Butyl-based rubber adhesive composition, adhesive tape, waterproof sheet for roofing, adhesive composition for fixing toilets, and joint body

Abstract

To provide a butyl-based rubber adhesive composition with excellent adhesion, tackiness, and holding power (shear force).SOLUTION: The present invention provides a butyl-based rubber adhesive composition, containing 100 pts.mass of a butyl-based rubber, 150-700 pts.mass of an inorganic compound, 20-300 pts.mass of a softener, and 5-70 pts.mass of a fibrous organic compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a butyl rubber adhesive composition. More specifically, it relates to a butyl rubber adhesive composition used for joining roof tiles and waterproof sheets, an adhesive composition for fixing toilets used for fixing toilets to the floor, and the like. The present invention also relates to an adhesive tape using the butyl rubber adhesive composition, a waterproof sheet for roofs using a butyl rubber adhesive composition, a joined body formed by joining a roof tile and a waterproof sheet with a butyl rubber adhesive composition, and a joined body formed by joining a toilet and the floor.

Background Art

[0002] Generally, a waterproof sheet made of synthetic rubber or the like is laid between the roof base and roof tiles on the roof of a building such as a house to prevent the intrusion of rainwater and the like. For joining this waterproof sheet and roof tiles, mechanical fastening methods such as nails, bolts, and rivets, a joining method using a solvent-based adhesive, or a joining method using an acrylic rubber-based or butyl rubber-based adhesive tape is used.

[0003] Among these, from the viewpoints of water resistance and workability, etc., a joining method using a rubber-based adhesive tape is often used. Patent Document 1 proposes a method of joining a roof tile and a waterproof sheet using a butyl rubber-based adhesive tape. However, when the entire roof is exposed to high temperatures due to strong sunlight in summer or the like, there is a problem that it creeps and deforms due to a decrease in the shear force of the adhesive.

[0004] In order to improve the shear force of the adhesive, a method of impregnating a non-woven fabric with the adhesive (Patent Documents 2 and 3) and a method of dispersing fibers in the adhesive have been proposed (Patent Document 4).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] Generally, adhesive force, tack, and holding force (shearing force) are called the three elements of adhesion. Among them, tack and holding force (shearing force) are elements in an antinomy. In the method of impregnating an adhesive into a nonwoven fabric as in Patent Documents 2 and 3, although the deformation of the adhesive is suppressed by the restraint of the nonwoven fabric and the shearing force is improved, there is a problem that the instantaneous adhesion to the adherend called tack decreases. Further, in the adhesive of Patent Document 4, although the tack is good because there is no restraint such as a nonwoven fabric, since it is composed only of butyl rubber and fibers, there is a problem with the shearing force. From the above, none of the methods could achieve a balance between the adhesive force, tack, and holding force (shearing force) called the three elements of adhesion.

[0007] An object of the present invention is to provide a butyl rubber adhesive composition excellent in adhesive force, tack, and holding force (shearing force). The butyl rubber adhesive composition can be suitably used, for example, for applications such as roofing waterproof sheets and for fixing toilets and floors that have been joined by mechanical fastening methods such as nails, bolts, and rivets. [Means for Solving the Problems]

[0008] The present inventors have intensively studied to solve the above problems. As a result, they have found that the above problems can be solved by using a composition with a specific formulation, and have completed the present invention.

[0009] That is, according to the present invention, the following inventions are provided. [1] A butyl rubber adhesive composition comprising 100 parts by mass of butyl rubber, 150 to 700 parts by mass of an inorganic compound, 20 to 300 parts by mass of a softening agent, and 5 to 70 parts by mass of a fibrous organic compound. [2] The butyl rubber adhesive composition according to [1], wherein the inorganic compound contains 30% by mass or more of a clay mineral. [3] The butyl rubber adhesive composition according to [1] or [2], wherein the average fiber length of the fibrous organic compound is 0.5 to 10 mm. [4] An adhesive tape comprising the butyl rubber adhesive composition according to any one of [1] to [3]. [5] A waterproof sheet for a roof having an adhesive layer containing the butyl rubber adhesive composition according to any one of [1] to [3] and a waterproof sheet laminated on the adhesive layer. [6] An assembly obtained by joining a roofing tile and a waterproof sheet with the butyl rubber adhesive composition according to any one of [1] to [3]. [7] A toilet fixing adhesive composition used for fixing a toilet to a floor with the butyl rubber adhesive composition according to any one of [1] to [3]. [8] An assembly obtained by joining a toilet and a floor with the adhesive tape according to [4]. [9] An assembly obtained by joining a toilet and a floor with the toilet fixing adhesive composition according to [7].

