) styrene-based copolymer resin 10
Parts by weight, (C-2) 20 parts by weight of an ethylene-vinyl acetate copolymer resin and (C-3) an ethylene-methyl methacrylate copolymer resin (trade name: ACLIFT WH206: MF)
R 2.0 g / 10 min / 190 ° C .: methyl methacrylate content 20 wt%: Sumitomo Chemical Co., Ltd.) The composition was changed to that of component (A) + (B) + (C) except that the composition was changed to that of Example 6. And a vinyl acetate component content of 22
A resin blend layer of weight% was prepared in the same manner as in Example 6. However, the thickness of the surface forming resin blend layer is 0.1
2 mm, and the thickness of the resin blend layer for forming the back surface is 0.1 mm.
24 mm. In addition, the same polypropylene fiber plain woven fabric as in Example 6 was used, but in Comparative Example 8, the preparation of the fiber woven fabric performed in Example 6 was changed to the following composition. Otherwise,
Resin blend layer (front): (back) as in Example 6
Thickness ratio: 1: 2, thickness 0.56 mm, mass 544 g / m
^Thus, a polyolefin resin laminated sheet 2 was obtained. The tensile yield value of the blend layer was 572 N / cm ² .

<Polyester Resin Pretreatment Composition> Trademark: Vylonal MD1250: Toyobo Co., Ltd. 100% by weight of polyester resin emulsion (solid content 30% by weight) Trademark: Aquanate 110: Nippon Polyurethane Industry Co., Ltd .: Hydrophilic Group-containing polyisocyanate compound (solids 100% by weight) 4 parts by weight Diluent: distilled water 20 parts by weight Spinning the above-mentioned pretreatment liquid using a gravure transfer roll coater with an 80 mesh wire for polypropylene (PP) short fiber spinning. Plain weave span consisting of yarn [Yarn density: 36 warp 24th twin yarn (492dtex) 36 / 2.54cm × weft 24th double yarn (492dtex) 36 / 2.54cm: Porosity 5.8%:
Mass 205g / m ² ※ (Co.) ground polymeric isotactic polypropylene S106LA (MFR15
g / 10 min / 230 ° C.) to 270 ° C. for melt spinning] and dried in a hot air drying oven at 80 ° C. for 2 minutes. The weight of the PET fiber woven fabric that had been subjected to the pretreatment on both sides was 219 g / m ² .

Table 6 shows the results of Comparative Examples 1 to 8.

[0127]

[Table 6]

Performance of [Comparative Examples 1] to [Comparative Example 8] In the present invention, as the resin blend layer (a) formed on the surface of the fiber woven fabric, (A) a polypropylene resin, and (B)
Component (A) + (B) + of styrene copolymer resin, (C) ethylene-vinyl acetate copolymer resin, and / or ethylene- (meth) acrylic acid (ester) copolymer resin
It is required to be a resin blend containing (C),
Since the sheets obtained in Comparative Examples 1 and 2 do not contain the component (B), it is difficult to effectively knead the resin with the component (A) and the component (C), and the resin has a poor appearance. It was a blend and further printing was not possible. In addition, the sheets obtained in Comparative Examples 3 and 4 did not contain high frequency weldability because they did not contain the component (C). Further, the sheets obtained in Comparative Examples 5 and 6 did not contain the component (A) and thus had poor abrasion resistance. Also,
The sheets obtained in Comparative Examples 7 and 8 are (A), (B),
(C) contains all components, but in Comparative Example 7, the content of the component (A) is too large and the content of the component (B) is too small, so that sufficient processability and flexibility cannot be obtained, Comparative Example 8
Since the content of the component (A) is too small and the content of the component (C) is too large, the sheet obtained in (1) cannot obtain sufficient wear resistance and heat creep resistance. Comparative Examples 3, 4,
In Examples 7 and 8, the styrenic copolymer resin-based pretreatment composition of Examples 1, 5, 9, and 13 was changed to a polyurethane-based resin and a polyester-based resin-based composition, whereby the texture of the resulting sheet was improved. At the same time as hardening, there was a problem that the tear strength was greatly reduced. Particularly, in Comparative Examples 3, 4, 7, and 8, the ratio of the thickness of the resin blend layer formed on the front side of the fiber woven fabric to the thickness of the resin blend layer formed on the back side was 1: 2. By
The abrasion durability of the obtained sheet was extremely poor.

