JP2000000936A - Waterproof sheet made of olefinic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a waterproof sheet made of an olefinic resin excellent in the balance of damage resistance, flexibility, blocking resistance, oil resistance, chemical resistance and heat fusion properties and generating no hydrogen chloride gas upon incineration. SOLUTION: In a waterproof sheet made of an olefinic resin comprising a laminate constituted of at least both outer layers and an intermediate layer, the intermediate layer of the laminate is a layer comprising an ethylene/ ethylenic unsaturated ester copolymer (I) and both outer layers of the laminate are layers comprising an olefinic resin (II) [excepting the ethylene/ethylenic unsaturated ester copolymer (I)] and the thickness ratio of the laminate is set so that the thickness of the intermediate layer is 0.2-50 with respect to the sum total thickness 1 of both layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof sheet made of an olefin resin used in the fields of construction and civil engineering. In more detail, waterproof sheets and general buildings used for waterproofing the inner surfaces of final disposal sites, ornamental ponds, pools, etc.
A waterproofing sheet used for roofing civil engineering structures, which has excellent balance of scratch resistance, flexibility, blocking resistance, oil resistance, and chemical resistance, and has excellent workability due to excellent heat fusion properties. The present invention relates to a resin waterproof sheet.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of global environmental protection, instead of vinyl chloride resin that generates hydrogen chloride gas during incineration,
Olefin-based resins that do not generate hydrogen chloride gas have been used. However, conventional olefin-based resin waterproof sheets are inferior in scratch resistance, flexibility, blocking resistance, oil resistance, chemical resistance, and heat-sealing properties to vinyl chloride resin waterproof sheets. There is a strong demand for improvement.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an excellent balance of scratch resistance, flexibility, blocking resistance, oil resistance, chemical resistance and heat-sealing properties. An object of the present invention is to provide a waterproof sheet made of an olefin-based resin which does not generate water.

[0004] The inventors of the present invention have intensively studied to obtain a waterproof sheet made of an olefin resin having excellent performance, using a specific ethylene copolymer for the intermediate layer, and using the olefin resin ( However, it has been found that a waterproof sheet made of an olefin-based resin composed of a laminate obtained by using the above-mentioned specific ethylene-based copolymer) achieves the object of the present invention, and has completed the present invention.

[0005]

That is, the present invention relates to a waterproof sheet made of an olefin resin comprising a laminate composed of at least both outer layers and an intermediate layer, wherein the intermediate layer of the laminate is ethylene-ethylene. A layer comprising the unsaturated unsaturated ester copolymer (I), wherein both outer layers of the laminate are made of an olefin resin (II) (excluding the ethylene-ethylene unsaturated ester copolymer (I)). And a thickness ratio of the intermediate layer to the total thickness of the two outer layers is 1 to 0.2 to 50. Further, the present invention is a waterproof sheet characterized in that at least one layer selected from a nonwoven fabric layer, an adhesive layer and a foam layer is laminated on at least one surface of the laminate. Hereinafter, the present invention will be described in detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin resin waterproof sheet of the present invention comprises a laminate of at least three layers composed of both outer layers and an intermediate layer. The intermediate layer of the laminate is a layer composed of the ethylene-ethylenically unsaturated ester copolymer (I). Examples of the ethylenically unsaturated ester of the ethylene-ethylenically unsaturated ester copolymer (I) include vinyl acetate or alkyl α, β-unsaturated carboxylate. The α, β-unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid or methacrylic acid. Specific examples thereof include methyl acrylate and acrylic acid. Ethyl, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,
T-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylic acid
Propyl, isopropyl methacrylate, n-methacrylate
-Butyl, t-butyl methacrylate, and isobutyl methacrylate. Among these,
Vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are preferred.

The ethylene-ethylenically unsaturated ester copolymer preferably contains 60 to 95% by weight of ethylene units, 40 to 5% by weight of ethylenically unsaturated ester units, and more preferably 70 to 95% by weight. 90% by weight, 30 to 10% by weight of ethylenically unsaturated ester unit
It is.