Brief Description of the Drawings

[0010] [Figure 1] It is a diagram for explaining the method of the creep resistance evaluation test. Figure 1A shows the state at the start of the test, and Figure 1B is a diagram for explaining the amount of displacement after standing.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, preferred embodiments for carrying out the present invention will be described. It should be noted that the embodiments described below show an example of typical embodiments of the present invention, and the scope of the present invention is not construed narrowly thereby.

[0012] [Butyl rubber adhesive composition] The butyl rubber adhesive composition of the present invention contains a butyl rubber, an inorganic compound, a softening agent, and a fibrous organic compound. More specifically, the butyl rubber adhesive composition includes 100 parts by mass of a butyl rubber, 150 to 700 parts by mass of an inorganic compound, 20 to 300 parts by mass of a softening agent, and 5 to 70 parts by mass of a fibrous organic compound. Hereinafter, each component will be described.

[0013] [Butyl rubber] By containing a butyl rubber, the butyl rubber adhesive composition according to the present invention exhibits effects such as little change in adhesive strength over time and good water resistance. In the present invention, the butyl rubber means a rubber containing a butyl polymer including monomer units derived from isobutylene. That is, the butyl rubber contains isobutylene monomer units. Further, the butyl rubber according to an embodiment of the present invention can contain isobutylene monomer units and isoprene monomer units, that is, it can contain a copolymer obtained by copolymerizing raw material monomers including isobutylene and isoprene. The butyl rubber may be, for example, butyl rubber, partially crosslinked butyl rubber, recycled butyl rubber, polyisobutylene, chlorinated butyl rubber, or brominated butyl rubber, and the butyl rubber adhesive composition can contain one or more butyl rubbers selected from these. Further, since the butyl rubber adhesive composition according to the present invention has good followability to the adherend by containing a butyl rubber, it is suitably used for joining adherends having different forms such as roof tiles and waterproof sheets, or floor materials and toilets.

[0014] In addition, the butyl rubber adhesive composition according to the present invention may contain rubber components other than butyl rubber. Examples of the rubber components other than butyl rubber include liquid rubbers such as liquid polyisoprene, liquid polybutadiene, liquid polychloroprene, and liquid polybutene, natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, chlorinated polyethylene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM), ethylene-vinyl acetate rubber, chloroprene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, silicone rubber, fluororubber, urethane rubber, styrene-based thermoplastic elastomer, and the like. These rubber components other than butyl rubber may be used not only singly but also in combination of two or more. The proportion of butyl rubber in all rubber components is preferably 50% by mass or more, more preferably 80% by mass or more. Specifically, the proportion of butyl rubber in all rubber components is, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass, and may be within the range between any two of the values exemplified herein.

[0015] <Inorganic compound> Examples of inorganic compounds include metal oxides such as alumina, aluminosilicate, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; hydrous inorganic substances such as aluminum hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate; calcium salts such as calcium sulfate and calcium silicate, glass beads, silica-based balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon balloons, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, zinc borate, various magnetic powders, fly ash, inorganic hollow fillers, perlite, obsidian, pearlite, pumice, diatomaceous earth, dehydrated sludge, boron, sodium tetraborate hydrate (borax), inorganic phosphorus-based compounds, silica, glass fibers (E glass fiber, C glass fiber, S glass fiber, D glass fiber), rock wool, ceramic fibers (silica alumina fiber, alumina fiber, silica fiber), zirconia fiber, carbon fiber, bulk alkali earth silicate fiber, gypsum fiber, carbon fiber, metal fiber, slag fiber, basalt fiber, and other fibrous inorganic compounds, and clay mineral-based inorganic compounds containing clay minerals. These inorganic compounds may be used alone or in combination of two or more.