[Effects of the Invention] As is clear from the above Examples and Comparative Examples, the present invention provides a polyolefin having a soft feel and excellent abrasion resistance, and capable of printing and high-frequency welder fusion. -Based resin laminated sheet, and it is possible to obtain a polyolefin-based resin laminated sheet excellent in the fracture strength and heat creep resistance of the fusion bonded portion,
The polyolefin-based resin laminate sheet obtained by the present invention can be suitably used particularly as a raw material for a flexible container, and further includes other industrial material sheets, such as an oil fence, a truck bed cover, a house tent, a cushion mat, and the like. It is a highly useful sheet even in the field where a soft polyvinyl chloride resin product was conventionally used as the sheet material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/36 C08K 3/36 4L048 C08L 23/08 C08L 23/08 23/10 23/10 23/16 23 / 16 25/04 25/04 53/02 53/02 D06M 15/233 D06M 15/233 // D03D 1/00 D03D 1/00 Z D06M 101: 34 D06M 101: 34 F term (reference) 4F100 AA20B AK03B AK03C AK03E AK03K AK04B AK04D AK04J AK05D AK07A AK07B AK07D AK07J AK12A AK12B AK12D AK17C AK17E AK25B AK25C AK25D AK25E AK25J AK28A AK28B AK28J AK29A AK41A AK51C AK51E AK52C AK52E AK64B AK66B AK68B AK68D AL01B AL01C AL01D AL01E AL02A AL02B AL05B AL05D AL06C AL06E AL09B AR00C AR00E BA02 BA03 BA05 BA07 DG01A DG03A DG07A DG11A DG12A EC032 EH171 EH461 EJ191 EJ192 EJ64A EJ861 GB31 GB56 GB90 JA12B JA20 JK09 JK12 JK13 JK20 JL06C JL06E YY00 4J002 BB06Y BB07Y BB12W BB14W BB15W BC04X BP01X DJ016 4J028 AA01A AB01A AC01A AC09A AC28A BA00A BA01B BB00A BB01B BC25B EB02 EB04 EB15 EC01 EC02 GA12 4J128 AA01 AB01 ACOB EB01 BA01 ACOB CA28 4L048 AA15 AA21 AB01 AB07 BA01 BA02 CA15 DA27 DA33

Claims (23)

