JP6864139B1 - Butyl rubber adhesive composition, adhesive tape, roof tarpaulin and joint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a butyl rubber-based pressure-sensitive adhesive composition which can be used for joining a roof tile and a waterproof sheet and has excellent adhesiveness and creep resistance. According to the present invention, a butyl rubber-based pressure-sensitive adhesive composition containing a butyl rubber, an olefin-based resin, and a tackifier resin, wherein the content of the olefin-based resin is 5 to 100 parts by mass of the butyl rubber. Melt mass flow rate (MFR) was measured under the conditions of 50 parts by mass, the content of the tackifier resin of 50 to 200 parts by mass, and the olefin resin at a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210. A butyl rubber-based pressure-sensitive adhesive composition having a weight of 40 g / 10 min or less is provided. [Selection diagram] Fig. 1

Description

The present invention relates to a butyl rubber-based pressure-sensitive adhesive composition used for joining a roof tile and a waterproof sheet, an adhesive tape using a butyl rubber-based pressure-sensitive adhesive composition, a roof waterproof sheet using a butyl rubber-based pressure-sensitive adhesive composition, and a butyl rubber-based adhesive. The present invention relates to a joined body formed by joining a roof tile and a waterproof sheet with an adhesive composition.

Generally, on the roof of a building such as a house, a waterproof sheet made of synthetic rubber or the like is laid between the roof base and the roof tile to prevent rainwater or the like from entering. For joining this waterproof sheet to roof tiles, there are mechanical fastening methods such as nails, bolts and rivets, joining methods using solvent-based adhesives, or joining methods using acrylic rubber-based or butyl rubber-based adhesive tapes. It is used.

Among these, a joining method using a rubber-based adhesive tape is often used from the viewpoint of water resistance and workability. 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 temperature due to strong sunlight in summer or the like, there is a problem that the adhesive tape is creep-deformed by heat.

Japanese Unexamined Patent Publication No. 2004-300674

An object of the present invention is to provide a butyl rubber-based pressure-sensitive adhesive composition that can be used for joining a roof tile and a tarpaulin and has excellent adhesiveness and creep resistance.

As a result of searching for various substances that can be blended in the butyl rubber-based pressure-sensitive adhesive composition in order to solve the above problems, the inventors of the present application have found a specific substance that was not contained in the conventional butyl rubber-based pressure-sensitive adhesive composition. It has been found that a butyl rubber-based pressure-sensitive adhesive composition having excellent adhesiveness and creep resistance can be obtained by blending the above, and the present invention has been completed.

The present invention is a butyl rubber-based pressure-sensitive adhesive composition containing a butyl rubber, an olefin-based resin, and a tackifier resin, wherein the content of the olefin-based resin is 5 to 50 parts by mass with respect to 100 parts by mass of the butyl rubber. The content of the imparting resin is 50 to 200 parts by mass, and the melt mass flow rate (MFR) of the olefin resin measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210 is 40 g / 10 min or less. A butyl rubber-based pressure-sensitive adhesive composition is provided.

The butyl rubber-based pressure-sensitive adhesive composition according to the present invention is suitably used for joining a roof tile and a waterproof sheet. The type of roof tile that can be fixed using this butyl rubber-based pressure-sensitive adhesive composition is not particularly limited, but the butyl rubber-based pressure-sensitive adhesive composition according to the present invention can be particularly preferably used for fixing pottery tiles.

The butyl rubber-based pressure-sensitive adhesive composition according to the present invention may be used as an pressure-sensitive adhesive tape for a tiled roof by being processed into a tape shape.
Further, the butyl rubber-based pressure-sensitive adhesive composition according to the present invention is suitably used for the pressure-sensitive adhesive layer of a roof waterproof sheet in which a pressure-sensitive adhesive layer and a waterproof sheet are laminated. The roof waterproof sheet may be formed by laminating the adhesive tape and the waterproof sheet.
Further, the butyl rubber-based pressure-sensitive adhesive composition according to the present invention may be used to form a bonded body formed by joining a roof tile and a tarpaulin.

The butyl rubber-based pressure-sensitive adhesive composition according to the present invention is excellent in tackiness and creep resistance.

1A to 1B are diagrams for explaining a method for evaluating creep resistance.

Hereinafter, suitable 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 narrowly interpreted by this.

