JP2000334901A - Olefinic waterproof sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic waterproof sheet good in the mutual bonding of sheets and capable of being fixed to a substrate by an adhesive. SOLUTION: In a waterproof sheet with a bending modulus of elasticity of 250-3,000 kgf/cm2 comprising an olefinic resin, a rear surface layer comprises a compsn. prepared by adding 0-300 pts.wt. of a filler to 50-95 pts.wt. of an olefinic resin and 50-5 pts.wt. of a non-halogen polar polymer. The olefinic resin of upper and rear surface layers is an olefinic thermoplastic elastomer obtained by a reactor method and the non-halogen polar polymer of the rear surface layer contains one or more kinds of a polymers selected from an ethylene/vinyl acetate copolymer resin with a vinyl acetate content of 50 wt.% or more, a carboxylic acid-containing ethylene copolymer resin, a maleic acid- containing ethylene copolymer resin and a styrenic thermoplastic elastomer with a styrene content of 20% or more. A base material is provided between both layers or laminated to the lowermost layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof sheet for buildings such as buildings and houses, and more particularly to an olefin-based waterproof sheet which is excellent in an adhesive method.

[0002]

2. Description of the Related Art Conventionally, asphalt has been used for the purpose of preventing rainwater from entering the roof of a building, the roof of a house, a veranda, and the like. However, the construction is complicated and the workability is inferior. And the asphalt itself is inferior in base followability.

[0003] Waterproof sheets such as vulcanized rubber sheets and polyvinyl chloride sheets have been used to compensate for the disadvantages of asphalt. These waterproof sheets are generally made of a long object having a predetermined width, and when these sheets are joined to each other, they exhibit a waterproof function and need to be fixed to a base to withstand wind pressure. In addition, the rising portion of the corner must be waterproof.

[0004]

In the case of the above vulcanized rubber sheets, it is necessary to use an adhesive to bond the rubber sheets, and it takes a long time to perform the bonding, and the bonding between the sheets due to uneven application of the adhesive. There is a drawback that there are many water leakage accidents from the department.

On the other hand, in the case of a polyvinyl chloride sheet, the sheets can be joined to each other by heat fusion or solvent welding, and the base and the corners can be fixed with an adhesive.
Although watertightness is high in stability, a plasticizer is added to obtain flexibility, and there is a problem that physical properties change due to volatilization of the plasticizer over a long period of time, resulting in poor long-term stability.

In recent years, a waterproof sheet made of an olefin material has been proposed. Although the waterproof sheet made of this olefin-based material can be joined by heat fusion, it is difficult to fix it to the base with an adhesive, and it is necessary to fix it mechanically. For this reason, there is a disadvantage that reliability is poor in that when water leaks due to a defect such as a hole or the like, it spreads over the whole. There is also a problem with the watertightness of the rising portion of the corner.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an olefin-based waterproof sheet which has good bonding between sheets and can be fixed to a substrate and an adhesive. The physical properties referred to in the present invention are mechanical properties such as tensile strength, elongation, tear strength, scratch resistance and abrasion resistance, and general performance such as flexibility and cold resistance.

[0008]

SUMMARY OF THE INVENTION The present invention provides a waterproof sheet in which a front layer and a back layer made of an olefin resin having a flexural modulus of 250 to 3000 kgf / cm ² are laminated. By comprising the polar polymer of halogen, an olefin-based waterproof sheet having good adhesiveness between sheets and excellent adhesiveness can be obtained.

In the first aspect, the flexural modulus is 250 to 30.
In a waterproof sheet made of an olefin-based resin of 00 kgf / cm ² , the preferred composition ratio of the olefin-based resin in the back layer and the non-halogen polar polymer is 50%.
To 95 parts by weight and 50 to 5 parts by weight of a non-halogen polar polymer. A stable bonding property and good adhesiveness can be obtained by using the filler in a total amount of 0 to 300 parts by weight with respect to 100 parts by weight. be able to.

According to the second aspect of the present invention, an olefin-based thermoplastic elastomer obtained by a reactor method is used as the olefin-based resin for the front layer and the back layer, whereby an olefin-based waterproof sheet excellent in physical properties and weather resistance can be obtained.