Both outer layers of the laminate are layers composed of an olefin resin (II) (except for the ethylene-ethylenically unsaturated ester copolymer (I)). Examples of the olefin-based resin include ethylene homopolymer, ethylene and an ethylene-based copolymer which is a copolymer of α-olefin, styrene, norbornene, butadiene, vinylcyclohexene, and other unsaturated cyclic monomers. Ethylene polymer (B); propylene / α-olefin random copolymer such as propylene homopolymer, propylene / ethylene random copolymer, propylene / butene-1 copolymer, propylene / ethylene / butene-1 copolymer Examples include polymers, propylene-based polymers (C) such as propylene-based block copolymers, and olefin homopolymers such as polybutene-1 and poly-4-methylpentene-1.
Further, a copolymer with a polyunsaturated compound such as a conjugated diene or a non-conjugated diene is also included together with the α-olefin.
These may be used alone or as a mixture of two or more. Among them, the ethylene polymer (B) or the propylene polymer (C) is preferable.

Both outer layers may be of the same polymer or of different polymers. For example, one outer layer may be composed of an ethylene polymer (B) and the other outer layer may be composed of a propylene polymer (C).

[0010] The ethylene polymer (B) is as follows:
Ethylene homopolymer (B1) or ethylene / α-olefin copolymer (B) having properties (b-1) to (b-2)
2) is more preferred. Component (B1) or (B2): (b-1) Melt flow rate (MFR): 0.1 to 5
0 g / 10 min (b-2) Density (d): 0.880 to 0.940 g / c
m ³

The density of the ethylene polymer is more preferably 0.890 to 0.935 g / cm ³ , most preferably 0.895 to 0.930 g / cm ³ , and its melt flow rate (MFR). Is more preferably 0.
3 to 20 g / 10 min, more preferably 0.5 to 10 g
/ 10 min, most preferably 0.8 to 5 g / 10 min. The density of the ethylene polymer mentioned here is defined by JIS
It is measured by the method specified in K6760-1981.

In the present invention, the melt flow rate is J
According to the method specified in IS K6760-1981, the load was 2.16 kg, and the measurement temperature was a value measured at 190 ° C. The ethylene / α-olefin copolymer (B2) is a copolymer of ethylene and one or more α-olefins. As the α-olefin, an α-olefin having 3 to 12 carbon atoms is preferable, and specific examples include propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene. -1, dodecene-1,4-methylpentene-1,4-
Methylhexene-1, vinylcyclohexane, vinylcyclohexene, styrene, norbornene, butadiene,
And isoprene. The content of the α-olefin is usually 0.01 to 50% by weight.

The ethylene / α-olefin copolymer comprises:
The above monomers and comonomers can be obtained by a solution polymerization method, a slurry polymerization method, a high pressure ionic polymerization method, and a gas phase polymerization method using a Ziglanatta catalyst or a metallocene catalyst.

The ethylene / α-olefin copolymer is produced by a catalyst using a transition metal compound.
In particular, those produced in the presence of a catalyst using a transition metal compound having a group having a cyclopentadiene-type anion skeleton are preferable. The transition metal compound is a so-called metallocene-based compound and usually has a general formula MLaXn-a (where M is a transition metal atom belonging to Group 4 of the periodic table of elements or a lanthanide series. L is a cyclopentadiene-type anion) A group having a skeleton or a group containing a hetero atom, at least one of which is a group having a cyclopentadiene-type anion skeleton, a plurality of Ls may be cross-linked to each other, and X is a halogen atom, hydrogen or carbon number. A hydrocarbon group of 1 to 20. n represents the valence of a transition metal atom, and a represents
It is an integer such that 0 <a ≦ n. ) And can be used alone or in combination of two or more. Further, the catalyst may comprise, in addition to the metallocene compound, an organoaluminum compound including an alumoxane compound, and / or an ionic compound such as trityl borate and anilinium borate, and / or an inorganic carrier such as SiO ₂ and Al ₂ O ₃ , and ethylene. And a particulate carrier containing an organic polymer carrier such as an olefin polymer such as styrene.

When importance is placed on transparency and flexibility, the ethylene / α-olefin copolymer is produced in the presence of a catalyst using a Ziegler-Natta solid catalyst component. Specifically, in the presence of a catalyst comprising a solid catalyst component containing a transition metal and an organoaluminum compound, usually at 30 to 300 ° C., normal pressure to 3000 kg / cm ² , in the presence or absence of a solvent, Those produced in the solid, liquid-solid or homogeneous liquid phase are preferred. As a manufacturing process at this time, a high-pressure ionic polymerization method is preferable.

The Mw / Mn ratio of the ethylene homopolymer (B1) or ethylene / α-olefin copolymer (B2) preferably used in the present invention, measured by GPC, is preferably 1.8 to 3.5. , More preferably 1.8 to 2.5,
Most preferably, it is 1.8 to 2.2. If the Mw / Mn ratio is too large, the scratching property and the like may decrease.