[Butyl rubber adhesive composition]
The butyl rubber-based pressure-sensitive adhesive composition according to the present invention can be used for fixing various types of tiled roofs. The butyl rubber-based pressure-sensitive adhesive composition of the present invention includes, for example, ceramic roof tiles (glazed roof tiles) having a glassy surface formed on the surface, roof tiles having a carbon film containing carbon as a main component on the surface, glazed roof tiles, and salt-baked roof tiles. It can be used for cement roof tiles, roof tiles containing polystyrene, and the like, but it can be particularly preferably used for pottery roof tiles.

The butyl rubber-based pressure-sensitive adhesive composition of the present invention contains butyl rubber, an olefin-based resin, and a tack-imparting resin. Hereinafter, each component will be described.

<Butyl rubber>
By containing butyl rubber, the butyl rubber-based pressure-sensitive adhesive composition according to the present invention has the effects that the adhesive strength does not change over time and the water resistance is good. Further, the butyl rubber-based pressure-sensitive adhesive composition according to the present invention has good followability to the adherend because it contains butyl rubber, so that the adherends having different forms such as roof tiles and tarpaulins are joined to each other. It is preferably used for.

The butyl rubber-based pressure-sensitive adhesive composition according to the present invention may contain a rubber component other than butyl rubber. As rubber components other than butyl rubber, for example, a small amount of double bonds were introduced into a diene rubber such as natural rubber, isoprene rubber, styrene-butadiene rubber, and chloroprene rubber, and a main chain such as butyl rubber and ethylene-propylene rubber. Examples include rubber (eg, ethylene-propylene-diene rubber). Not only one type of these rubbers but also two or more types may be used. The ratio of butyl rubber to the total rubber component is preferably 50% by mass or more, more preferably 80% by mass or more.

<Olefin resin>
The olefin resin has a mass flow rate (MFR) of 40 g / 10 min or less, preferably 30 g / 10 min or less, and more preferably 20 g / 10 min or less at 190 ° C. and a load of 2.16 kg as defined by JIS K7210. preferable. By incorporating such an olefin-based resin in the butyl rubber-based pressure-sensitive adhesive composition, creep resistance can be enhanced. The lower limit of MFR is not particularly specified, but MFR is preferably 1 g / 10 min or more, more preferably 2 g / 10 min or more, further preferably 3.5 g / 10 min or more, still more preferably 5 g / 10 min or more. This is because if the MFR value is too small, the adhesive strength of the butyl rubber-based pressure-sensitive adhesive composition decreases.

The content of the olefin resin is 5 to 50 parts by mass with respect to 100 parts by mass of butyl rubber. If the content of the olefin resin is less than 5 parts by mass, sufficient creep resistance cannot be obtained, and if the content of the olefin resin exceeds 50 parts by mass, the adhesive force required as an adhesive for roof tiles. Cannot be obtained.

The olefin resin is a homopolymer or copolymer of an olefin. In the olefin copolymer, all of the constituent monomers may be olefins, or some of them may be olefins. The carbon number of the olefin is preferably 2 to 10, and more preferably 2 to 6. Examples of the olefin include ethylene, propylene, butene, 4-methyl-1-pentene and the like. Examples of the olefin resin include polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / butene copolymer, and ethylene / 4-methyl-1-pentene copolymer.

The olefin resin preferably contains a copolymer of ethylene and a monomer other than ethylene. Examples of the monomer other than ethylene include vinyl acetate, butene, 4-methyl-1-pentene and the like. The olefin resin is more preferably a mixture of polyethylene, an ethylene / vinyl acetate copolymer, an ethylene / butene copolymer, and an ethylene / 4-methyl-1-pentene copolymer. In this case, the adhesiveness and creepability tend to be particularly good.

<Adhesive-imparting resin>
The tackifier resin is used to improve the tackiness of the butyl rubber-based pressure-sensitive adhesive composition. The tackifier resin is not particularly limited, and one or more known tackifier resins can be freely selected and used. Examples of the tackifying resin include rosin-based resin, hydride-based resin, terpene-based resin, hydride-based terpene-based resin, aromatic-modified terpene resin, terpenphenol resin, styrene-based resin, kumaron resin, phenolformaldehyde resin, and asphalt. , C5 petroleum resin (aliphatic resin) obtained by copolymerizing C5 distillates such as penten, isoprene, piperin, 1,3-pentadien produced by thermal decomposition of petroleum naphtha, and petroleum naphtha produced by thermal decomposition. C9 petroleum resin (aromatic resin) obtained by copolymerizing C9 distillates such as inden and vinyl toluene, C5 / C9 petroleum resin (aliphatic hydrocarbon resin), and hydrogen of these petroleum resins. Examples thereof include styrene petroleum resin and alicyclic saturated hydrocarbon resin. Among these tackifier resins, alicyclic saturated hydrocarbon resins are preferable from the viewpoint of the balance between creep resistance and tackiness.