Claim 3 shows a preferred non-halogen polar polymer in the back layer, wherein the non-halogen polar polymer is an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 50% by weight or more, and a carboxylic acid-containing ethylene copolymer. By containing one or more selected from the group consisting of a resin, a maleic acid-containing ethylene copolymer resin, and a styrene-based thermoplastic elastomer having a styrene content of 20% or more, stable bonding and adhesion can be obtained.

According to a fourth aspect, an interlayer between the front surface layer and the back surface layer,
Alternatively, dimensional stability and heat insulation can be improved by laminating the base material between the surface layers, the back layer, or the lowermost layer.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described. The olefin-based waterproof sheet of the present invention is made of an olefin-based resin having a flexural modulus of 250 to 3000 kgf / cm ² , and the back layer is made of an olefin-based resin and a non-halogen polar polymer.

The olefin resin of the surface layer and the back layer is
A single polymer having a flexural modulus of 250 to 3000 kgf / cm ² or a mixture of two or more resins may be used to make the above range.

Examples of the olefin resin include polyethylene, polypropylene, polybutene-1, a copolymer resin of ethylene and an α-olefin having 3 or more carbon atoms, a copolymer resin of propylene and an α-olefin having 3 or more carbon atoms, Propylene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-vinyl acetate copolymer resin, ethylene-acrylate copolymer resin,
Ethylene-methacrylic acid copolymer resin, olefin-based thermoplastic elastomer, amorphous α-olefin resin and the like. Paraffin oil for the purpose of softening these resins,
It is also possible to add a plasticizer such as mineral oil. Also,
For the purpose of improving physical properties and workability, a partially cross-linked material may be used.

Among the above olefin resins, olefin thermoplastic elastomers obtained by a reactor method are particularly preferred. The olefin-based thermoplastic elastomer obtained by this reactor method has a high concentration of a rubber component uniformly dispersed therein and has excellent physical properties, and also has excellent long-term durability due to the absence of volatile substances.

Examples of the non-halogen polar polymer to be added to the back layer include ethylene vinyl acetate copolymer resins having a vinyl acetate content of 50% by weight or more, carboxylic acid-containing ethylene copolymer resins, maleic acid-containing ethylene copolymer resins, Styrene thermoplastic elastomer, thermoplastic polyurethane, ionomer, polyester, polyamide, ethylene vinyl alcohol resin, polymethacrylic ester, acrylic rubber, acrylonitrile rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber having a styrene content of 20% by weight or more , Hydrogenated acrylonitrile-
Butadiene rubber and the like.

Among the above non-halogen polar polymers,
Ethylene vinyl acetate copolymer resin having a vinyl acetate content of 50 to 90% by weight, ethylene copolymer resin having a carboxylic acid content of 1 to 20% by weight, maleic acid content of 1 to 20% by weight
Ethylene copolymer resin, and a styrene-based thermoplastic elastomer having a styrene content of 20 to 70% by weight are preferable in view of bonding strength. The carboxylic acid-containing polymer and the maleic acid-containing polymer may be those obtained at the polymerization stage, those modified by grafting or the like, and may be used as terpolymers of monomers other than ethylene.

The ratio of the olefin resin and the non-halogen polar polymer in the back layer is 50 to 50%.
Non-halogen polar polymer 50 to 5 to 95 parts by weight
Parts by weight. If the amount of the non-halogen polar polymer is less than 5 parts by weight, sufficient adhesiveness cannot be obtained, and if it exceeds 50 parts by weight, the bonding strength is reduced.

As the filler, calcium carbonate, talc, mica, clay, mica, aluminum hydroxide, magnesium hydroxide, zinc borate, barium sulfate and the like can be used. These particles preferably have a particle size of about 0.3 to 10 μm, and those having been subjected to various surface treatments such as an organic acid, a coupling agent, and a titanium coating can also be used. The addition of a filler improves the adhesiveness. 50 to 95 parts by weight of the olefin resin and a non-halogen polar polymer 50
The amount of the filler to be added is preferably 0 to 300 parts by weight, particularly preferably 30 to 150 parts by weight, based on 100 parts by weight in total of 5 to 5 parts by weight.

