JP2001040106A - Bonding process for waterproof sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide such a process for bonding waterproof sheets made of a polyolefin resin or an olefinic thermoplastic elastomer as giving excellent workability and adhesion as well as highly reliable waterproofness. SOLUTION: A bonding process for joining parts between waterproof sheets made of a polyolefin resin or an olefinic thermoplastic elastomer, comprises applying, as a primer, a solution of 3-15% by solid content of either a brominated compound of isobutylene p-methylstyrene copolymer or a blend of the brominated compound and 10-100 pts.wt. of a natural or synthetic rubber, and bonding each other via a naturally vulcanizable adhesive tape having, as the main component, a butyl rubber with self-adhering property at an ordinary temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for bonding a waterproof sheet, and more particularly, to a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, which is usually joined by heat fusion, with excellent workability and adhesiveness. The present invention relates to a bonding method using a highly reliable waterproof and adhesive.

[0002]

2. Description of the Related Art In recent years, polyolefin-based thermoplastic elastomers (hereinafter abbreviated as polyolefin-based TPEs) have been
Labor saving and energy saving in rubber product manufacturing,
Furthermore, consideration for environmental issues, that is, polyolefin TP
The share in rubber products is steadily increasing due to the non-polluting and recycling properties of E.

[0003] However, polyolefin resins and polyolefin-based TPEs are non-polar and chemically very inert polymers, so their adhesiveness is extremely poor.
There was no good adhesive for practical use. Therefore, the bonding between these sheets generally uses bonding by heat fusion.

As a chemical bonding method, a method of oxidizing the surface of a polyolefin resin or a polyolefin-based TPE sheet with a chemical oxidizing agent, corona discharge, flame, ozone gas or the like, and then bonding with an adhesive is used. I came.

[0005] Further, as a method of bonding without these pretreatments, good adhesion, for example, cyclized rubber, aromatic petroleum resin,
Various primer compositions comprising an ethylene-vinyl acetate copolymer and chlorinated polypropylene have been proposed.

[0006]

However, when the above-mentioned bonding by heat fusion is adopted, it is disadvantageous in terms of cost because a heating facility is required.
In addition, since the sheet material must be heat-sealed at a high temperature during the bonding operation, there is a problem in terms of safety with respect to the on-site operation. Further, there is a disadvantage that unevenness of the adhesive force easily occurs due to variations in the melting time, temperature, humidity and pressure bonding force.

[0007] On the other hand, the chemical bonding method cannot perform uniform treatment, and has a problem in the process. In addition, the above-mentioned various primer compositions are used in combination with an adhesive, have problems in workability, and cannot be said to be sufficient.

Accordingly, the present inventors have proposed a polyolefin-based T
No pretreatment was performed on PE, and extensive research was conducted on an adhesive composition having excellent durability and high adhesive performance. As a result, a brominated product of isobutylene and p-methylstyrene copolymer (EXPRO) was converted to a polyolefin-based product. They have found that they have excellent adhesion performance to TPE.

That is, the present invention solves various problems in joining polyolefin-based TPEs by using the above-mentioned adhesive composition containing bromide of isobutylene and p-methylstyrene copolymer as a main component. It is an object of the present invention to provide a method for bonding a polyolefin-based TPE waterproof sheet that is excellent in workability and adhesion without causing unevenness in bonding and has high waterproofness.

[0010]

The features of the present invention that achieves the above object and conforms to the above object are as follows. That is, one of them is the bonding of a bonded portion of a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, and the main component is a bromide of isobutylene and p-methylstyrene copolymer alone or a natural or synthetic rubber. Of a 3 to 15% solid content, which is a blend containing 10 to 100 parts by weight, is applied as a primer and then bonded via a naturally vulcanized tape adhesive mainly composed of butyl rubber, which is self-adhesive at room temperature. Another method is to use a waterproof sheet made of polyolefin resin or olefin-based thermoplastic elastomer and EPD.
In the adhesion of the joint portion of the M-based vulcanized rubber waterproof sheet, the main component is bromide of isobutylene and p-methylstyrene copolymer alone or natural or synthetic rubber is added to the bromide.
Solid content of 3 to 15% which is a blend containing １００100 parts by weight
Is applied as a primer and then bonded via a naturally vulcanized tape-like adhesive mainly composed of butyl rubber, which is self-adhesive at room temperature.

[0011]

By using the above-mentioned bonding method, in bonding the respective waterproof sheet joints, the joint of the waterproof sheet made of polyolefin resin or olefin-based thermoplastic elastomer (TPE) does not require a pretreatment such as oxidation. It is excellent in durability and can have high adhesive performance.
In particular, by using a chlorinated polypropylene solution or the like as a primer on a polyolefin-based TPE and using a natural vulcanization type tape adhesive mainly composed of butyl rubber, which has self-adhesiveness and improves cohesion over time after joining, It has good workability, does not require a heating operation, is safe, has excellent adhesiveness, and can perform adhesion excellent in waterproof sealability.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be specifically described.