The content of the tackifier resin is 50 to 200 parts by mass with respect to 100 parts by mass of butyl rubber. If the content of the tackifier resin is less than 50 parts by mass, the adhesive strength required as an adhesive for roof tiles cannot be obtained, and if the content of the tackifier resin exceeds 200 parts by mass, sufficient creep resistance is obtained. Cannot be obtained.

The softening point of the tackifier resin is preferably 80 to 130 ° C. When the softening point is 80 ° C. or higher, sufficient creep resistance is obtained, and when it is 130 ° C. or lower, sufficient adhesive strength is obtained. In the present specification, the "softening point" of the tackifier resin means a value measured in accordance with JIS K2531.

The butyl rubber-based pressure-sensitive adhesive composition according to the present invention includes an inorganic filler, a softening agent (plasticizer), an antiaging agent, and a processing aid used in ordinary rubber compositions, as long as the object of the present invention is not impaired. , Additives such as lubricants can be included.

(A) Inorganic filler The type of the inorganic filler is not particularly limited as long as the object of the present invention is not impaired, and any known inorganic filler can be freely selected and used. .. Examples of the inorganic filler include silica, diatomaceous earth, alumina, zinc oxide, magnesium oxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, calcium silicate, carbon black, talc, mica, bentonite, activated clay, and glass fiber. Glass beads, aluminum nitride, carbon fibers, etc. can be mentioned. The content of the inorganic filler is, for example, 10 to 600 parts by mass, preferably 50 to 500 parts by mass, and more preferably 100 to 400 parts by mass with respect to 100 parts by mass of butyl rubber.

(B) Softener The type of softener is not particularly limited as long as the object of the present invention is not impaired, and any known softener can be freely selected and used. Examples of the softening agent include paraffin-based, naphthenic-based, aroma-based process oils, rapeseed oils, phthalates, adipates, alkylsulfonic acids, sebacic acids, and the like. The content of the softener is, for example, 10 to 400 parts by mass, preferably 20 to 300 parts by mass, and more preferably 50 to 200 parts by mass with respect to 100 parts by mass of butyl rubber.

[Adhesive tape]
The butyl rubber-based pressure-sensitive adhesive composition according to the present invention can be suitably used for a pressure-sensitive adhesive tape for a tiled roof. For example, each component contained in a butyl rubber-based pressure-sensitive adhesive composition is kneaded using a kneading device or the like to form a tape-like kneaded product to obtain an adhesive tape for a tile roof having adhesiveness on both sides. Can be done.

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 apparatus include a Banbury mixer, a kneader mixer, a double roll and the like. Further, 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 a method include molding methods such as roll molding and extrusion molding.

Since the adhesive tape obtained as described above uses the butyl rubber-based pressure-sensitive adhesive composition according to the present invention, it has excellent adhesiveness and creep resistance. As a result, it is possible to improve the durability of the joint body in which the roof tile and the waterproof sheet are joined by using this adhesive tape.

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

<Adhesive layer>
The pressure-sensitive adhesive layer comprises the above-mentioned butyl rubber-based pressure-sensitive adhesive composition. Details of the butyl rubber-based pressure-sensitive adhesive composition will be omitted. As the pressure-sensitive adhesive layer, the above-mentioned pressure-sensitive adhesive tape can also be used.

<Waterproof sheet>
In the roof waterproof sheet according to the present invention, the waterproof sheet is laminated on the adhesive layer. The type of the material used for the waterproof sheet is not particularly limited as long as the object of the present invention is not impaired, and one or two or more known materials can be freely selected and used. 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-based pressure-sensitive adhesive composition.

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 example of the present invention, and the scope of the present invention is not narrowly interpreted by this.