The propylene polymer (C) includes a propylene homopolymer (C1), a propylene-ethylene random copolymer (C2), a propylene-α-olefin random copolymer (C3), and a propylene block copolymer. Combination (C4) or a mixture thereof is more preferred.

In the propylene-ethylene random copolymer (C2), the content of propylene units is 70 mol%
The propylene-ethylene random copolymer described above is more preferable.

Among the propylene-α-olefin random copolymers (C3), (1) α-olefins having 4 or more carbon atoms
An olefin unit content of 8 to 35 mol%, (2) an ethylene unit content of 5 mol% or less, and (3) a cold xylene-soluble portion (hereinafter also referred to as CXS) of 0.1 to 70% by weight. Certain propylene-α-olefin random copolymers or propylene-ethylene-α-olefin random copolymers are more preferred.

The α-olefin of the propylene-α-olefin random copolymer (C3) used in the present invention includes butene-1, pentene-1, hexene-1,4-
C4 to C10 such as methylpentene-1 and octene-1
Α-olefins, and one or more of these are used. For example, when performing gas phase polymerization,
Butene-1 is preferable because it is difficult to liquefy.

The content of the (1) α-olefin unit having 4 or more carbon atoms in the propylene-α-olefin random copolymer (C3) used in the present invention is more preferably 10%.
２５25 mol%. Propylene-α used in the present invention
-The content of the (2) ethylene unit in the olefin random copolymer (C3) is more preferably 3 mol% or less. The (3) CXS of the propylene-α-olefin random copolymer (C3) used in the present invention is more preferably 1 to 50% by weight.

In addition, a propylene-based block copolymer (C
Among 4), the following propylene-based block copolymers are more preferable. Propylene block copolymer: In the first step, the propylene-ethylene copolymer portion (a component) having an ethylene unit content of 1.5 to 6.0% by weight is fully polymerized (a component and the following b component). (Total) of 40 to 85% by weight, and then in the second step, the content of ethylene unit is 7 to 17%.
% By weight of propylene-ethylene copolymer part (component b)
Is a block copolymer obtained by producing 15 to 60% by weight of the total polymerization amount (the sum of the component a and the component b), and b
The intrinsic viscosity of the component ([η] b) is 2 to 5 dl / g, the intrinsic viscosity of the component b ([η] b) and the intrinsic viscosity of the component a ([η]
a) a propylene-based block copolymer having a ratio ([η] b / [η] a) of 0.5 to 1.8. The propylene-based block copolymer is a propylene-based block copolymer in the first step. A copolymer obtained by sequentially polymerizing an ethylene copolymer portion (a component) and a propylene-ethylene copolymer portion (b component) having a different ethylene unit content in the second step, It is not a typical block copolymer in which one terminal of a copolymer and another terminal of a copolymer are connected by a bond, but a kind of a blend-type copolymer. The propylene-based block copolymer is also called an impact-resistant propylene copolymer.

Particularly, when the content of the ethylene unit in the component a is 2.5 to 4.5% by weight, it is preferable from the viewpoint of the balance between flexibility and heat resistance. In particular, when the content of the ethylene unit in the component b is 8 to 15% by weight, it is preferable from the viewpoint of the balance between the impact resistance at low temperatures and the transparency.

The ethylene unit content is measured by a ¹³ C-NMR method according to the method described on page 616 of a polymer handbook (1995, published by Kinokuniya Bookstore). The content (Ea) of the ethylene unit of the component a is analyzed by sampling the copolymer after the completion of the polymerization in the first step. The content (Eb) of the ethylene unit of the component b is determined by sampling the block copolymer after completion of the polymerization in the second step, and measuring the ethylene unit content (Ea) of the block copolymer.
b) is analyzed, and it is determined from the following equation from the ratio of the component a (Pa) and the ratio of the component b (Pb). Ea × Pa / 100 + Eb × Pb / 100 = Eab Eb = (Eab−Ea × Pa / 100) × 100 / Pb

The proportion of the propylene-ethylene copolymer part (component a) produced in the first step and the propylene-ethylene copolymer part (component b) produced in the second step is such that the component a is 40 to 85% by weight. , Preferably 55-83% by weight, b
15-60% by weight of the component, preferably 17-45% by weight
It is.