[Claims] 1. A base fabric including a fiber fabric, and a coating layer formed on at least one surface of the base fabric and made of a polyolefin resin blend, wherein the polyolefin resin blend layer comprises: (A) polypropylene (B) Styrene copolymer resin, and (C) ethylene-vinyl acetate copolymer resin and / or ethylene- (meth) acrylic acid (ester) copolymer resin The component (A), which is formed from a polyolefin-based resin blend containing:
The content of the component (A) is 30 to 70% by weight based on the total weight of the components (B) and (C), and the content of the component (B) is 10%.
-50% by weight, the content of the component (C) is 5-40% by weight, and copolymerized vinyl acetate and (meth) acrylic in the component (C) contained in the resin blend. The total content with an acid ester is 3 to 25 weight%, The soft polyolefin resin laminated sheet characterized by the above-mentioned. 2. The soft polyolefin resin sheet according to claim 1, wherein a pollution prevention layer is formed as an outermost layer on at least one of the polyolefin resin blend coating layers. 3. A surface layer comprising a surface polyolefin-based resin blend (a) is formed on a surface of a base fabric including the fiber cloth, and a back surface comprising a back-surface polyolefin-based resin blend (b) on the back surface of the base fabric. Each of the front and rear polyolefin resin blend layers (a) and (b) comprises: (A) a component comprising a polypropylene resin; (B) a component comprising a styrene copolymer resin; And (C) a component comprising an ethylene-vinyl acetate copolymer resin and / or an ethylene- (meth) acrylic acid (ester) copolymer resin. In the blend layer (a), the content of the component (A) is 3 with respect to the total weight of the components (A), (B) and (C) contained therein. 70
% By weight, the content of the component (B) is 10 to 50% by weight,
The content of the component (C) is 5 to 40% by weight, and the copolymerized vinyl acetate and (meth) acrylic acid (ester) in the component (C) contained in the resin blend (a). ) Is 3 to 10% by weight, and in the back surface polyolefin resin blend layer (b), the amount of the component (A), (B) and (C) is based on the total weight of the component The content of (A) is 30 to 70
% By weight, the content of the component (B) is 10 to 50% by weight,
And the content of the component (C) is 5 to 40% by weight;
The component (C) contained in the resin blend (b) has a total content of copolymerized vinyl acetate and (meth) acrylic acid (ester) of 10 to 25% by weight. The flexible polyolefin-based resin laminated sheet according to the above. 4. The thickness ratio of the surface layer formed from the polyolefin resin blend (a) to the back layer formed from the polyolefin resin blend (b) is 1: 1 to 3: 1. The flexible polyolefin-based resin laminated sheet according to claim 3. 5. The flexible polyolefin-based resin laminated sheet according to claim 3, wherein a pollution prevention layer is formed as an outermost layer on at least one of the front surface layer and the back surface layer. 6. The contamination prevention layer comprises at least one selected from an acrylic resin, an acrylic urethane resin, an acrylic silicone resin, a thermoplastic resin containing an acrylic resin, a fluoroolefin resin, and a polyurethane resin. The flexible polyolefin-based resin laminated sheet according to claim 2 or 5. 7. The polypropylene resin for the component (A) is a propylene homopolymer, an ethylene-propylene copolymer, a propylene-α-olefin copolymer, a propylene-ethylene / propylene copolymer elastomer, propylene-ethylene. The soft polyolefin-based resin laminated sheet according to claim 1 or 3, which is at least one selected from propylene / non-conjugated diene-based copolymer elastomers. 8. The propylene homopolymer for the component (A), an ethylene-propylene copolymer, and propylene-α-
The flexible polyolefin-based resin laminate sheet according to claim 7, wherein the olefin copolymer is a polypropylene-based resin having syndiotactic stereoregularity polymerized in the presence of a single-site catalyst. 9. The propylene homopolymer for the component (A), an ethylene-propylene copolymer, and propylene-α-
The flexible polyolefin-based resin laminate sheet according to claim 7, wherein the olefin copolymer is a polypropylene-based resin having isotactic stereoregularity polymerized in the presence of a single-site catalyst. 10. The styrenic copolymer resin for component (B) is an ABA type styrene block copolymer resin (A represents a styrene polymer block, B represents a butadiene polymer block, and isoprene polymer. Represents a united block or a vinyl isoprene polymer block), an AB type styrene block copolymer resin (A and B have the same meanings as described above), a styrene random copolymer resin, and the styrene copolymer. 1 selected from hydrogenated resins of polymer resins
