JPH02135272A - Bonding composition and bonding - Google Patents

Abstract

PURPOSE:To obtain a bonding composition suitable for vulcanization bonding between a rubber composition and a metal treated with an adhesive for vulcanization bonding by adding an organic peroxide-based vulcanizing agent to a specific ethylene-propylene-diene terpolymer rubber composition. CONSTITUTION:(A) 100 pts.wt. raw material rubber comprising (i) 60-90 pts.wt. ethylene-propylene-diene terpolymer rubber and (ii) 40-10 pts.wt. butyl rubber is blended with (B) 5-20 pts.wt. halogenated alkylphenol resin or 5-20 pts.wt. alkylphenol resin and halogen donor and further (C) an organic peroxide-based vulcanizing agent to give an organic peroxide vulcanizable ethylene-propylene- diene terpolymer rubber composition and the aimed composition useful for vulcanization bonding between the rubber composition and a metal treated with an adhesive for vulcanization bonding to metal.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to an organic peroxide vulcanized ethylene/propylene/diene ternary copolymer rubber composition and a vulcanization adhesive between the rubber composition and a metal. The present invention relates to an adhesive rubber composition and an adhesive cement composition used for vulcanization bonding with metal treated with an adhesive.

The present invention also provides an organic peroxide vulcanized ethylene-propylene-diene ternary copolymer rubber composition using the adhesive rubber composition and/or the adhesive cement composition;
The present invention relates to a method of adhering the rubber composition to metal treated with an adhesive for vulcanization adhesion of metal.

<Prior Art> Adhesive molded products of metal and rubber compositions are known. The manufacturing of such products usually involves vulcanizing a sheet of unvulcanized rubber composition by laminating metal treated with a phenolic adhesive to a sheet of unvulcanized rubber composition. If the tackiness of a sheet made of a rubber composition is poor, the rubber composition may contain a tackifier or a adhesive of the rubber composition, which is one of the adherends, may be applied. A method has been adopted in which metal and the sheet are bonded together and vulcanized.

On the other hand, ethylene-propylene-diene ternary copolymer rubber (
E'PDM (hereinafter referred to as E'PDM) has extremely excellent corrosion resistance and chemical resistance, so EDP is applied to a core made of metal such as iron.
Linings, rolls, etc. made of M-based rubber compositions vulcanized and bonded are extremely useful.

<Problem to be solved by the invention> A core made of metal such as iron treated with a phenolic adhesive,
When manufacturing linings, rolls, etc. made by vulcanizing and adhering sheets made of organic peroxide-vulcanized EPDM rubber compositions, unvulcanized EPDM has poor adhesiveness, so EPD
Even if a tackifier is blended into the M-based rubber composition or a co-glue is applied, the adhesion between the metal and the rubber sheet is poor before vulcanization and peeling occurs. Conventionally, a rubber sheet is wrapped around a core body and then tightened with a rope, or as shown in Figures 1 and 2, a rubber sheet 2 is wrapped around a metal core body 1 and then the rubber A metal side plate 3 is crimped onto the sheet 2, tightened with bolts 4, and vulcanization is performed while preventing the rubber sheet 2 from peeling off. The bottle 4 was removed, and in the example shown in FIG. 2, the bolt 4 was removed and the hole 5 made in the rubber sheet 2 was repaired. Therefore, productivity was extremely poor.

The present invention has been made in view of the above-mentioned facts, and consists of an organic peroxide vulcanized EPDM rubber composition and a metal treated with an adhesive for vulcanization bonding between the rubber composition and metal. During vulcanization adhesion, an adhesive composition is placed between the metal and the rubber composition to prevent the rubber composition from peeling off from the metal before vulcanization, and an organic peroxide using the adhesive composition is used. The purpose of the present invention is to provide a method for adhering a vulcanized EPDM rubber composition to a metal treated with an adhesive for vulcanization of the rubber composition and metal, and is therefore intended to improve productivity. be.