First, the present invention relates to the bonding of waterproof sheets made of a polyolefin resin or an olefin-based thermoplastic elastomer, or the bonding between the waterproof sheets and the EPTM-based vulcanized rubber waterproof sheet, wherein isobutylene and p-methylstyrene copolymer are bonded together. Combined bromide alone or bromide 100
A solution having a solid content of 3 to 15%, which is a blend containing 10 to 100 parts by weight of natural or synthetic rubber with respect to parts by weight, is applied in advance as a primer, and then a natural additive mainly composed of butyl rubber which is self-adhesive at room temperature is used. It consists of a method of bonding via a sulfuric tape adhesive.

Here, one of the materials of the waterproof sheet to be joined in the present invention is a polyolefin resin or an olefin-based thermoplastic elastomer. Specifically, the polyolefin resin may be a high-density polyethylene, a low-density polyethylene, a polypropylene, or the like. The olefin-based thermoplastic elastomer is a blend of polyethylene or polypropylene and ethylene propylene rubber, or a copolymer of both, based on a monomer, and a material that has the properties of both resin and rubber. It is. In addition, the present invention joins waterproof sheets made of the above materials,
Another material includes joining the waterproof sheet to an EPDM vulcanized rubber waterproof sheet.

As specific examples of the olefin-based thermoplastic elastomer, TPR (trade name, manufactured by Uniroyal),
Telcar (BF Goodrich Chemical
al), Somel (Dupont), TPO (E
xxon Chemical Co., Ltd.) and Esplen (Sumitomo Chemical Co., Ltd.).

Next, as described above, the present invention particularly provides a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, and isobutylene and p-methylstyrene as primers for bonding the sheet and an EPDM vulcanized rubber sheet. A brominated copolymer is used as a main component.

The above bromide of isobutylene and p-methylstyrene copolymer can be used alone,
10 to 100 parts by weight of natural or synthetic rubber is added to 100 parts by weight of bromide of isobutylene and p-methylstyrene copolymer.
Used as a blend containing parts by weight. Incorporation of a predetermined amount of rubber in this manner can increase the initial adhesive force, and is extremely advantageous in terms of workability and prevention of peeling of the sheet after the work.

The above bromide of isobutylene and p-methylstyrene copolymer which can be suitably used in the present invention has a bromine and benzyl group content of 0.4 to 1.3.
Mooney viscosity ML _{1 + 8} (125 ° C) is 30 ~
55.

On the other hand, rubbers to be blended with brominated isobutylene and p-methylstyrene copolymers include natural rubber, butyl rubber, chlorinated or brominated butyl rubber, polyisobutylene, ethylene-propylene-diene, chloroprene rubber and the like. These are bromide 100
It is used by blending 10 to 100 parts by weight with respect to parts by weight.

As the primer, besides the above brominated product of isobutylene and p-methylstyrene copolymer and rubber, a solvent such as toluene, xylene, cyclohexane and n-hexane, and a reinforcing agent for increasing the cohesive force of the adhesive are used. As an agent, carbon black, calcium carbonate, silica,
Blend fillers such as talc and clay, and further blend metal oxides such as ZnO and MgO or polyvalent polyamines such as tetraethylenetetramine and hexamethylenetetramine or methylolated alkylphenol and brominated alkylphenol as vulcanizing agents. Thereby, the adhesive strength can be improved.

For further improving the tackiness, the following tackifying resins, plasticizers and process oils can be used. That is,
Aliphatic, alicyclic, aromatic petroleum resins, and resins having good compatibility with bromide of isobutylene and p-methylstyrene copolymer such as phenolic resin, or plasticizers such as dioctyl phthalate, dibutyl phthalate and dioctyl adipate Adhesives can be made tacky by the addition of a class and paraffinic or naphthenic process oil. The concentration of the primer is appropriately selected from the viewpoints of coating properties, drying properties and adhesiveness, but is most preferably 3 to 15%.

Next, the natural vulcanization-based tape adhesive mainly composed of butyl rubber, which is used in combination after the application of the primer, includes butyl rubber, halogenated butyl rubber (chlorinated or brominated), ethylene propylene rubber and polyisobutylene. It is a mixture of two or more kinds, and the initial Mooney viscosity ML _{1 + 8} (100 ° C.) of the mixture is preferably in the range of 3 to 25. Initial Mooney viscosity ML _{1 + 8} (1
(00.degree. C.) is less than 3, there is a problem that the bonding operation is difficult due to the softness, and the initial adhesiveness is insufficient.