The olefin-based waterproofing sheet of the present invention can be used as a laminate between a surface layer and a back surface layer, or between a surface layer and a back layer, or on the lowermost layer, that is, on the back surface of the back layer, or on both the interlayer and the lowermost layer. By laminating the base material, dimensional stability and heat insulation are improved. In order to improve the dimensional stability in this way, it is preferable to laminate the base material between the layers, the lowermost layer, or both, but it is more preferable to laminate the layers from the viewpoint of joining the sheets. As the base material, woven fabric, nonwoven fabric, paper, synthetic resin sheet, metal foil, organic or inorganic porous material, or the like is used.

When the substrate is a woven or non-woven fabric, synthetic fibers,
Natural fibers, glass fibers and the like are used, and a blend of these can also be used. The material of the synthetic fiber includes polyolefin, polyester, polyamide, acrylic resin and the like, and a blend of these is also used.

In the case of a woven fabric, the distance between the warp and the weft is set to 3 by a plain weave, a twill weave, a leno weave, or a method of orthogonally solidifying the fibers with an adhesive using a yarn having a thickness of 100 to 2000 denier. Preferably woven to about 20 / inch. In the case of a non-woven fabric, it is preferable to use a non-woven fabric of a dry type, a wet type, a spun bond type or the like, with a basis weight of about ²⁰ to 200 g / m ² .

In order to improve the heat insulating property and the flatness after construction without being affected by the unevenness of the base, it is preferable to laminate an organic or inorganic porous material or a nonwoven fabric on the lowermost layer. Among porous bodies, an organic porous body (foam) is preferable. The foam is
Those having an expansion ratio of about 2 to 50 times and made of polyolefin, polystyrene, polyamide, acrylic resin and the like are preferable. As the inorganic porous material, a material obtained by forming glass wool, rock wool, or the like into a sheet is used. The thickness of the porous body is preferably about 1 to 50 mm.
The nonwoven fabric is made of polyolefin, polyester, polyamide, acrylic resin, or the like, and has a basis weight of 100 to
Those with 500 g / m ² are preferred.

The olefin-based waterproof sheet of the present invention has improved weather resistance by adding a light stabilizer, an ultraviolet absorber, an ultraviolet shielding agent, a pigment and the like. As a light stabilizer,
Hindered amines are generally used and have a molecular weight of 200-4.
000 can be used alone or in combination of two or more. The addition amount is usually about 500 to 5000 ppm. UV absorbers include benzotriazoles, benzophenones, salicylates and the like.
It is common to add about 0 to 7000 ppm. As the ultraviolet shielding agent, a metal oxide or the like is used, and zinc oxide as fine particles is generally added in an amount of about 100 to 2000 ppm. Pigments differ depending on the color to be colored, titanium oxide,
Carbon, red iron, cyanine green, cyanine blue, titanium yellow and the like are used. These light stabilizers, ultraviolet absorbers, ultraviolet shielding materials, pigments and the like are preferably used alone or in combination of plural formulations to improve weather resistance.

In the waterproof sheet of the present invention, various additives can be used for improving processability and function. For example,
Antioxidants, lubricants, antistatic agents, flame retardants and the like.

The waterproof sheet of the present invention comprises a front surface layer, a back surface layer, and a base material layer, and each layer may be a single layer or two or more layers. Therefore, when the front surface layer and the back surface layer are multiple layers, a substrate may be laminated between the layers. Further, the resin layers of the front surface layer and the back surface layer may be the same composition or different compositions. The combination of the surface layer being an olefin-based thermoplastic elastomer composition, the intermediate base layer being a woven fabric, and the back layer being a composition comprising an olefin-based thermoplastic elastomer and a non-halogen polar polymer is preferred. It is.

In order to improve the adhesion between the back layer and the base,
Various treatments such as corona treatment, electron beam treatment, and plasma treatment for the back surface of the back surface layer, and acrylic, styrene, acrylic styrene, vinyl acetate, ethylene vinyl acetate,
Various primers of urethane type, epoxy type, styrene butadiene type and polyester type can be applied.

On the surface of the surface layer, sheets or films of fluororesin type, acrylic resin type, polycarbonate type, polyester type, nylon type and polyolefin type can be laminated. By laminating these sheets and films, dirt prevention, abrasion resistance and weather resistance can be improved.