Means for Solving the Problems> The present invention provides an organic peroxide vulcanized EPDM rubber composition;
An adhesive rubber composition used for vulcanization adhesion between the rubber composition and metal treated with an adhesive for vulcanization adhesion to metal, comprising:
Contains 5 to 20 parts by weight of a halogenated alkylphenol resin, or 5 to 20 parts by weight of an alkylphenol resin and a halogen donor, per 100 parts by weight of raw rubber consisting of 60 to 90 parts by weight of EPDM and 40 to 10 parts by weight of butyl rubber. The present invention further provides an adhesive rubber composition characterized by containing an organic peroxide-based vulcanizing agent.

The present invention also provides an adhesive cement composition used for vulcanization bonding between an organic peroxide vulcanized EPDM rubber composition and a metal treated with an adhesive for vulcanization bonding between the rubber composition and metal. The solid content is 5 to 5 parts by weight of halogenated alkylphenol resin per 100 parts by weight of raw material rubber consisting of 60 to 90 parts by weight of EPDM and 40 to 10 parts by weight of butyl rubber.
It is characterized by containing 0 parts by weight or 5 to 50 parts by weight of an alkylphenol resin and a halogen donor, roughly containing an organic peroxide-based vulcanizing agent, and having a solid content of 10 to 25% by weight. The present invention provides a cement composition for bonding.

Furthermore, the present invention provides an organic peroxide vulcanized EPDM rubber composition using the adhesive rubber composition and/or the adhesive cement composition, and an adhesive for vulcanization bonding between the rubber composition and metal. This provides a method for adhering to metals treated with.

The present invention will be explained in detail below.

A first aspect of the present invention provides an adhesive rubber composition containing EPDM, butyl rubber, a halogenated alkylphenol resin, or an alkylphenol resin, a halogen donor, and an organic peroxide-based vulcanizing agent.

E PDM is a synthetic rubber represented by formula (I),
It is a non-polar rubber.

1I3 (In the above formula, It, m and n are positive integers, and X is 1,4-hexadiene) Specifically, Nisbrene 305 (manufactured by Sumitomo Chemical Co., Ltd.), JSREP -24 (manufactured by Japan Synthetic Rubber Co., Ltd.), Mitsi EPT4070 (manufactured by Mitsui Petrochemical Industries, Ltd.), and the like.

Vulcanization of EPDM is performed using an organic peroxide-based vulcanizing agent, although sulfur vulcanization is also possible since the diene component (X) is present.

Butyl rubber is a synthetic rubber shown in formula (11), and E
Like PDM, it is a non-polar rubber.

CH3CHs -f-Ctb C-h book CH2-C-Cl1-C)+2
+ll(II)CH8 (In the above formula, m and n are positive integers) Butyl rubber is classified according to the degree of unsaturation, molecular weight, and presence or absence of stabilizers, but in the present invention, the diene concentration is 1.5. ~2.5mo
f1%, Mooney viscosity (ML, ., 125°C) 41~
Use one with a size of about 56.

Specifically, ExxonButyl 268 (ExxonCh
em, Go, ), exonbutyl 365 (Ex
xonC, b e m , G o , ), etc.

Butyl rubber is a fairly stable polymer chemically due to its low number of double bonds. Therefore, vulcanization is slow, and in order to achieve sufficient vulcanization with sulfur vulcanization, it is necessary to use high temperatures and strong vulcanization accelerators, or to vulcanize for a long time.
However, vulcanization methods such as quinoid (P-quinone dioxime, P, P' dihenzoylquinone dioxime) vulcanization and resin (modified phenol resin) vulcanization can also be applied.

Halogenated alkylphenol resin has the formula CII+
) is a mixture of polymethylolphenols shown in E
It acts as a vulcanizing agent for PDM and butyl rubber, and is also a tackifier.

(II+) (In the above formula, n is 0 or a positive integer, X and Y are a hydrogen atom or an alkyl group, and Z is a halogen atom or an alkyl group. However, a halogen atom and an alkyl group are always present.) Specifics A specific example is Takki Roll 250 (manufactured by Nichikagaku Kogyo Co., Ltd.).

Furthermore, an alkylphenol resin is a compound in which Z is a hydrogen atom or an alkyl group in the formula (II+), and is a tackifier, but when a halogen donor described below coexists with it, like a halogenated alkylphenol resin, E
Acts as a vulcanizing agent for PDM and butyl rubber.

Specific examples include Hytanol 2501 (manufactured by Hitachi Chemical Co., Ltd.).