[0016] As the clay mineral-based inorganic compound, at least one selected from natural or synthetic inorganic clay minerals is used. Examples of clay minerals include smectite-based clays such as bentonite, montmorillonite, and hectorite; fibrous clays such as sepiolite and palygorskite; sericite (muscovite), illite, glauconite, chlorite, talc, zeolite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, cristobalite, smectite, kaolin, and clay (hydrous aluminum silicate). These clay minerals may be used alone or in combination of two or more.

[0017] The inorganic compound preferably contains 30% by mass or more of a clay mineral. The proportion of the clay mineral in the inorganic compound is specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass, and may be within the range between any two of the values exemplified herein.

[0018] The content of the inorganic compound is 150 to 700 parts by mass with respect to 100 parts by mass of the butyl rubber, preferably 230 to 595 parts by mass, and more preferably 300 to 470 parts by mass. If it is less than 150 parts by mass, it will be too soft and the creep resistance will deteriorate. If it exceeds 700 parts by mass, it will be too hard and the tack will deteriorate. The content of the inorganic compound is specifically, for example, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700 parts by mass with respect to 100 parts by mass of the butyl rubber, and may be within the range between any two of the values exemplified herein.

[0019] <Softening agent> As long as the object of the present invention is not impaired, the type of the softening agent is not particularly limited, and any known softening agent can be freely selected and used singly or in combination of two or more. Examples of the softening agent include paraffinic, naphthenic, aromatic process oils, rapeseed oil, phthalic acid esters, adipic acid esters, alkyl sulfonic acid esters, sebacic acid esters, process oils, mineral oils, and the like. These softening agents may be used singly or in combination of two or more.

[0020] The content of the softening agent is 20 to 300 parts by mass, preferably 50 to 170 parts by mass, and more preferably 80 to 145 parts by mass with respect to 100 parts by mass of the butyl rubber. If it is less than 50 parts by mass, it will be too hard and the tack (stickiness) will deteriorate. If it exceeds 300 parts by mass, it will be too soft and the creep resistance will deteriorate. Specifically, the content of the softening agent is, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300 parts by mass with respect to 100 parts by mass of the butyl rubber, and it may be within the range between any two of the values exemplified herein.

[0021] <Fibrous organic compound> The shape of the fibrous organic compound only needs to be fibrous, and examples of the cross-sectional shape of the fiber include circular, elliptical, polygonal, etc. Assuming the average fiber length of the fibrous organic compound is L and the average diameter is D, the L / D of the fiber is, for example, more than 10, preferably 50 or more, and more preferably 100 or more. The upper limit is not particularly defined, but is, for example, 10000. The average diameter of the fibrous organic compound is, for example, 1 to 100 μm, preferably 2 to 50 μm, and more preferably 5 to 20 μm. The average fiber length of the fibrous organic compound is, for example, 0.1 to 15 mm, preferably 0.5 to 10 mm. Specifically, the average fiber length of the fibrous organic compound is, for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0 mm, and it may be within the range between any two of the values exemplified herein.

[0022] Examples of the fibrous organic compound include meta-aramid fiber, para-aramid fiber, amide fiber, pulp fiber, cellulose fiber (pulp fiber), polyparaphenylene benzobisoxazole fiber, polyarylate fiber, and the like. These fibrous organic compounds may be used alone or in combination of two or more. Note that the fibrous organic compound is preferably contained in the composition with the fibers being dispersed.

[0023] The average fiber length and average diameter of the fibrous organic compound are sufficiently large numbers, that is, the length is measured for 20 or more fibrous organic compounds, and the average value thereof is taken as the average fiber length and average diameter.

[0024] The fiber length and diameter of the fibrous organic compound can be measured using, for example, a field emission scanning electron microscope (FE-SEM).

[0025] The content of the fibrous organic compound is 5 to 70 parts by mass, preferably 10 to 55 parts by mass, and more preferably 15 to 40 parts by mass with respect to 100 parts by mass of the butyl rubber. If it is less than 5 parts by mass, it will be too soft and the creep resistance will deteriorate. If it exceeds 70 parts by mass, the adhesiveness will deteriorate. Specifically, the content of the fibrous organic compound is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 parts by mass with respect to 100 parts by mass of the butyl rubber, and it may be within the range between any two of the values exemplified herein.