The flexible polyolefin-based resin laminated sheet according to claim 1, comprising at least one kind. 11. The soft resin according to claim 1, wherein the polyolefin resin blend containing the components (A), (B) and (C) further contains 1 to 15% by weight of synthetic amorphous silica. Polyolefin resin laminated sheet. 12. The soft polyolefin according to claim 1, wherein the fiber cloth is a multifilament yarn or a short fiber spun yarn, and has a woven fabric porosity of 0 to 35%. Resin laminated sheet. 13. The flexible polyolefin-based resin laminated sheet according to claim 1, wherein the fiber cloth is resin-coated with a treatment agent containing a styrene-based copolymer resin. . 14. The fiber fabric treating agent is a styrene copolymer resin solution dissolved in an organic solvent, wherein the styrene copolymer resin is an ABA type styrene block copolymer. Coalesced resin (A represents a styrene polymer block, B represents a butadiene polymer block, an isoprene polymer block, or a vinyl isoprene polymer block), an AB type styrene block copolymer resin (A
And B are as defined above. 14.) The flexible polyolefin-based resin laminated sheet according to claim 13, which is at least one selected from styrene random copolymer resins and hydrogenated resins of these styrene-based copolymer resins. 15. The flexible polyolefin-based resin laminated sheet according to claim 1, wherein the fiber cloth is made of polyester fibers. 16. The flexible polyolefin resin laminated sheet according to claim 1, wherein the fiber cloth is made of polypropylene fibers. 17. The fiber according to claim 16, wherein the polypropylene fiber is a fiber spun from a polypropylene resin having isotactic stereoregularity or syndiotactic stereoregularity polymerized in the presence of a single-site catalyst. Soft polyolefin resin laminated sheet. 18. The method according to claim 1, wherein the light emitting device comprises:
In order to produce the flexible polyolefin-based resin laminated sheet according to the item, the polyolefin-based resin blend is mixed with the component (A)
And the component (B) are pre-blended, and the component (C) is blended with the pre-blend (A + B), or the component (B) and the component (C) are pre-blended,
The pre-blend (B + C) is prepared by blending the component (A) with the component (A). At this time, the component (A), (B), and (C) in the polyolefin resin blend are added to the component (A), The amount of (A) is 30 to 70% by weight, and the amount of component (B) is 10 to 50% by weight.
And the amount of the component (C) is 5 to 40% by weight,
And a total content of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymer component in the component (C) in the resin blend is adjusted to 3 to 25% by weight. A method for manufacturing a resin sheet. 19. The method for producing a flexible polyolefin-based resin sheet according to claim 18, further comprising forming a pollution prevention layer as an outermost layer on at least one of the polyolefin-based resin blend coating layers. 20. A polyolefin resin blend for a surface layer (a) and a polyolefin resin for a back layer for producing the flexible polyolefin resin laminate sheet according to any one of claims 3 and 7 to 17. Each of the resin blends (b) is pre-blended with the component (A) and the component (B), and the component (C) is added to the pre-blend (A + B).
Or the component (B) and the component (C) are pre-blended, and the pre-blend (B +
Prepared by blending said component (A) with C),
At this time, the blending amount of the component (A) was 3 with respect to the total weight of the components (A), (B) and (C) in each of the polyolefin resin blends (a) and (b).
0 to 70% by weight, and the amount of the component (B) is 10 to 70% by weight.
50% by weight, the compounding amount of the component (C) is 5 to 40% by weight, and vinyl acetate and (meth) contained as a copolymer component in the component (C) in the surface layer resin blend (a). The total content of acrylic acid (ester) is 3 to 1
0% by weight, and the total content of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymer component in the component (C) in the resin blend (b) for the backside layer is 10 to 25. Weight%, forming a surface layer comprising the surface layer polyolefin resin blend (a) on the surface of the fiber cloth-containing base cloth;
A method for producing a soft polyolefin-based resin laminated sheet, comprising: forming a back surface layer made of the polyolefin-based resin blend for back surface (b) on the back surface of the base fabric. 21. The method according to claim 20, wherein the thickness ratio between the front layer and the back layer is adjusted to 1: 1 to 3: 1. 22. At least one of the front surface layer and the back surface layer
On the layer, further form a contamination prevention layer as an outermost layer,
A method for producing a flexible polyolefin-based resin laminated sheet according to claim 20. 23. An anti-fouling layer comprising an acrylic resin,
Acrylic urethane resin, acrylic silicone resin,
The method for producing a flexible polyolefin-based resin laminated sheet according to claim 19, wherein the sheet is formed from at least one selected from an acrylic-based resin-containing plastic resin, a fluoroolefin-based resin, and a polyurethane-based resin.