In order to obtain a propylene-ethylene block copolymer having a component b of 17 to 45% by weight, it is possible to prepare a block copolymer having a component b of 17 to 45% by weight in the polymerization step. For example, it is also possible to produce a block copolymer having a proportion of the component b of 27 to 60% by weight by polymerization, and to adjust the proportion of the component b by adding only the component a during melt-kneading. The intrinsic viscosity ([η] b) of the component b of the propylene block copolymer used in the present invention is 2
５5 dl / g, the ratio ([η] b / [η] a) between the intrinsic viscosity ([η] b) of the component b and the intrinsic viscosity ([η] a) of the component a
Is required to be 0.5 to 1.8 from the viewpoint of transparency. In particular, when the intrinsic viscosity ([η] b) of the component b of the propylene-ethylene copolymer is 2.5 to 4.0 dl / g, it is more preferable from the viewpoint of the balance between the suppression of low molecular weight components and the processability. .

In particular, when the [η] b / [η] a ratio is 0.8 to
When it is 1.5, it is more preferable from the viewpoint of transparency.

The intrinsic viscosity is measured using a Ubbelohde viscometer at 135 ° C. in tetralin. The intrinsic viscosity ([η] a) of the component a is analyzed by sampling the copolymer after the completion of the polymerization of the component a in the first step. The intrinsic viscosity ([η] b) of the component b is determined by sampling the block copolymer after completion of the polymerization in the second step, analyzing the intrinsic viscosity ([η] ab) of the block copolymer, and further calculating the ratio of the component a. (P
It is determined from the following formula from the ratio (Pb) of the components a) and b. [Η] a × Pa / 100 + [η] a × Pa / 100 =
[Η] ab [η] b = ([η] ab- [η] a × Pa / 100) ×
100 / Pb

The weight average molecular weight of the xylene-soluble component at 20 ° C. in the propylene block copolymer used in the present invention is 260.
The content of the component of not more than 00 is not more than 6% by weight.
-It is preferable in terms of suppressing the amount of extraction with hexane or the like.
In particular, when used as a food packaging material, the weight-average molecular weight of 2600 °
More preferably, the content of the component of 0 or less is 3.5% by weight or less.

The propylene-based block copolymer used in the present invention has a content of ethylene unit of component b (Eb) and a content of ethylene unit of component a (Ea) from the viewpoint of transparency and impact resistance at low temperature. (Eb-Ea) is preferably in the range of 3 to 15% by weight, and (Eb-Ea) is 5 to 10 from the viewpoint of balance between transparency and impact resistance at low temperatures.
% By weight is particularly preferred.

The propylene polymer (C) used in the present invention
Is a so-called Ziegler-Natta catalyst, which is a catalyst for stereoregular polymerization of an α-olefin known as a catalyst system, that is, a transition metal compound belonging to Groups IV to VIII of the periodic table and a typical metal belonging to Groups I to II of the periodic table. And an organic compound, preferably a third component of an electron donating compound, and the polymerization method may be any method such as a solvent polymerization method in which polymerization is performed in a solvent or a gas phase polymerization method in which polymerization is performed in a gas phase. Can be manufactured by For example, it can be obtained by the production methods described in JP-A-63-19255 (Example 1), JP-A-60-76515 and the like. The propylene-based block copolymer (C4) used in the present invention can be prepared in the same polymerization vessel in the presence of, for example, a Ziegler-Natta type catalyst.
After polymerization of the components, it can be produced by a batch polymerization method in which the b component is subsequently polymerized, or a continuous polymerization method in which the a component and the b component are continuously polymerized using a polymerization tank comprising at least two tanks. is there.

