JP2002038107A - Method for sticking polyolefin-based waterproof sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sticking method excellent in operability and adhesion, and capable of providing high waterproof reliability by improving preservation stability of a tape-shaped adhesive in the adhesion of waterproof sheet comprising a polyolefin resin or an olefinic thermoplastic elastomer. SOLUTION: This sticking method at an sticking part of the waterproof sheet comprising the polyolefin resin or the olefinic thermoplastic elastomer comprises coating a primer and sticking the sheet through a tape-shaped adhesive. A simple brominated product of a copolymer of isobutylene and p- methylstyrene, or a blend comprising 100 pts.wt. copolymer and 10-100 pts.wt. natural or synthetic rubber is used as the main component of the primer and the tape-shaped adhesive having autoadhesive properties, and a metal oxide and a phenol resin are formulated with one of the primer and the tape-shaped adhesive, and the other thereof respectively so that the primer and the adhesive may be naturally cured by the contact of the primer with the tape-shaped adhesive.

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 polyolefin-based waterproofing sheet, and more particularly, to workability and adhesion in bonding a waterproofing sheet composed of a polyolefin resin or an olefin-based thermoplastic elastomer which is usually bonded by heat fusion. The present invention relates to a primer / tape contact curing type bonding method using an adhesive having excellent waterproofness and high waterproofness.

[0002]

2. Description of the Related Art In recent years, polyolefin-based thermoplastic elastomers (polyolefin-based TPEs) have recently been used to reduce labor and energy consumption in the production of rubber products, and also to be environmentally friendly. The share in the product is steadily increasing.

However, polyolefin-based resins and polyolefin-based TPEs are polar and chemically very inactive polymers, and therefore have extremely poor adhesion, and there has been no good adhesive for practical use. for that reason,
In the bonding of these polyolefin-based TPEs, bonding by heat fusion is generally used.

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

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

However, if the above-mentioned bonding by heat fusion is adopted, heating equipment is required, so that it is undeniable that it is disadvantageous in terms of cost, and the sheet material is heated at a high temperature during the bonding operation. Because of the need for fusion, there is a problem in terms of safety with respect to work on site. 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, since the above-mentioned various primer compositions are used in combination with an adhesive, there is a problem in workability, and they 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. It was found that it had excellent adhesion performance to TPE, and it was found that a brominated product of isobutylene and p-methylstyrene copolymer was used alone and natural or synthetic rubber was added to 100 parts by weight of the brominated product.
Solid content of 3 to 1 consisting of a blend containing 0 to 100 parts by weight
A method of bonding a waterproof sheet was proposed in which a 5% solution was 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. (Japanese Patent Application No. 11-212973)

[0009] However, when the bonding method according to the above proposal was put into practical use, the tape was gradually vulcanized and the adhesiveness was lowered when the naturally vulcanized tape-like adhesive was stored for a long period of time. I ran into a problem.

[0010] Therefore, studies were again conducted to solve this problem, and as a result, when a bromide of isobutylene and a p-methylstyrene copolymer was present in the presence of a metal oxide such as MgO or ZnO and a phenol resin, Vulcanizes easily,
In the case of only one of the compounding systems, it has been found that the composition is extremely stable. By paying attention to this fact, a phenol resin or a metal oxide such as MgO or ZnO in the primer is compounded, and the primer is added to the tape. A phenol resin or a metal oxide such as MgO or ZnO different from the above was blended to examine the curability of the tape. As a result, when plasticizers such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and process oils such as paraffin and naphthene are blended for the purpose of imparting self-adhesion at the time of heating or at ordinary temperature in the tape, To vulcanize to
The present invention has been reached.

That is, the present invention uses the above-mentioned adhesive composition containing bromide of isobutylene and p-methylstyrene copolymer as a main component for a primer and a tape-like adhesive which is self-adhesive at room temperature, while using a metal. Oxide and phenolic resin are mixed and mixed, and polyolefin T
An object of the present invention is to solve the above-mentioned problems in bonding PE and to provide a method for bonding a polyolefin-based TPE waterproof sheet that is excellent in workability and adhesiveness and has high waterproofness.

[0012] That is, the bonding method of the present invention which achieves the above object and conforms to the above object is to apply a primer in bonding a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, and then apply the primer at room temperature. Upon bonding via a self-adhesive tape-like adhesive, the main components of the primer and the tape-like adhesive are respectively added to a bromide of isobutylene and a p-methylstyrene copolymer alone or to 100 parts by weight of the bromide. On the other hand, a blend containing 10 to 100 parts by weight of a natural or synthetic rubber, one of a metal oxide and a phenol resin is blended with a primer, and the other is blended with a tape adhesive to form a primer and a tape. It is characterized by being naturally cured by contact with an adhesive.