As the natural vulcanizing agent, a commonly used sulfur used in combination with an accelerator such as tyrium or dithiocarbamate, or an oxime-peroxide accelerator or a compound containing a peroxide and an accelerator thereof Can be used. In addition, a tackifier, a plasticizer, and a process oil for improving the self-adhesion of the tape may be blended.

Aliphatic, alicyclic and aromatic petroleum resins, and highly compatible resins such as rosin and phenolic resins, or plasticizers such as dioctyl phthalate, dibutyl phthalate and dioctyl adipate, and paraffinic and naphthenic It is a system process oil, and a filler such as carbon black, calcium carbonate, silica, talc, clay, or the like can be added as necessary to enhance the cohesive strength of the adhesive.

Thus, a natural vulcanization type having self-adhesive properties with a primer mainly containing a bromide of the above-mentioned isobutylene and p-methylstyrene copolymer alone and a blend containing 10 to 100 parts by weight of a natural or synthetic rubber. The use of a tape-type adhesive makes it easy to perform the initial bonding work, and, over time, naturally vulcanizes with the radiant heat of sunlight, so that it can be applied to both hard-to-adhesive polyolefin-based TPE and EPDM-based vulcanized rubber waterproof sheets. It adheres firmly and can obtain excellent waterproof performance.

Hereinafter, examples of the present invention will be further described.

[0027]

EXAMPLES First, EXPRO (isobutylene and p-methylstyrene copolymer manufactured by Exxon Chemical Co., Ltd.) having a bromine and benzyl group content of 0.7 mol% and a Mooney viscosity ML 1 _{+ 8} (125 ° C.) of 45 was used. Using a bromide), the inorganic compound shown in Table 1 was kneaded with a roll, and then dissolved with toluene together with a resin or a plasticizer to obtain primers represented by P-1 to P-5 having a solid content of 10%.

[0028]

[Table 1]

Next, butyl rubber (I
IR), a predetermined amount of a filler, a tackifier resin, a plasticizer or a process oil, and a vulcanizing agent, and after kneading with a kneader, a 1.0 mm-thick tape-like adhesive T-
1, T-2 and T-3 were obtained. The vulcanization accelerators BZ, TRA, and TT in Table 2 are those manufactured by Ouchi Shinko Co., Ltd.

[0030]

[Table 2]

Each primer thus obtained was applied to a polyolefin-based thermoplastic elastomer (TPE) sheet with a brush at a rate of 100 g / m ² and dried at room temperature for 1 hour, and then joined by combining the tape adhesive obtained above. . Thereafter, another polyolefin-based TPE sheet to which the primer was applied was joined, and pressure-bonded using a hand roll to obtain Examples 1 to 6, respectively. The obtained joint was cured in an oven at room temperature and an oven at 80 ° C. for 72 hours, and then subjected to a 180 peeling test at a peeling rate of 50 mm / min. Table 3 shows the results. In addition, the example which adhere | attached only by the tape-shaped adhesive agent without using a primer was made into Comparative Examples 1-3.

[0032]

[Table 3]

As shown in Table 3, the comparative examples in which the primer was not used exhibited peeling at the interface between the sheets, whereas the examples showed cohesive failure, showing excellent adhesive strength. Table 4 shows the adhesive strength when the olefin-based TPE was joined with various commercially available adhesives in comparison with the above table.

[0034]

[Table 4]

Using the same formulation as above, the following synthetic rubbers (a) Denka M-120 (chloroprene manufactured by Denki Kagaku) (b) Essobutyl 268 (butyl rubber manufactured by Esso Chemical) (c) Chlorinated butyl HT- 1066 (manufactured by Esso Chemical Co., Ltd.)
(Chlorinated butyl rubber) (d) Visnex L-120 (polyisobutylene manufactured by Esso Chemical Co.) was blended with isobutylene and a bromide of P-methylstyrene copolymer (EXPRO) at the compounding ratio shown in Table 5. The basic composition of the synthetic rubber blend-compounded primer-based adhesive is 100% rubber, 1 stearic acid, 20 light calcium carbonate, 5 zinc white, and 5% solution of Heirez T-100 × 30 in toluene.

Using this primer, another polyolefin-based TPE sheet was joined with a tape-like adhesive in the same manner as described above, and pressed with a hand roll. Then, the bonded article was cured in an oven at room temperature and in an oven at 80 ° C. for 72 hours, and then subjected to a 180 ° peeling test at a peeling rate of 50 mm / min. The results are shown in Table 5. However,
In the table, A / A indicates tape breakage, and F indicates interfacial peeling of the TPE sheet.