Vulcanization with a halogenated alkylphenol resin or alkylphenol resin is performed by dehydration condensation occurring at the methylol group during heating, and at this time, crosslinking occurs at the unsaturated moieties in EPDM or butyl rubber.

The halogen donor is an essential activator for the alkylphenol resin to function as a resin vulcanizing agent.

Specific examples include tin chloride, chlorinated polyethylene, and chlorosulfonated polyethylene.

The organic peroxide-based vulcanizing agent acts as a vulcanizing agent for EPDM.

The organic peroxide-based vulcanizing agent used in the present invention may be any vulcanizing agent as long as the crosslinking reaction does not proceed to an extreme extent at the temperature during processing, but preferably dialkyl vulcanizing agents have a temperature of 100°C or higher at which the half-life is 1 hour. Peroxide is fine.

Specifically, dicumyl peroxide, 13-bis(t
-butylperoxyisopropyl)benzene, 4.4-
di-t-butylperoxyvalerate n-butyl, 2,5-
Examples include dimethyl-2,5-di(t-butylperoxy)hexane.

The content ratios of the above components contained in the adhesive rubber composition of the present invention are as follows.

Raw material rubber contains EPDM and butyl rubber,
EPDM is 60 to 90 parts by weight in 100 parts by weight of raw rubber, and the remainder is butyl rubber. If the EPDM is less than 60 parts by weight, the adhesive strength with the organic peroxide-vulcanized EPDM rubber composition, which is one of the adherends, will be poor after vulcanization.
If the amount exceeds 90 parts by weight, the adhesiveness of the adhesive rubber composition itself will be poor, so that the adhesive for vulcanization of the organic peroxide-vulcanized EPDM rubber composition and metal may not be treated before vulcanization. Poor adhesion to metals.

The amount of halogenated alkylphenol resin or alkylphenol resin is 5 to 20 parts by weight per 100 parts by weight of raw material rubber.
Contain part by weight. If the amount is less than 5 parts by weight, the desired adhesion between the organic peroxide vulcanized EPDM rubber composition and the metal treated with the adhesive for vulcanization adhesion to metal cannot be obtained during unvulcanization; In addition, because the resin vulcanization of butyl rubber is not performed sufficiently, the adhesion to metal after vulcanization is poor. On the other hand, if it exceeds 20 parts by weight, the adhesive rubber composition will stick to mill rolls during mixing or rolling, resulting in poor workability and processability.

When an alkylphenol resin is used, a halogen donor is also included. It is preferable that the halogen donor is contained in an amount equivalent to or more with respect to the alkaline phenol resin,
It may be in excess. To give concrete numbers, when using an inorganic substance such as tin chloride as a halogen donor, 1 to 2 parts by weight per 100 parts by weight of raw material rubber, and when using an organic substance such as chlorinated polyethylene, 10 parts by weight per 100 parts by weight of raw material rubber.
It is preferably 5 to 10 parts by weight relative to 0 parts by weight.

The organic peroxide-based vulcanizing agent is preferably contained in a net amount of 0,005 to 0.020 mol per 100 parts by weight of the raw rubber. Within this range, vulcanization progresses appropriately.

The adhesive rubber composition of the present invention contains the above-mentioned components, and in addition, vulcanization aids, anti-aging agents, softeners such as process oil, fillers such as carbon black, etc. There is no problem in including it within a range that does not impair it.

The second aspect of the present invention contains EPDM, butyl rubber, a halogenated alkylphenol resin, or an alkylphenol resin and a halogen donor, and an organic peroxide-based vulcanizing agent as a solid content, and the solid content is 10 to 25% by weight. % adhesive cement composition.

The above-mentioned essential components contained in the adhesive cement composition of the present invention are as described above, but in addition to these, a solvent is always contained. The solvent used here may be any solvent as long as it can dissolve the rubber and is volatile, and specific examples include toluene and xylene.

Further, the adhesive cement composition of the present invention may contain a vulcanization aid, an anti-aging agent, a softener, a filler, etc. in addition to the above-mentioned essential components.

The content ratios of the components contained in the adhesive cement composition of the present invention are as follows.

The raw rubber is the same as the adhesive rubber composition described in the first embodiment, and EPDM is contained in 60 to 100 parts by weight of the raw rubber.
The amount is 90 parts by weight, and the remainder is butyl rubber.