The "part" in this embodiment is based on the mass standard. The details of the materials used in this example are shown below.
(1) Butyl rubber-Butyl rubber ("Butyl 268" manufactured by JSR Corporation)
(2) Olefin resin-A-10: A mixture of polyethylene, ethylene-vinyl acetate copolymer, ethylene-butene copolymer, and ethylene-4-methyl-1-pentene copolymer ("Sun" manufactured by Asahi Kasei Co., Ltd. Fine PAK "MFR = 10g / 10min)
-A-20: A mixture of polyethylene, ethylene-vinyl acetate copolymer, ethylene-butene copolymer, and ethylene-4-methyl-1-pentene copolymer ("Sunfine PAK" manufactured by Asahi Kasei Co., Ltd. MFR = 20 g / 10min)
-A-28: A mixture of polyethylene, ethylene-vinyl acetate copolymer, ethylene-butene copolymer, and ethylene-4-methyl-1-pentene copolymer ("Sunfine PAK" manufactured by Asahi Kasei Co., Ltd. MFR = 28 g / 10min)
-A-45: A mixture of polyethylene, ethylene-vinyl acetate copolymer, ethylene-butene copolymer, and ethylene-4-methyl-1-pentene copolymer ("Sunfine PAK" manufactured by Asahi Kasei Co., Ltd. MFR = 45 g / 10min)
-B-0.8: LDPE ("F22NH" manufactured by Ube Maruzen Polyethylene Co., Ltd. "
MFR = 0.8g / 10min)
-B-2: LDPE ("F222NH" manufactured by Ube-Maruzen Polyethylene Co., Ltd. "
MFR = 2g / 10min)
-B-3.5: LDPE ("F320" manufactured by Ube Maruzen Polyethylene Co., Ltd.
MFR = 3.5g / 10min)
B-5: LDPE ("F522N" manufactured by Ube-Maruzen Polyethylene Co., Ltd.
MFR = 5g / 10min)
B-10: LDPE (“J1019” MFR = 10g / 10min manufactured by Ube Maruzen Polyethylene Co., Ltd.)
B-20: LDPE ("J2522" MFR = 20g / 10min manufactured by Ube Maruzen Polyethylene Co., Ltd.)
B-25: LDPE ("J2516" MFR = 25g / 10min manufactured by Ube Maruzen Polyethylene Co., Ltd.)
B-50: LDPE (“J5019” MFR = 50g / 10min manufactured by Ube Maruzen Polyethylene Co., Ltd.)
(3) Adhesive-imparting resin ・ A1: Aromatically modified terpene resin (“YS resin TO-85” manufactured by Yasuhara Chemical Co., Ltd., softening point 85 ° C.)
-A2: Aromatic modified terpene resin ("YS resin TO-115" manufactured by Yasuhara Chemical Co., Ltd., softening point 115 ° C.)
-A3: Aromatic modified terpene resin ("YS resin TO-125" manufactured by Yasuhara Chemical Co., Ltd., softening point 125 ° C.)
-B1: Rosin ester resin ("Super Ester L" manufactured by Arakawa Chemical Industry Co., Ltd., softening point less than 23 ° C)
-B2: Rosin ester resin ("Super Ester A-75" manufactured by Arakawa Chemical Industry Co., Ltd., softening point 75 ° C)
-C1: Alicyclic saturated hydrocarbon resin ("Arcon P-90" manufactured by Arakawa Chemical Industry Co., Ltd., softening point 90 ° C.)
-C2: Alicyclic saturated hydrocarbon resin ("Arcon P-115" manufactured by Arakawa Chemical Industry Co., Ltd., softening point 115 ° C.)
-C3: Alicyclic saturated hydrocarbon resin ("Arcon P-140" manufactured by Arakawa Chemical Industry Co., Ltd., softening point 145 ° C)
(4) Additives-Inorganic filler: Calcium carbonate ("TA044" manufactured by Chichibu Lime Industry Co., Ltd.)
-Softener: Process oil ("AH-16" manufactured by Idemitsu Kosan Co., Ltd.)

[Preparation of Butyl Rubber Adhesive Composition]
Each Example / Comparative Example was kneaded at 110 ° C. for 1 hour using a kneader mixer having a capacity of 3 liters according to the blending amounts shown in Tables 1 and 2 to obtain a kneaded product as a butyl rubber-based pressure-sensitive adhesive composition. It was. Further, the obtained kneaded product was processed into a tape having a width of 25 mm and a thickness of 1 mm by an extruder having a die temperature set to 70 ° C. to prepare an adhesive tape.