[0013] Here, the joints of the waterproof sheet to which the above method is applied include a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, and an EP.
Joint with DM-based vulcanized rubber waterproof sheet and EPDM
It also includes joints between the vulcanized rubber waterproof sheets, and is extremely useful for bonding these joints.

[0014]

By applying the above-mentioned bonding method and using a primer and a self-adhesive tape-like adhesive together, the two come into contact with each other, are naturally cured, and have good storage stability of the tape. By natural vulcanization with radiant heat from the above, it is firmly adhered to a polyolefin-based waterproof sheet having poor adhesion and to both the polyolefin-based waterproof sheet and the EPDM-based vulcanized rubber waterproof sheet, and excellent adhesion can be performed.

[0015]

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 a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer or a joint between the waterproof sheet and an EPDM-based vulcanized rubber waterproof sheet or an EPDM-based vulcanized rubber waterproof sheet. A bromide of isobutylene and p-methylstyrene copolymer alone or a blend containing 10 to 100 parts by weight of a natural or synthetic rubber per 100 parts by weight of a bromide, wherein one of a metal oxide or a phenolic resin is compounded. After the solution was applied in advance as a primer, the same bromide or blend having self-adhesion at room temperature was used as a main component, and another one different from the above compounded with a metal oxide or phenol resin was compounded. This is a method of bonding via a 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 to the present invention, in addition to joining the waterproof sheets made of the above-mentioned materials, the above-mentioned waterproof sheet is joined to an EPDM-based vulcanized rubber waterproof sheet as another material. Bonding is also included.

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 furthermore, isobutylene as a primer and a tape-like adhesive for bonding the sheet and an EPDM-based vulcanized rubber sheet. And a bromide of p-methylstyrene copolymer (EXPRO, manufactured by Exxon Chemical Co., Ltd.) as main components.

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.
It is also used as a blend containing parts by weight.

The rubber to be blended with the bromide of isobutylene and p-methylstyrene copolymer includes natural rubber,
Various rubbers such as butyl rubber, chlorinated or brominated butyl rubber, polyisobutylene, ethylene-propylene-diene, and chloroprene rubber are listed, and these are brominated (E
XPRO) is used by blending in a range of 10 to 100 parts by weight with respect to 100 parts by weight. Incorporation of a predetermined amount of rubber in this manner can increase the initial adhesive strength, and is extremely advantageous in terms of workability and prevention of peeling of the sheet after the work.

The brominated isobutylene / 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 of _{1 + 8} (125 ° C) of 30 to 55 in mol%
It is.

As the primer, in addition to the brominated isobutylene and p-methylstyrene copolymers and the rubber, a solvent such as toluene, xylene, cyclohexane and n-hexane which dissolves the rubber, and the cohesive force of the adhesive are used. A filler such as carbon black, calcium carbonate, talc, or clay is compounded and used as a reinforcing agent for increasing the carbon content. Further, as a vulcanizing agent for bromide and bromide blend rubber, metal oxides such as MgO and ZnO (3 to 20 ph) are used.
r) or a phenol resin (methylolated alkylphenol resin or brominated alkylphenol resin 5 to 5)
40 phr), and the following tackifying resins, plasticizers, and process oils can be used to improve the adhesion of the primer. 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, dioctyl adipate, and Adhesiveness can be imparted to the adhesive by blending a paraffin-based process oil.

Next, a tag used in combination after the application of the primer
As in the case of the above primer, bromine and benzene
Content of 0.4 to 1.3 mol%, Mooney viscosity
ML _{1 + 8}Isobutyle having (125 ° C) of 30 to 55
Of bromine and p-methylstyrene copolymer (Exxon
Chemical company; EXPRO) alone and natural or synthetic rubber
The main component is a blend containing 0 to 100 parts by weight.
Yes, metal oxides such as MgO and ZnO or phenol
Resin (methicalolated alkylphenol resin or odor
Alkylated phenolic resin)
But one of them is blended,
-Viscosity is ML_{1 + 8}(100 ° C) is in the range of 3 to 25
Preferably. If it is 3 or less, it is soft, so
Problem in the industry, if it is more than 25, there is a problem with the initial adhesion
Occurs. It also improves the self-adhesion and adhesion of the tape.
May be blended with tackifier resin, plasticizer and process oil.
No. Aliphatic, alicyclic and aromatic petroleum resins, and
Resins with good compatibility such as gin or dioctyl lid
Rate, dibutyl phthalate, dioctyl adipate, etc.
Plasticizers and paraffin, naphthene, etc.
As a reinforcing agent to increase the cohesive strength of oil and adhesive
Carbon black, calcium carbonate, silica, talc,
Fillers such as clay can also be used as needed
You.