The amount of halogenated alkylphenol resin or alkylphenol resin is 5 to 50 parts by weight per 100 parts by weight of raw material rubber.
Contain part by weight. If the amount is less than 5 parts by weight, the desired adhesion between the organic peroxide vulcanized EPDM rubber composition and the metal treated with the adhesive for vulcanization adhesion to metal cannot be obtained when unvulcanized; If the amount exceeds parts by weight, the solid content remaining after the solvent in the cement composition is volatilized will have no stickiness, which is not preferable.

When using an alkylphenol resin, the halogen donor to be contained is preferably contained in an amount equivalent to or more than the alkylphenol resin, and when using an inorganic substance such as tin chloride, 1 to 2 parts by weight per 100 parts by weight of raw rubber, When using an organic substance such as chlorinated polyethylene, it is preferably contained in 5 to 10 parts by weight based on 100 parts by weight of raw rubber.

The organic peroxide-based vulcanizing agent is preferably contained in a net amount of 0.005 to 0.020 parts by mole per 100 parts by weight of the raw rubber. Within this range, vulcanization progresses appropriately.

Further, the adhesive cement composition of the present invention has a solid content of 10
Contains ~25% by weight. Here, the solid content refers to all components except the solvent in the cement composition. If the solid content is less than 10% by weight, the cement composition must be coated multiple times in order to obtain sufficient adhesive strength, resulting in poor productivity. On the other hand, if it exceeds 25% by weight, the viscosity of the cement composition becomes high, making it difficult to apply and having poor workability.

A third aspect of the present invention provides the adhesive rubber composition and/or
Alternatively, the present invention provides a method for adhering an organic peroxide vulcanized EPDM rubber composition using the adhesive cement composition and a metal treated with an adhesive for vulcanization adhesion between the rubber composition and metal. be.

That is, the adhesive rubber composition is placed on a metal that has been treated with an adhesive for vulcanization of an organic peroxide-vulcanized EPDM rubber composition and metal, and then unvulcanized organic peroxide is applied to the metal. Vulcanized EP
A method of disposing a DM rubber composition and performing vulcanization adhesion (Method 1)
), the adhesive cement composition is applied to the metal treated with the adhesive for vulcanization of the organic peroxide vulcanized EPDM rubber composition and the metal, and the unvulcanized organic peroxide is applied to the metal. A method of disposing a vulcanized EPDM rubber composition and performing vulcanization adhesion (Method 2), a method in which a vulcanized EPDM rubber composition is placed on the metal treated with an adhesive for vulcanization adhesion between the organic peroxide vulcanized EPDM rubber composition and the metal, The adhesive cement composition is applied, the adhesive rubber composition is placed thereon, and then unvulcanized organic peroxide is added! ijt E
A method of disposing a PDM rubber composition and performing vulcanization adhesion (
Method 3).

Here, disposing the adhesive rubber composition or the sensitive peroxide vulcanized EPDM rubber composition as the adherend means forming the rubber composition into a sheet and pasting it.

Further, the adhesive cement composition may be applied by a conventional method such as a printing method, a rolling method, or the like.

Vulcanization is done by hot water vulcanization, steam vulcanization, etc. at a temperature of 140~
160°C, pressure 2.6-18. Ok g/cm
It may be carried out for about 60 to 240 minutes under the conditions of '.

The metal to which the method of the present invention is applied is one of the adherends,
It may be made of any metal, such as stainless steel, iron, aluminum, etc.

Adhesives for treating metals are adhesives for vulcanization of organic peroxide vulcanized EPDM rubber compositions and metals, such as Metalloc P (manufactured by Toyo Kagaku Kenkyusho Co., Ltd.) and Metallocutta FB (manufactured by Toyo Kagaku Kenkyusho Co., Ltd.). (manufactured by Toyo Kagaku Kenkyusho Co., Ltd.), Chemrock 205
(manufactured by Lord Far East Co., Ltd.), Chemlock 2
Phenolic adhesives such as 46 (manufactured by Lord Far East Co., Ltd.) are commercially available, and these may be used.

Further, the treatment of metal with an adhesive herein refers to applying an adhesive to the surface of the metal to be adhered by a method such as a printing method or a roll method.