The thickness of the waterproof sheet of the present invention is preferably in the range of 0.3 to 3.0 mm, more preferably in the range of 1.0 to 2.0 mm, from the viewpoint of flexibility and physical properties.

The waterproof sheet of the present invention can be processed by known equipment, and can be formed by, for example, a calender, an extruder, or a laminator.

[0032]

EXAMPLES Next, the present invention will be described specifically with reference to examples and comparative examples, but the present invention is not particularly limited by these examples.

Examples 1 to 17 The surface layer composed of No. 1 to 7 shown in Table 1 and the back layer composed of No. 8 to 18 shown in Table 2 were combined with
Each was formed into a 0.75 mm sheet using four inverted L-shaped calendars at 200 ° C. Combinations shown in Table 4 were laminated on each of the obtained surface layer sheet and back layer sheet using a laminator to obtain a sheet having a thickness of 1.5 mm and a width of 1200 mm.

Examples 18 to 34 Except that the surface layer and the back layer shown in Tables 1 and 2 were combined as shown in Table 5, and a glass cloth base material (KS-5221 manufactured by Kanebo Co., Ltd.) was laminated between them. This is the same as Examples 1 to 17.

Examples 35 to 41 Similarly, a glass cloth base material (S-520 manufactured by Kanebo Co., Ltd.) was provided between the surface layer No. 1 in Table 1 and the back layer No. 8 in Table 2.
7) was laminated, and various foams (foaming ratio: 10 times, thickness: 3 mm) shown in Table 6 were further laminated on the lowermost layer (the back surface of the back surface layer). However, the width for laminating the foam was 1150 mm, and the 50 mm side of the sheet was a portion to be heat-sealed, and the foam was not laminated on that portion.

Examples 42 to 48 Similarly, a polyester cloth base material (E220 manufactured by Kurabo Industries) was provided between the surface layer No. 1 in Table 1 and the back layer No. 8 in Table 2.
0) was laminated, and various primers shown in Table 7 were applied to the back surface of the back surface layer by a gravure coater at 20 g / m ^2, and the same as in Example 1. However, the width for applying the primer was 1150 mm, 50 mm on one side of the sheet was a portion to be heat-sealed, and no primer was applied to that portion.

Comparative Examples 1 to 6 The same procedures as in Example 1 were carried out, except that the surface layer of No. 1 in Table 1 and the back layers composed of Nos. 19 to 24 shown in Table 3 were laminated.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

The components used in the examples and comparative examples are as follows, and all the blending parts are parts by weight. TPO-1: Montell JPO Co. Ltd. Flexural modulus 860Kgf / cm ^{2 TPO-2} :( Ltd.) manufactured by Tokuyama flexural modulus 800Kgf / cm ² TPO-3: manufactured by Mitsui Chemicals Inc. flexural modulus 900 kgf / cm ² TPO-4: Chisso Corp. Flexural modulus of elasticity 4800 Kgf / cm ² LLDPE: Dow Chemical Corp. Density 0.860 g / cm ³ EVA: Tosoh Corp. VA content 20% EEA: JPO Corp. EA content 20% PP: JPO Co. density 0.90g / cm ³ EVA-1: Dainippon ink Co. VA content 70% EVA-2: Nippon synthetic chemical Industry Co., Ltd. VA content 55% POL-1: Ethylene acrylate maleic anhydride copolymer manufactured by Sumitomo Chemical Industries, Ltd. POL-2: Ethylene methacrylic acid copolymer manufactured by Mitsui DuPont POL-3: SEBS block copolymer Styrene content 50 % CaCO ₃ : Particle size 3 μm Organic acid surface treatment Al (OH) ₃ : Particle size 2 μm Organic acid surface treatment Pigment: Gray Titanium oxide 50% by weight Light stabilizer: HALS oxidation Inhibitor: 1: 1 mixture of phenol and phosphorus