Thus, the storage stability of the tape is good by using the above-mentioned phenolic resin and the self-adhesive tape-like adhesive in combination, and the polyolefin is hardly adhered by natural vulcanization by radiant heat of sunlight over time. A strong waterproofing property is obtained by firmly adhering to both a water-based waterproofing agent and a polyolefin-based waterproofing material and an EPDM-based vulcanized rubber waterproofing material.

Hereinafter, examples of the present invention will be further described to show that the adhesive is excellent.

[0028]

EXAMPLE 1 First, EX having a bromine and benzyl group content of 0.75 mol% and a Mooney viscosity of _{1 + 8} (125 ° C.) of 45 was used.
The inorganic compound shown in Table 1 was kneaded with a roll using PRO (a bromide of isobutylene and p-methylstyrene copolymer manufactured by Exxon Chemical Co., Ltd.), and then dissolved with toluene together with a phenol resin or a plasticizer. 15% of P-1
The primer shown in P-3 was obtained.

[0029]

[Table 1]

Next, a predetermined amount of a brominated product of isobutylene and p-methylstyrene copolymer, a filler, a tackifier resin, a plasticizer or a process oil, and a vulcanizing agent are blended in a formulation shown in Table 2 and mixed with a kneader. After kneading, each of the tape-shaped adhesives T-1, T-2, T-3 having a thickness of 1.0 mm was extruded by an extruder.
I got T-1 and T-2 are examples of the present invention containing either a metal oxide or a phenol resin, and T-3 is a comparative example containing both a metal oxide and a phenol resin.

[0031]

[Table 2]

Each of the primers P-1 thus obtained
To P-3 are polyolefin-based thermoplastic elastomers (T
PE) 100 g / m ² applied to the sheet with a brush, and 1
After drying for an hour, the tape-like adhesive obtained above is optionally used,
Combined and joined. Thereafter, another polyolefin-based TPE sheet to which the primer was applied was joined and pressure-bonded using a hand roll. The resulting conjugate is brought to room temperature and 80
In an oven at 72 ° C., after curing for 72 hours each, peeling speed 5
T-peeling was performed at 0 mm / min. Table 3 shows the results.
The adhesion is expressed in kg / 25 mm.

[0033]

[Table 3] However, A / A: adhesive tape cohesive failure, A / T: primer / tape peeling,

From Table 3 above, T-3 containing both phenolic resin and metal oxide is the same as T-3 containing only one.
Adhesive strength after curing at 80 ° C. for 72 hours is inferior to that of 1, T-2. From this, it can be seen that vulcanization proceeds when T-3 is left for a while, storage is not possible, and it is not suitable as an adhesive. . This can be more clearly understood, especially from the comparison of 3, 4 in Table 3. In addition, in 8 and 12 in the table, as for T-3, the adhesive hardened over time and was unsuitable as an adhesive, whereas T-1 and T-1 in which only one of them was blended was not suitable as an adhesive. It can be seen that T-2 sufficiently retains the adhesive force even after a lapse of time, can be used as an adhesive, and is easily stored.

On the other hand, for comparison, Table 4 shows the adhesiveness to olefin-based TPE, as a comparative example, in the case of bonding using only various commercially available adhesives having the respective main component compositions. In the table, F is TP
This is the interface peeling of the E sheet.

[0036]

[Table 4]

From the comparison between the above Tables 3 and 4, the Comparative Example bonded with only a commercially available adhesive causes interfacial peeling between sheets, whereas each of Examples of the present invention causes cohesive failure.
It shows excellent adhesion.

Example 2 Using the same formulation as in Example 1, the following synthetic rubbers were used: (a) Essobutyl 268 (butyl rubber manufactured by Esso Chemical) (b) Chlorinated butyl HT-1066 (manufactured by Esso Chemical)
(Chlorinated butyl rubber) (c) Bifnetux L-120 (polyisobutylene manufactured by Esso Chemical Co., Ltd.) was blended at a mixing ratio shown in Table 5 with a bromide (EXPRO) of isobutylene and a P-methylstyrene copolymer. The basic composition of this synthetic rubber blended primer adhesive is 100 parts of rubber, 20 parts of stearic acid, 20 parts of light calcium carbonate, 20 parts of phenolic resin, and 1 part of toluene.
5% solution.