The organic peroxide vulcanized EPDM rubber composition, which is the other adherend to which the method of the present invention is applied, contains E as an essential component.
This is a rubber composition containing PDM and an organic peroxide-based vulcanizing agent. Here, the EPDM-based rubber composition is not limited to one in which all the raw rubber contained in this rubber composition is EPDM, but 70% by weight or more of the raw rubber is EPDM.
refers to something that is. Other raw rubbers to be blended into EPDM include SBR, NR, and the like.

Note that the EPDM and the organic peroxide-based vulcanizing agent are as described above in the section of the adhesive rubber composition.

Further, the organic peroxide vulcanized EPDM rubber composition may contain commonly used vulcanization aids, desensitizers, fillers, etc., as necessary.

The bonding method of the present invention, as shown in Methods 1 to 3,
A metal treated with an adhesive for vulcanization adhesion between an organic peroxide vulcanized EPDM rubber composition and a metal and an unvulcanized organic peroxide vulcanized EPDM rubber composition are used as adherends. In this method, the adhesive rubber composition of the present invention and/or the adhesive cement composition of the present invention are placed between the adherends, and vulcanization bonding is performed. The cement composition contains butyl rubber as a raw material rubber,
Furthermore, since it contains a tackifier, halogenated alkylphenol resin or alkylphenol resin, it has tackiness, and therefore, before vulcanization,
Organic peroxide vulcanization EP as described as conventional method
Means for preventing peeling of an unvulcanized organic peroxide-vulcanized EPDM rubber composition from a metal treated with an adhesive for vulcanization adhesion between a DM rubber composition and a metal (tightening with a rope, etc.) There is no need to crimp and bolt the side plates.

In addition, vulcanization of EPDM with an organic peroxide-based vulcanizing agent,
This is done simultaneously (co-vulcanization) with the breeding peroxide vulcanized EPDM rubber composition that is the adherend and the adhesive rubber composition and/or the adhesive cement composition. Together with the butyl rubber contained in the product or adhesive cement compound, the metal-rubber composite is integrated by vulcanization, as it also undergoes resin vulcanization with a halogenated alkylphenol resin, or an alkylphenol resin and a halogen donor.

The vulcanization adhesion between iron treated with a phenolic adhesive and an organic peroxide vulcanized EPDM rubber composition was performed using a conventional cement composition of an organic peroxide vulcanized EPDM rubber composition. The tackiness before vulcanization and the tackiness after vulcanization were evaluated using the method of the present invention and are shown in Table 1.

table ■ <Example> EXAMPLES The present invention will be specifically explained below with reference to Examples.

(Example 1) Two types of phenolic adhesives (Chemrock 2) were added to SS-41.
05 and Chemlock 246 (both manufactured by Lord Far East Co., Ltd.) were sequentially applied, and on top of that, a cement composition, which is a co-cement for the rubber composition that is the adherend and whose formulation is shown in Table 2, was applied. Table 3 with or without coating
A sheet made of an organic peroxide vulcanized EPDM-based rubber composition having the formulation shown in Figure 1 was pressure-bonded. Regarding this, the tackiness was measured and evaluated by the following method. Next, the above metal-
The rubber composite was press-vulcanized at 160° C. for 60 minutes, and the vulcanized metal-rubber composite was subjected to an adhesion test using the method described below. The results are shown in Table 5.

(Measurement and evaluation method of tackiness when unvulcanized) The following two methods were used.

(2) A rubber sheet was pressure-bonded to Picmatac phenolic adhesive-treated 5S-41 for 20 seconds with a load of 500 g.

This was peeled off at 20° C. and at a peeling speed of 30 mm/mir+ using a Pikmatac meter manufactured by Toyo Seiki Co., Ltd.

(2) Qualitative Evaluation A rubber sheet was pressed onto the phenolic adhesive treated 5S-41 using a rubber stitcher roll, and its tackiness was qualitatively evaluated using the following criteria.

◎; Strongly adhered. If you try to remove it by hand, the rubber will break.

○: Adhesive. If you try to remove it by hand, the rubber will come off without cutting.

△: Adhesive, but can be easily removed by hand.

×: Adhesive, but peels off under its own weight.

XX: No adhesion at all.