Specifically, for example, in the presence of (x) an organosilicon compound having a Si—O bond, a compound of the general formula Ti (OR
¹ ) A titanium compound and / or an ether compound represented by _n X _4-n (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and n is a number satisfying 0 <n ≦ 4). A trivalent titanium compound-containing solid catalyst component obtained by treating a solid product obtained by reducing with an organomagnesium compound with a mixture of an ester compound and an ether compound with titanium tetrachloride, (y) an organoaluminum compound (z) Si-oR ² bonds (R ² is a hydrocarbon group having 1 to 20 carbon atoms.) the catalyst system consisting of a silicon compound having, or (x) the general formula Ti (oR ¹⁾ _n X _{4- n} (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, n is a number satisfying 0 <n ≦ 4), and a titanium compound represented by the general formula AlR ² _m Y _3-m (R ² is a hydrocarbon group having 1 to 20 carbon atoms, Y is And a solid product containing a hydrocarbyloxy group insoluble in a hydrocarbon solvent obtained by reduction with an organoaluminum compound represented by the following formula: After polymerization treatment, a hydrocarbyloxy group-containing solid catalyst component obtained by treating in a slurry state at a temperature of 80 to 100 ° C. in the presence of an ether compound and titanium tetrachloride in a hydrocarbon solvent, (y) an organoaluminum compound In the presence of a Ziegler-Natta type catalyst having at least titanium, magnesium and halogen as essential components such as a catalyst system comprising a catalyst system, the molar ratio of Al atoms in component (y) / Ti atoms in component (x) is 1 to 2000, preferably 5 to 1500,
The molar ratio of Al atoms in component (z) / component (y) is set to 0.0
The polymerization temperature is 20 to 150 ° C, preferably 50 to 95 ° C.
° C., the polymerization pressure is atmospheric pressure ~40kg / cm ² G, preferably under conditions of 2~40kg / cm ² G, and supplies the hydrogen to propylene and ethylene and the molecular weight regulator in the first step propylene - ethylene copolymer After the production of the polymer part (component a), propylene, ethylene and hydrogen are supplied in the second step to produce the propylene-ethylene copolymer part (component b).

The propylene polymer (C) used in the present invention
Is in the presence of an organic peroxide, in the absence of a known method,
For example, it is possible to change the fluidity represented by the melt flow rate.

The propylene polymer (C) is used by blending an ethylene resin, an amorphous polyolefin, a petroleum resin or a hydrogenated product thereof, or a recycled product thereof, as long as the effects of the present invention are not impaired. be able to.
Examples of the ethylene-based resin include polyethylene and a copolymer of ethylene and an α-olefin having 4 or more carbon atoms.

Examples of the amorphous polyolefin include amorphous polypropylene and polybutene-1 or copolymers of propylene and butene-1 with other α-olefins, and include propylene and / or butene-1. An amorphous olefin polymer having a ratio of 50% by weight or more is preferred.

These amorphous polyolefins are boiled n-
Heptane insoluble content, that is, Soxhlet extracted insoluble content with boiling n-heptane is 70% by weight or less, preferably 6% by weight.
Those having 0% by weight or less are preferred. Amorphous polyolefins can be used alone or in combination of two or more.

Specific examples of the amorphous polyolefin include polypropylene and polybutene having predetermined characteristics such as the above-mentioned propylene component and / or butene-1 component content.
1, propylene-ethylene copolymer, butene-1-ethylene copolymer, propylene-butene-1 copolymer, propylene-butene-1-ethylene-3 terpolymer, propylene-hexene-1-ethylene-3 And amorphous polyolefins such as butene-1-hexene-1-ethylene-3-terpolymer. For example, Ube Tack UT2385 and UT2780 manufactured by Ube Lexen Co., Ltd. can be used.

[0038] Oil and resin or a hydrogenated product thereof, a thermoplastic resin polymerized to solidify the cracked oil fraction produced by pyrolysis of petroleum, aliphatic a C ₅ fraction as a raw material, Examples thereof include an aromatic system using a C ₉ fraction as a raw material, a copolymer system of both, a dicyclopentadiene system, and a hydrogenated system obtained by hydrogenating these. Specifically, for example, commercially available products such as Heylets and Petrozine manufactured by Mitsui Petrochemical Industries, Ltd., and Alcon manufactured by Arakawa Chemical Industries, Ltd. can be used.

Among these petroleum resins or hydrogenated products thereof, hydrogenated systems are superior in color tone and odor.

In the present invention, a method for preparing a mixture of the propylene polymer (C) constituting at least one layer of the outer layer and the above-mentioned resin is not particularly limited, and known methods such as a kneader and a Banbury can be used. Heat melting and kneading can be performed by using a kneader such as a mixer or a roll, a single-screw or twin-screw extruder, or the like. Further, various resin pellets may be dry-blended.

The intermediate layer and the outer layers of the present invention may further contain various resins, if necessary, as long as the effects of the present invention are not impaired. For example, a high-density polyethylene can be used to improve rigidity, and an olefin-based resin such as a low-density elastomer can be used alone or in combination of two or more to improve impact strength.