[0026] In the butyl rubber adhesive composition according to the present invention, additives such as tackifiers, vulcanizing agents, anti-aging agents, vulcanization accelerators, and lubricants that are usually used in ordinary rubber compositions can be contained within a range that does not impair the object of the present invention. When adding a vulcanizing agent or a vulcanization accelerator, the total amount is preferably 0.05 parts by mass or less, or 0.01 parts by mass or less.

[0027] The butyl rubber adhesive composition can be obtained by kneading a butyl rubber, an inorganic compound, a softening agent, a fibrous organic compound, and other necessary additives using a kneading device (for example, a kneader mixer, etc.).

[0028] [Adhesive tape] The butyl rubber adhesive composition according to the present invention can be suitably used for an adhesive tape for a tile roof. For example, by kneading each component contained in the butyl rubber adhesive composition using a kneading device or the like and forming the kneaded product into a tape shape, an adhesive tape for a tile roof having adhesiveness on both sides can be obtained. At this time, the adhesive tape may not include a base material.

[0029] The kneading device used when kneading each component is not particularly limited, and a known kneading device can be freely selected for kneading. Examples of the kneading device include a Banbury mixer, a kneader mixer, and two-roll mills. Also, the method of forming the kneaded product into a tape shape is not particularly limited, and a known forming method can be freely selected and used. Examples of such methods include forming methods such as roll forming and extrusion forming.

[0030] Since the adhesive tape obtained as described above uses the butyl rubber adhesive composition according to the present invention, it has excellent adhesiveness and creep resistance. As a result, the durability of the joined body in which the roofing tile and the waterproof sheet are joined using this adhesive tape can also be improved.

[0031] [Waterproof sheet for roof] The waterproof sheet for roof according to the present invention has an adhesive layer and a waterproof sheet. Hereinafter, each component will be described.

[0032] <Adhesive layer> The adhesive layer is made of the above-described butyl rubber adhesive composition. Details of the butyl rubber adhesive composition will be omitted. Note that it is also possible to use the above-described adhesive tape as this adhesive layer.

[0033] <Waterproof sheet> In the waterproof sheet for roofs according to the present invention, the waterproof sheet is laminated on the adhesive layer. The material used for the waterproof sheet is not particularly limited as long as the object of the present invention is not impaired, and known materials can be freely selected and used singly or in combination of two or more. Examples of such materials include ethylene-propylene-diene rubber (EPDM), polyvinyl chloride (PVC), and the like. Among these materials, EPDM is particularly preferable. This is because the waterproof sheet using EPDM has good adhesiveness to the butyl rubber adhesive composition.

[0034] <Toilet> The above-mentioned butyl rubber adhesive composition can be used, for example, for fixing a toilet to the floor. According to one embodiment of the present invention, there is provided a joined body in which a toilet and a floor are joined by the above-mentioned butyl rubber adhesive composition (adhesive composition for fixing a toilet) or an adhesive tape containing the butyl rubber adhesive composition. The joined body constitutes a part of a toilet, and a toilet provided with a joined body in which a toilet and a floor are fixed (joined) can be provided. The toilet and the floor may be joined only by the above-mentioned butyl rubber adhesive composition, or may be joined in combination with a mechanical fastening method such as nails, bolts, and rivets.

Examples

[0035] Hereinafter, the present invention will be described in more detail based on examples. It should be noted that the examples described below show an example of a typical embodiment of the present invention, and the scope of the present invention is not construed narrowly thereby.

[0036] "Parts" in this example are based on mass standards. In addition, details of the materials used in this example are shown below, respectively. (1) Butyl rubber · Butyl rubber ("Butyl 268" manufactured by JSR Corporation) (2) Inorganic compound · Calcium carbonate: "TA044" manufactured by Chichibu Cement Co., Ltd. · Clay (containing aluminum silicate): "FA-80" manufactured by Community Maebashi Feldspar Co., Ltd. (3) Plasticizer · Process oil: "AH-16" manufactured by Idemitsu Kosan Co., Ltd. (4) Fibrous compound <Fibrous organic compound> · Pulp fiber, average fiber length 1.2 mm: "Neo Fiber NS-10" manufactured by Oji Plastic Co., Ltd. · Aramid fiber, 0.25, 0.5, 3, 10, 12 mm: "Twaron Shortcut Fiber" manufactured by Teijin Limited <Fibrous inorganic compound> · Glass fiber, average fiber length 3 mm: "ECS03-350" manufactured by Central Glass Co., Ltd.