Each evaluation was performed by the following tests. <Dimensional stability> Measure the dimensional change after 48 hours in an oven at 80 ° C. ：: 0.2% or less △: 0.2 to 0.5% ×: 0.5% or more <Jointability> Hot air fusion Was used to measure the joining strength when joining at a joining width of 50 mm. ：: bonding strength is 50% or more of the strength of the sheet itself ×: 〃 less than 50% <Adhesiveness> The epoxy resin was used to adhere to the slate plate, and the peel strength after 48 hours was measured. ：: Peel strength of 2 kg / 25 mm or more ×: 未 満 Less than 2 kg / 25 mm <Flexibility> The prepared sheet was constructed and evaluated for ease of construction. ◎: Easy to construct ×: Difficult to construct <Flatness> The prepared sheet was constructed and the flatness after construction was visually evaluated. ◎: Undulation is not noticeable △: Undulation is slightly noticeable ×: Undulation is noticeably large

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

From Examples 1 to 17 and Comparative Examples 1 to 6, it can be seen that the present invention has improved adhesiveness. Also, from Examples 18 to 34, by laminating the base cloth on the intermediate layer,
It can be seen that the dimensional stability is improved. Further, the flatness is improved by laminating the base cloth on the intermediate layer and laminating the foam on the lowermost layer.

[0049]

As is apparent from the above description, the olefin-based waterproofing material of the present invention has a flexural modulus of 250 to 300.
A surface layer and a back surface layer composed of an olefin resin of 0 kgf / cm ² are laminated, and the back layer is formed of an olefin resin 5.
By adding 0 to 300 parts by weight of the filler to 0 to 95 parts by weight and 50 to 5 parts by weight of the non-halogen polar polymer, the workability is good and the bonding strength between the waterproof sheets is high, An olefin-based waterproof sheet having improved adhesion to a base can be obtained.

Further, since the olefin resin of the front layer and the back layer is an olefin thermoplastic elastomer obtained by a reactor method, it is possible to obtain an olefin waterproof sheet excellent in physical properties, weather resistance and long-term durability. it can.

Further, the non-halogen polar polymer in the back layer is an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 50% by weight or more, a carboxylic acid-containing ethylene copolymer resin,
By containing one or more selected from a maleic acid-containing ethylene copolymer resin and a styrene-based thermoplastic elastomer having a styrene content of 20% or more, stable bonding between sheets and adhesion to a base are further improved. An excellent olefin-based waterproofing sheet.

By laminating the substrate between the surface layer and the back layer, or between the surface layer and the back layer, that is, the intermediate layer, the dimensional stability is improved, and the substrate is laminated on the lowermost layer. By doing so, heat insulation and flatness after construction are improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) (C08L 23/00 23:26) F term (reference) 4F100 AG00 AK01B AK03A AK03B AK12B AK41 AK68B AK70B AL01B AL09A AL09B AT00C BA03 BA07 BA10A BA10B CA23B DG12 GB07 JA20B JB16A JB16B JK04A JK04B JK07A JK07B JL11 YY00A YY00B 4J002 AC072 AC082 AC112 BB001 BB031 BB051 BB061 BB071 BB082 BB092 BB121 BB141 BB151 BB171 BB222 BB232 BC022 BE032 BF032 BG042 BG052 BG102 CF002 CK022 CL002 DE076 DE146 DE236 DG046 DJ036 DJ046 DJ056 DK006 FD016 GF00 GL00

Claims (4)

[Claims] 1. A waterproof sheet comprising an olefin resin having a flexural modulus of 250 to 3000 kgf / cm ^{2 and} a surface layer and a back layer laminated on each other.
An olefin-based waterproof sheet characterized by adding 0 to 300 parts by weight of a filler to 95 parts by weight and 50 to 5 parts by weight of a non-halogen polar polymer. 2. The olefin resin of the surface layer and the back layer,
2. The olefin waterproof sheet according to claim 1, wherein the olefin waterproof sheet is an olefin thermoplastic elastomer obtained by a reactor method. 3. The non-halogen polar polymer in the backside layer comprises an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 50% by weight or more, a carboxylic acid-containing ethylene copolymer resin, a maleic acid-containing ethylene copolymer resin, and a styrene content of The olefin-based waterproof sheet according to claim 1 or 2, wherein the olefin-based waterproof sheet contains one or more selected from 20% or more of a styrene-based thermoplastic elastomer. 4. The method according to claim 1, wherein the base material is laminated between the surface layer and the back surface layer, between the surface layer, the back surface layer, or the lowermost layer. Olefin waterproof sheet.