In order to further improve the physical properties of the intermediate layer and both outer layers of the present invention, 2,6-di-t-butyl-
p-cresol (BHT), tetrakis [methylene-3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (IRGANOX 101
0) and n-octadecyl-3- (4'-hydroxy-
A phenolic stabilizer represented by 3,5′-di-t-butylphenyl) propionate (IRGANOX 1076); bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tris (2,2)
Phosphite-based stabilizers represented by 4-di-t-butylphenyl) phosphite and the like; lubricants represented by higher fatty acid amides and higher fatty acid esters; glycerin esters and sorbitanates of fatty acids having 8 to 22 carbon atoms; An antistatic agent such as polyethylene glycol ester; a processability improver represented by a fatty acid metal salt such as calcium stearate; an antiblocking agent represented by silica, calcium carbonate, talc and the like are added. Among these, the addition of a lubricant and a stabilizer has a preferable effect.

If necessary, an inorganic filler may be further added to the intermediate layer and both outer layers of the laminate as long as the effects of the present invention are not impaired. Examples of the inorganic filler include a spherical filler, a plate-like filler, and a fibrous filler. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, perlite, shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, and amorphous zeolite. Examples of the plate-like filler include talc and mica, and examples of the fibrous filler include needle-like fillers such as wollastonite, and fibrous fillers such as magnesium oxysulfate, potassium titanate fiber, and fibrous calcium carbonate. Stuff,
Further, a completely fibrous material such as glass fiber may be used. Further, it is preferable to add 0.1 to 10% by weight of carbon black for the purpose of improving weather resistance.

The resin components such as high-density polyethylene and low-density elastomer and additives such as antioxidants, anti-blocking agents, lubricants, and processability improvers, which are blended according to various purposes, are melt-kneaded in advance. It may be subjected to film processing, may be individually dry-blended or made into one or more master batches, and may be subjected to film processing after dry-blending, and any method may be used.

The laminate constituting the olefin resin waterproof sheet of the present invention is such that the thickness ratio of the intermediate layer to the total thickness of both outer layers is 1 to 50, more preferably 0.5 to 50. -20, more preferably 1-5. The thickness can be measured by observing the cross section of the laminate with a microscope. If the ratio is too small, the flexibility may be poor, and if it is too large, the heat resistance may be poor. Further, the total thickness of the laminate is preferably 0.05 to 10 mm, more preferably 0.1 to 5 mm. If the thickness is too small, the strength may be poor, and if it is too large, the flexibility may be poor.

The laminate constituting the waterproof sheet made of an olefin resin of the present invention can be colored as required. In this case, all layers can be colored,
It is also possible to color only a specific layer, for example, only an intermediate layer.

Further, the present invention may be a waterproof sheet obtained by laminating at least one layer selected from a nonwoven fabric layer, an adhesive layer and a foam layer on at least one surface of the laminate.

In order to produce a laminate of the olefin-based resin waterproof sheet of the present invention as a raw material, a co-extrusion method or an extrusion coating method (in general, using an inflation film production apparatus or a T-die film production apparatus). A technique such as an extrusion lamination method can be employed. In addition, using the multilayer or single-layer film obtained by using these apparatuses, a desired multilayer film is manufactured by a known technique such as a lamination method such as a dry lamination method, a wet lamination method, a sand lamination method, and a hot melt lamination method. It is also possible.

[0049]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. The evaluation method was performed as follows. (1) Density (d) According to the method specified in JIS K6760. (2) Melt flow rate (MFR) The propylene-based polymer was measured according to JIS K7210 under the condition-14. Further, the ethylene-based polymer is heated at a temperature of 190 according to the method specified in JIS K6760.
C. was performed. (3) Molecular weight distribution (Mw / Mn) of ethylene polymer GPC (Gel Permeation Chroma)
(Tography) measurement was performed by Waters 150
Using a C-type GPC measuring device, GM made by Tosoh
H6-HT, using o-dichlorobenzene as the solvent, 14
It was measured at 5 ° C. The calibration curve was prepared by a standard method using standard polystyrene manufactured by Tosoh Corporation. Molecular weight distribution (Q value)
Was calculated as the ratio of weight average molecular weight / number average molecular weight. (4) Content of Vinyl Acetate Unit A press sheet was prepared, and the absorbance of the characteristic absorption in the infrared absorption spectrum was corrected for the thickness and determined by a calibration curve method. As the characteristic absorption, a peak at 609 cm ⁻¹ for vinyl acetate was used. (5) Heat-fusing property during construction (high-frequency seal test) A high-frequency welder Y made by Yamamoto Vinita was manufactured.
Sealing was performed using D2700T. The bonding conditions were as follows: air pressure: 2 kg / cm ² G, welding delay: 3 seconds, welding time: 4
Seconds, cooling time: 2 seconds, voltage: 5500 V, tuning adjustment: 5. The seal bar size was 10 mm x 150 mm. The film after bonding is cut to a width of 10 mm in the MD direction, and one end of the bonded portion of the test piece is peeled in advance,
Both were attached to the grips of a tensile tester. The test piece was pulled at both ends of the peeling at a rate of 100 mm / min with a tensile tester, and the strength when T peeling was performed was determined.