Using this primer, another polyolefin-based TPE sheet was joined with a tape-like adhesive (T-1) in the same manner as in Example 1 and pressure-bonded using a hand roll. Then, after the cured product was cured in an oven at room temperature and an oven at 80 ° C. for 72 hours, the peeling rate was 50 mm / min.
At 180 ° peeling test. The results are shown in Table 5.

[0040]

[Table 5] However, A / A: tape breakage, F: TPE sheet / adhesive interface peeling,

Example 3 The primer obtained in Example 1 was replaced with a polyolefin TP
Apply 100 g / m ² to the E sheet with a brush and leave at room temperature for 1 hr.
After drying, the tape adhesive obtained in Example 1 was joined. And then, the EPDM coated with the primer
A system vulcanized rubber waterproof sheet was joined and crimped using a hand roll. The resulting bonded article was cured in an oven at room temperature and at 80 ° C. for 72 hours each, and then peeled at a rate of 50 mm / min.
(180 ° C. oven test). Table 6 shows the results
As shown in FIG.

[0042]

[Table 6] However, A / A: tape breakage, F: TPE sheet / adhesive interface peeling,

Example 4 EPDM-based vulcanized rubber waterproof sheets were joined to each other using the primer and the tape adhesive obtained in and of Example 1 and the joined article was heated at room temperature and in an oven at 80 ° C. for 7 minutes, respectively.
After curing for 2 hours, T peeling was performed at a peel rate of 50 mm / min. The results were as shown in Table 7.

[0044]

[Table 7] However, A / A: tape breakage, F: interface peeling,

From the above tables, it can be seen that in each of the examples in which the primer of the present invention and the tape-shaped adhesive were used in combination, the result of the adhesiveness test was cohesive failure, and the adhesive strength was excellent.

[0046]

As described above, according to the present invention, a primer is applied to a joint portion of a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, and then a self-adhesive tape adhesive is applied at normal temperature. In bonding, a bromide of isobutylene and p-methylstyrene copolymer alone or a blend containing 10 to 100 parts by weight of a natural or synthetic rubber with respect to 100 parts by weight of the bromide as a primer and a tape-like adhesive The main component is to mix one of the metal oxide and the phenolic resin into the primer and mix the other with the tape-like adhesive so that the primer and the tape-like adhesive are allowed to cure naturally by contact. The storage stability of the tape is improved by using the primer and the self-adhesive tape adhesive together. , By air vulcanized in welfare and heat from sunlight in time, poorly adhesive polyolefin tarpaulins and polyolefin tarpaulins and E
Strongly adheres to both PDM-based vulcanized rubber waterproof sheets, and demonstrates excellent adhesion to waterproof sheet joints made of polyolefin resin or olefin-based thermoplastic elastomer, which were difficult to bond with adhesives in the past. It does not require pretreatment such as oxidation, has excellent durability and good workability, and is safe without special heating work.
It has a remarkable effect that makes it possible to bond with extremely excellent waterproof sealing properties.

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 and increasing the initial adhesive force by using it as a blend. This has the effect of preventing workability and preventing the sheet from peeling immediately after the work. Thus, the bonding method of the present invention is expected to have a remarkable effect on the bonding of a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, which has recently been used from an environmental point of view.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F211 AA03 AA09 AA13E AA37 AA45 AA45E AC03 AD05 AG01 TA05 TC09 TD11 TH22 TN53 TN56 TN63 4J040 CA012 CA032 DA141 DB071 DB091 EB032 HA136 JA09 MA11 PA03 PA23

Claims (3)

[Claims] In a bonding of a waterproof sheet made of a polyolefin resin or an olefin-based thermoplastic elastomer, a primer is applied, and then the primer is applied via a self-adhesive tape adhesive at room temperature. And a tape-shaped adhesive, respectively, isobutylene and p
A brominated methylstyrene copolymer alone or 10 to 10 parts by weight of a natural or synthetic rubber with respect to 100 parts by weight of the brominated product;
The main component is a blend containing 0 parts by weight, and one of a metal oxide and a phenolic resin is blended into a primer, and the other is blended into a tape-like adhesive. A method for bonding a polyolefin-based waterproofing sheet, characterized by curing. 2. The method for bonding a polyolefin waterproof sheet according to claim 1, wherein the waterproof sheet to be joined is a waterproof sheet made of a polyolefin resin or an olefin thermoplastic elastomer, and an EPDM vulcanized rubber waterproof sheet. 3. The method for bonding polyolefin waterproof sheets according to claim 1, wherein the waterproof sheets to be bonded are EPDM vulcanized rubber waterproof sheets.