[0037]

[Table 5]

Further, the primer obtained above was applied to a polyolefin-based TPE sheet with a brush at 100 g / m ² , dried at room temperature for 1 hour, and then the tape-like adhesive obtained above was joined. Then, the EPDM-based vulcanized rubber waterproof sheet to which the primer was applied was joined, and pressure-bonded using a hand roll. Room temperature and 80 ° C.
After curing in an oven for 72 hours each, peeling speed 50m
A 180 ° peel test peeling was performed at m / min.
The results were as shown in Table 6 below.

[0039]

[Table 6]

According to Table 6 above, the comparative example in which the primer was not used caused peeling at the interface between the sheets.
In each of the examples in which the primer of the present invention was used in combination, cohesive failure was observed, and it is understood that the examples have excellent adhesive strength.

[0041]

As described above, the present invention provides a primer for bonding a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, or a bromide of isobutylene and p-methylstyrene copolymer alone or a natural or synthetic rubber. 3-15% of solid content of blend containing
Is applied as a primer, and then bonded via a naturally vulcanized tape-like adhesive mainly composed of butyl rubber, which is self-adhesive at room temperature, and is made of a polyolefin resin or an olefin-based thermoplastic elastomer. Conventionally, a chlorinated polypropylene solution is used as a primer for joining sheets together with a natural vulcanization type tape adhesive mainly composed of butyl rubber, which has self-adhesive properties and improves cohesion over time. Demonstrates excellent adhesion at the joint of waterproof sheet made of polyolefin resin or olefin-based thermoplastic elastomer, which was difficult to bond with an adhesive, does not require pretreatment such as oxidation, and has excellent durability and construction It has good water resistance, is safe without the need for heating work, has excellent high adhesion, and is extremely waterproof and sealable. To exert a significant effect that the accounts if possible adhesion.

The bromide of isobutylene and p-methylstyrene copolymer is used by blending 10 to 100 parts by weight of a natural or synthetic rubber with respect to 100 parts by weight to increase the initial adhesive strength. This has the effect of being able to provide workability and the ability to peel off the sheet immediately after construction. Thus, in recent years, remarkable effects are expected to be applied to waterproof sheets made of polyolefin resins and olefin-based thermoplastic elastomers whose use is being promoted from an environmental point of view.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 7/02 C09J 7/02 Z 123/22 123/22 (72) Inventor Junichi Kamoto Nagata-ku, Kobe-shi 4-1-2, Hamazoe-dori Mitsuhoshi Belt Co., Ltd. (72) Inventor Tsuneo Kubo 4-11-3, Gakugaoka, Tarumizu-ku, Kobe F-term (reference) 4D075 CA12 DA04 DB36 DC02 EA35 EA41 EB10 EB12 EB14 EB47 EB56 EC30 4F071 AA11A AA12A AA13A AA14B AA15B AA16B AA18B AA20B AA21A AA22A AA75A AA75B AA79A AH03 AH04 CA01 4J004 AA05 DAA07 AA17 AB04 BA02 FA08 FA10 4J018 CB131 CB131 CB131 CB131 CB131 LA06 MA12 MB03 NA12 PA10 PA23

Claims (4)

[Claims] 1. A bonding method for bonding a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, wherein a solution having a solid content of 3 to 15% containing bromide of isobutylene and p-methylstyrene copolymer as a main component is used. A method for bonding a waterproof sheet, wherein the method is applied as a primer and then bonded via a naturally vulcanized tape-like adhesive mainly composed of butyl rubber, which is self-adhesive at room temperature. 2. In the bonding of a waterproof sheet made of a polyolefin resin or an olefin thermoplastic elastomer, a natural or synthetic rubber is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of a bromide of isobutylene and p-methylstyrene copolymer. Solid content of 3 to 3 parts by weight including blend
A method for bonding a waterproof sheet, comprising applying a 15% solution as a primer, and thereafter bonding through a naturally vulcanized tape-like adhesive mainly composed of butyl rubber, which is self-adhesive at room temperature. 3. A method of bonding a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer to a joining part of an EPDM-based vulcanized rubber waterproof sheet, comprising a solid containing bromide of isobutylene and a p-methylstyrene copolymer as a main component. A method for bonding a waterproof sheet, comprising applying a solution of 3 to 15% as a primer as a primer, and thereafter bonding through a natural vulcanized tape-like adhesive mainly composed of butyl rubber, which is self-adhesive at room temperature. . 4. A method of bonding a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer to a joining part of an EPDM vulcanized rubber waterproof sheet with respect to 100 parts by weight of a bromide of isobutylene and p-methylstyrene copolymer. A solution having a solid content of 3 to 15% consisting of a blend containing 10 to 100 parts by weight of natural or synthetic rubber is applied as a primer, and then a natural vulcanized tape-like adhesive mainly composed of butyl rubber, which is self-adhesive at room temperature. A method for bonding a waterproof sheet, wherein the bonding is performed via an agent.