(6) Transparency All hazes were measured according to JIS K7105-1981. (7) Scratch test Using a shake tester TAITEC's RECIPRO SHAKER R-10,
Prepared film and fine particle silica in polyethylene
It was rubbed with a film containing 000 ppm for 1 minute. The rubbing speed was a shaking speed of 120 reciprocations / minute and a shaking width of 40 mm. The difference in haze before and after the rubbing test was measured, and the result was evaluated as scratching. Haze is JIS K
All hazes were measured according to 7105-1981. (8) Blocking resistance The films are superposed on each other, a load of 7 kg / 220 cm ² is applied, the film is promoted to adhere at 23 ° C. for 18 hours, and then left in an atmosphere at 23 ° C. and 50% humidity for 30 minutes or more. did. The load (g / 100 cm ² ) required for peeling the sample was measured using a blocking tester manufactured by Shimadzu Corporation at a peeling load rate of 20 g / min. (9) Flexibility (1% SM; 1% secant modulus; 1% Se
can Modulus) A 2 cm wide sample piece was cut out in the processing direction (MD) of the film and attached to a tensile tester at a distance between chucks of 6 cm and 5 m
It is pulled at a speed of 1 m / min.
It was calculated by the formula of 0 × (stress) / (cross-sectional area) [kg / cm ² ]. The smaller the value, the better the flexibility. (10) Chemical resistance The film is cut, heat-sealed, width 3 cm, length 1
A 0 cm bag was made. The bag was placed in humidified xylene for 1 minute and 30 seconds. The opening went out of the xylene to prevent the xylene from directly entering the bag. The amount of xylene was 200 cc, the vessel used a 500 cc stainless steel beaker, and the temperature of xylene was kept at 45 ° C. A weight was placed inside the bag so that the bag did not float. After the test, the bag was taken out, the surface was wiped off, the state of the bag was observed, and the weight was measured.

Example 1 Ethylene-vinyl acetate copolymer (EVA: Evatate K2010, manufactured by Sumitomo Chemical Co., Ltd., MFR = 3 g / 1) as an ethylene-ethylenically unsaturated ester copolymer (I)
Ethylene-hexene-1 produced with a metallocene catalyst as an ethylene / α-olefin copolymer (B2) in an intermediate layer containing 0 minutes and a vinyl acetate unit content of 25% by weight).
Copolymer (PE-1: Sumikasen E FV401 manufactured by Sumitomo Chemical Co., Ltd., density 0.902 g / cm ³ , MFR
Using 4.1 g / 10 min, Mw / Mn 2.1) as both outer layers, two types and three layers of waterproof sheets were produced. The sheet was produced by a coextrusion method using three 30 mmφ extruders.
The thickness ratio of each layer is 15 μm / 70 μm / 15 μm, and the thickness ratio of the intermediate layer is 2.
It was 3. Table 1 shows the evaluation results of this sheet.

Example 2 An ethylene-hexene-1 copolymer (PE-2: Sumikasen Hiα CW2004 manufactured by Sumitomo Chemical Co., Ltd.) produced in Example 1 as an ethylene / α-olefin copolymer (B2) using a solid catalyst. Density 0.909 g / cm ³ ,
The same method as in Example 1 was repeated except that MFR 2.1 g / 10 min and Mw / Mn 2.3) were used as both outer layers. Table 1 shows the results.

Example 3 Ethylene-hexene-1 copolymer (PE-3: Sumikasen α FZ201 manufactured by Sumitomo Chemical Co., Ltd.) produced in Example 1 as an ethylene / α-olefin copolymer (B2) using a solid catalyst. −0 density 0.911 g / cm ³ , M
The same method as in Example 1 was repeated except that FR (2.0 g / 10 min, Mw / Mn 3.2) was used as both outer layers. Table 1 shows the results.

Comparative Examples 1 to 4 The same method as that of Example 1 except that a single-layer waterproof sheet was prepared using the same resin as used in Examples 1 to 3 and the resin shown in Table 1. Was repeated. Table 1 shows the results.