[Evaluation]
Adhesiveness and creep resistance were evaluated according to the methods shown below. The results are shown in Tables 1 and 2. As shown in the table, all the examples had good adhesiveness and creep resistance, whereas all the comparative examples had poor adhesiveness and creep resistance. Further, comparing Examples 2 and 4 with Examples 10 to 11, the olefin resin has particularly good adhesiveness and creep resistance when it contains a copolymer of ethylene and other monomers. It turned out to be. Further, referring to Examples 6 to 8, the adhesive strength becomes particularly good when the MFR is 2 g / 10 minutes or more, and the adhesive strength becomes even better when the MFR is 3.5 g / 10 minutes or more, and 5 g / 10 It was found that the adhesive strength became even better when the time was more than a minute.

<Adhesive>
An adhesive tape (lined with PET film (100 μm thickness) on one side) processed into a shape of width 25 mm × length 100 mm × thickness 1 mm is attached to a pottery tile processed into a shape of width 30 mm × length 125 mm for testing. I got a piece. This test piece was crimped once with a 2 kg rubber roller, left for 20 minutes, and then the adhesive strength when the adhesive tape was peeled off in the 180 ° direction at a speed of 300 mm / min was measured (measurement temperature 21 ° C). Adhesiveness was judged according to the criteria of. The greater the adhesive strength, the better the adhesiveness.
⊚: Adhesive strength is 45N / 25mm or more ○: Adhesive strength is 30N / 25mm or more, less than 45N / 25mm ×: Adhesive strength is less than 30N / 25mm

<Creep resistance>
Adhesive tape (without PET film) 3 processed into a shape of width 25 mm x length 80 mm x thickness 1 mm is attached between two stainless steel plates (SUS304: 100 mm x 30 mm x 2.5 mmt) 1 and 2. One stainless steel plate 1 was fixed, and a 200 g weight 4 was hung on the other stainless steel plate 2 (see FIG. 1A), and left in an environment of 50 ° C. for 1 hour. Then, the amount of deviation D (distance slipped off) of the other stainless steel plate 2 with respect to one stainless steel plate 1 after being left for 1 hour was measured (see FIG. 1B), and the creep resistance was determined according to the following criteria. The smaller the amount of deviation, the better the creep resistance.
⊚: Misalignment amount D is less than 2 mm ○: Misalignment amount D is 2 mm or more and less than 4.5 mm ×: Misalignment amount D is 4.5 mm or more

1,2: Stainless steel plate 3: Adhesive tape 4: Weight D: Amount of deviation

Claims (6)

A butyl rubber-based pressure-sensitive adhesive composition containing butyl rubber, an olefin-based resin, and a tack-imparting resin.
The content of the olefin resin is 5 to 50 parts by mass, and the content of the tackifier resin is 50 to 200 parts by mass with respect to 100 parts by mass of the butyl rubber.
The olefin resin, temperature 190 ° C. in conformity with JIS K7210, melt mass flow rate measured under a load of 2.16 kg (MFR) is Ri Der below 40 g / 10min,
The olefin resin, you containing a copolymer of a monomer other than ethylene and ethylene, butyl rubber-based pressure-sensitive adhesive composition. The butyl rubber-based adhesive according to claim 1 , wherein the olefin-based resin is a mixture of polyethylene, an ethylene-vinyl acetate copolymer, an ethylene-butene copolymer, and an ethylene / 4-methyl-1-pentene copolymer. Agent composition. The butyl rubber-based pressure-sensitive adhesive composition according to claim 1 or 2 , wherein the tack-imparting resin has a softening point of 80 to 130 ° C. An adhesive tape comprising the butyl rubber-based pressure-sensitive adhesive composition according to any one of claims 1 to 3. A pressure-sensitive adhesive layer made of the butyl rubber-based pressure-sensitive adhesive composition according to any one of claims 1 to 3.
A waterproof sheet for a roof, comprising a waterproof sheet laminated on the pressure-sensitive adhesive layer. A bonded body formed by bonding a roof tile and a tarpaulin with the butyl rubber-based pressure-sensitive adhesive composition according to any one of claims 1 to 3.

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