(Method for measuring adhesion after vulcanization) In the case of metal-rubber, the metal-rubber composite after vulcanization was measured using an autograph at 20°C.
90" and 471J peeling was performed at a peeling speed of 50 mm/min at .degree.

The force when the rubber layer peels off from the metal (kgf/1nc
h) was measured, and the distortion of the rubber attached to the metal surface (with rubber) was measured.
is shown in %. Note that 0% with rubber means an interface separation of ¥1''.

(Example 2) Two types of phenolic adhesives (Metalloc P
and Metalotsutta FB, both Toyo Kagaku Kenkyusho Co., Ltd.
Co-cement of the adhesive rubber composition, the formulation of which is shown in Table 2, is applied on top of the cement composition, and then the adhesive rubber composition whose composition is shown in Table 4 is applied. It was crimped. Regarding this, the tackiness before vulcanization was measured and evaluated in the same manner as in Example 1, vulcanization was performed, and an adhesion test after vulcanization was conducted. The results are shown in Table 6.

Separately, the adhesive rubber composition used here (Example 2) and a sheet made of an organic peroxide vulcanized EPDM rubber composition (B-1) whose formulation is shown in Table 3 are bonded together, Vulcanization was performed in the same manner as in Example 1, and an adhesion test was conducted using the method described below.

The results are shown in Table 7.

(Method for measuring adhesion after vulcanization) In the case of rubber-rubber, the rubber-rubber composite after vulcanization was measured using an autograph at 20
180° peeling was performed at a peeling rate of 50 mm/min at .

The force (kgf/1 nch) when the rubber layers were peeled off from each other was measured, and the M (with rubber) of the other rubber adhering to the surface of one rubber layer was expressed in %.

(Example 3) Two types of phenolic adhesives (Metalloc P and Metalloc FB, both manufactured by Toyo Kagaku Kenkyusho Co., Ltd.) were sequentially applied to SS 41, and on top of that, the cement composition whose formulation is shown in Table 2 was applied. An adhesive rubber composition (C-7) whose composition is shown in Table 4 was pressure-bonded with or without coating. Regarding this, the tackiness before vulcanization was measured and evaluated in the same manner as in Example 1, vulcanization was performed, and an adhesion test after vulcanization was conducted. The results are shown in Table 8.

(Example 4) Two types of phenolic adhesives (Metalloc P
and Metalloc FB, both manufactured by Toyo (Higaku Kenkyusho Co., Ltd.), were applied sequentially, and then the cement composition shown in Table 2 with or without application was applied, and the composition shown in Table 3 was applied. The organic peroxide vulcanized EPDM rubber composition shown (B-1
) was pressed together. Regarding this, the tackiness before vulcanization was measured and evaluated in the same manner as in Example 1, vulcanization was performed, and an adhesion test after vulcanization was conducted. The results are shown in Table 9.

(Name) Nisblen 305 JSREP-24 exonbutyl 268 FEF carbon (I60) SRF carbon (I50) EP-30 Takki Roll 130G Escolettes 1102 Takki Roll 250 Polybutene HV-300 MPMA W-90 Parkadox I4 [Combination (Manufacturer salt) sumitomo chemical industry japanese synthetic rubber Exxon chew, Go.

Asahi Ka-bon Asahi Ka-bon Sumitomo Chemical Sumitomo Chemical Esso Kagaku Nichi Kagaku Kogyo Nippon Petrochemical Mitsubishi Rayon Idemitsu Koko Sankayaku Nuri raw material explanation] (Chemical composition, etc.) Mooney viscosity (ML, (100℃) 62, iodine value 1
8 Mooney viscosity (ML, 100℃) 67, iodine value 14 Mooney viscosity (ML1*6' 125℃) 51,
Unsaturation degree 1.5111 or 1% carbon black carbon black alkylphenol/aldehyde resin alkylphenol/formaldehyde resin paraffin resin brominated alkylphenol/formaldehyde resin polybutene trimethylolpropane trimethacrylate baraffin oil bis(t-butylperoxyisopropyl) Hensen Example 1 In the vulcanization adhesion between 5S-41 and a sheet made of an organic peroxide-vulcanized EPDM-based rubber composition, the adhesion of the organic peroxide-vulcanized EPDM-based rubber composition (B-1) when unvulcanized was determined. In order to compensate for the lack of properties, a tackifier is added to the rubber composition (B-2 to B-6), and a co-cement composition of the rubber composition (A-1 to B-6) is added between the adherends. The case where A-6) was applied was studied. In addition, this is
This is a commonly used countermeasure when adhering a rubber composition to another adherend when the adhesiveness of the rubber composition is insufficient.