[0055]

[Table 1]

[0056]

As described above in detail, according to the present invention, as compared with a conventionally known waterproof sheet, scratch resistance, flexibility, blocking resistance, oil resistance, chemical resistance, and heat melting property. An olefin resin waterproof sheet having an excellent balance of adhesion can be provided. The waterproof sheet made of an olefin-based resin of the present invention is excellent in heat sealability, especially high-frequency sealability, so that it can be constructed with simple equipment.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2D018 DA03 4F100 AK03A AK03B AK03C AK04A AK04B AK07A AK07B AK07J AK44C AK44J AK62A AK62B AK63C AK64A AK64B AK66A AK66B BAE BADBA02A02 BA03 BA02A01 BA02 BA03A02A02 JB01 JB20 JK07 JK12 JK13 JL12 JL13D YY00A YY00B 4J002 BB031 BB051 BB071 BB121 BB141 BB151 BB161 BP021 GF00

Claims (10)

[Claims] An olefin resin waterproof sheet comprising a laminate comprising at least both outer layers and an intermediate layer, wherein the intermediate layer of the laminate has an ethylene-ethylenically unsaturated ester copolymer (I). Wherein both outer layers of the laminate are layers composed of an olefin resin (II) (excluding the ethylene-ethylenically unsaturated ester copolymer (I)), and the thickness ratio thereof is A waterproof sheet made of an olefin-based resin, comprising a laminate in which the thickness of the intermediate layer is 0.2 to 50 with respect to the total thickness of the outer layer of 1. 2. The olefin resin waterproof sheet according to claim 1, wherein the olefin resin (II) in both outer layers is an ethylene polymer (B) or a propylene polymer (C). 3. An ethylene polymer (B) comprising the following (b-1):
Ethylene homopolymer (B1) having the properties of (b-2)
The waterproof sheet made of a polyolefin resin according to claim 2, which is an ethylene / α-olefin copolymer (B2). Component (B1) or (B2): (b-1) Melt flow rate (MFR): 0.1 to 5
0 g / 10 min (b-2) Density (d): 0.880 to 0.940 g / c
m ³ 4. The olefin according to claim 3, wherein the Mw / Mn ratio of the ethylene homopolymer (B1) or the ethylene / α-olefin copolymer (B2) measured by GPC is 1.8 to 3.5. Waterproof sheet made of resin. 5. An ethylene / α-olefin copolymer (B)
The olefin resin waterproof sheet according to claim 3, wherein 2) is produced in the presence of a polymerization catalyst using a transition metal compound having a group having a cyclopentadiene-type anion skeleton. 6. An ethylene / α-olefin copolymer (B)
5. The olefin resin waterproof sheet according to claim 3, wherein 2) is produced in the presence of a Ziegler-Natta solid catalyst. 7. The propylene-based polymer (C) is a propylene homopolymer (C1), a propylene-ethylene random copolymer (C2), a propylene-α-olefin-based random copolymer (C3), a propylene-based block. The olefin resin waterproof sheet according to claim 2, which is a copolymer (C4) or a mixture thereof. 8. The propylene-α-olefin random copolymer (C3) has (1) a content of α-olefin units having 4 or more carbon atoms of 8 to 35 mol%, and (2) a content of ethylene units. Is 5 mol% or less, and (3) the propylene-α-olefin random copolymer or propylene-ethylene-α- has a cold xylene-soluble portion of 0.1 to 70% by weight.
The olefin resin waterproof sheet according to claim 7, which is an olefin random copolymer. 9. The olefin resin waterproof sheet according to claim 7, wherein the propylene-based block copolymer (C4) is the following propylene-based block copolymer. Propylene block copolymer: In the first step, the propylene-ethylene copolymer portion (a component) having an ethylene unit content of 1.5 to 6.0% by weight is fully polymerized (a component and the following b component). Propylene-ethylene copolymer part (b component) having an ethylene unit content of 7 to 17% by weight in the second step.
A block copolymer obtained by forming 15 to 60% by weight of the sum of the component and the component b), wherein the intrinsic viscosity ([η] b) of the component b is 2 to 5 dl / g, and the intrinsic viscosity of the component b A propylene-based block copolymer having a ratio ([η] b / [η] a) of ([η] b) to the intrinsic viscosity ([η] a) of the component a is 0.5 to 1.8. 10. A waterproof sheet comprising at least one layer selected from a non-woven fabric layer, an adhesive layer and a foam layer on at least one surface of the laminate according to claim 1.