[0037] [Preparation of butyl rubber adhesive composition] For each example and comparative example, according to the compounding amounts shown in the table, using a 3-liter kneader mixer, knead at 110 °C for 1 hour to obtain a kneaded product which is a butyl rubber adhesive composition. Further, the obtained kneaded product was processed into a tape shape with a width of 25 mm and a thickness of 1 mm using an extruder with a die temperature set at 70 °C to produce an adhesive tape.

[0038] [Table 1]

[0039] [Table 2]

[0040] [Table 3]

[0041] [Table 4]

[0042] [Table 5]

[0043] [Evaluation] The adhesion properties were evaluated according to the method shown below. The results are shown in Tables 1 to 2. <Adhesiveness (adhesive force)> An adhesive tape processed into a shape of width 15 mm × length 100 mm × thickness 1 mm (lined with a PET film (100 μm thick) on one side) was bonded to a ceramic tile processed into a shape of width 30 mm × length 125 mm to obtain a test piece. This test piece was pressure-bonded back and forth once with a 2 kg rubber roller, and after leaving it for 20 minutes, the adhesive force when the adhesive tape was peeled off in the 180° direction at a speed of 300 mm / min was measured, and the adhesiveness was judged according to the following criteria. Note that the greater the adhesive force, the better the adhesiveness. ◎: Adhesive force is 30 N / 15 mm or more ○: Adhesive force is 25 N / 15 mm or more and less than 30 N / 15 mm △: Adhesive force is 20 N / 15 mm or more and less than 25 N / 15 mm ×: Adhesive force is less than 20 N / 25 mm

[0044] <Tackiness (tack)> An adhesive tape processed into a shape of width 15 mm × length 100 mm × thickness 1 mm (lined with a PET film (100 μm thick) on one side) was obtained as a test piece. The adhesive surface (the surface not lined with the PET film) of this test piece was used to measure the tack with a probe tack tester manufactured by Nichiban Co., Ltd. (probe diameter 25 mm 2 , upward stop time 0.1 second, upward speed 10 mm / second, load: 9.8 g), and the tack (tackiness) was judged according to the following criteria. ◎: Probe tack value is 5 N / 25 mm 2 or more ○: Probe tack value is 4 N / 25 mm 2 or more and less than 5 N / 25 mm 2 △: Probe tack value is 2 N / 25 mm 2 or more and less than 4 N / 25 mm 2 ×: Probe tack value is less than 2 N / 25 mm 2

[0045] <Creep resistance (holding force · shear force)> ​​​An adhesive tape (without PET film) processed into a shape of width 25 mm × length 80 mm × thickness 1 mm was bonded between two stainless steel plates (SUS304: 100 mm × 30 mm × 2.5 mm t). One stainless steel plate was fixed, and a 200 g weight (hammer) was hung on the other stainless steel plate (see Fig. 1A), and it was left for 1 hour in an environment of 50°C. Then, the displacement amount (the distance of slip-down) of the other stainless steel plate with respect to one stainless steel plate after leaving for 1 hour was measured (see Fig. 1B), and the creep resistance was judged according to the following criteria. Note that the smaller the displacement amount, the better the creep resistance. ◎: Displacement amount is less than 2 mm ○: Displacement amount is 2 mm or more and less than 4 mm △: Displacement amount is 4 mm or more and less than 6 mm ×: Displacement amount is 6 mm or more, or it has fallen

Claims

【Claim 1】 A butyl rubber adhesive composition comprising: 100 parts by mass of butyl rubber; 150 to 700 parts by mass of an inorganic compound; 20 to 300 parts by mass of a softening agent; 5 to 70 parts by mass of a fibrous organic compound; A butyl rubber adhesive composition containing the above components.

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