As is clear from Table 5, the rubber composition (B
-1) When the co-cement composition (A-1) is applied,
The tackiness before vulcanization and the adhesion after vulcanization are higher than when no cement composition is applied (Reference Example 1), but
It was not sufficient (Comparative Example 1). In addition, a tackifier is added to the rubber composition that is the adherend (B-2 to
B-6) However, even if the co-cement compositions (A-2 to A-6) were applied, the unvulcanized adhesion was not sufficiently improved;
To make matters worse, the adhesiveness after vulcanization was significantly reduced (Comparative Examples 2 to 6).

Example 2 shows the adhesive rubber composition and cement composition placed between adherends when vulcanizing and adhering 5S-41 and a sheet made of an organic peroxide vulcanized EPDM rubber composition (B-1). This is a study of the composition of the product.

As is clear from Tables 6 and 7, the compositions (C-5, A-11) shown as examples of the present invention are used as the adhesive rubber composition and the cement composition (Example 1 of the present invention).
The tackiness before vulcanization and the adhesion after vulcanization were excellent.

On the other hand, even if the adhesive rubber composition and the cement composition contain EPDM and butyl rubber as raw material rubber, the tackifier is other than Tackyroll 250 (halogenated alkylphenol resin) (C- 1~C
-4, A-7 to A-10), the unvulcanized adhesion between 5S-41 and the adhesive rubber composition is improved, but the adhesion after vulcanization is significantly reduced. (Comparative Examples 7-1
0). This includes formulations A-7 to A-10 and formulation C-
The tackifier (resin) contained in 1 to C-4 is EP
This is because resin vulcanization of DM and butyl rubber cannot be performed.

Furthermore, even when Tackirol 250 is contained in the adhesive rubber composition and the cement composition, the ratio of EPDM to butyl rubber deviates from the range shown in the present invention (C-6,
A-12), the unvulcanized adhesion and the post-vulcanized adhesion between 5S-41 and the adhesive rubber composition are improved; The adhesive strength after vulcanization with the rubber composition (B-1) as the adherend was significantly reduced (Comparative Example 11). This is because the butyl rubber content in Formulation C-6 is high, so after vulcanization, the rubber composition (B
This is because the affinity with -1) is insufficient.

Example 3 shows the case where the adhesive rubber composition (C-7) of the present invention is placed between adherends during vulcanization adhesion between 5S-41 and an organic peroxide vulcanized EPDM rubber composition. This paper examines the necessity of cement compositions and the content of halogenated alkylphenol resins in cement compositions.

As is clear from Table 8, the adhesive rubber composition (C-7) of the present invention has sufficient adhesion for practical use (unadded) even without the use of a cement composition. (during vulcanization) and adhesion (after vulcanization) were obtained (Invention Example 2).

In addition, when a cement composition is applied, the content of the halogenated alkylphenol resin in the cement composition is within the range shown for the adhesive cement composition of the present invention (A-
13 to A-16), the unvulcanized adhesion was further increased than the case without the cement composition (invention example 2), and the post-vulcanized adhesion was equivalent and sufficient. (Invention example 3~
6).

Example 4 shows the cement composition when only the cement composition is placed between the adherends during vulcanization adhesion of 5S-41 and a sheet made of organic peroxide vulcanized EPDM rubber composition (B-1). This study investigated the content of halogenated alkylphenol resin in the composition.

As is clear from Table 9, when the halogenated alkylphenol resin content is within the range shown for the adhesive cement composition of the present invention (A-13 to A-16), no adhesive rubber composition is used. Also, the unvulcanized tackiness and post-vulcanized adhesion of 5S-41 and a sheet made of organic peroxide vulcanized EPDM rubber composition (B-1) are practically sufficient. (Invention Examples 7 to 10).

<Effects of the Invention> The present invention provides an adhesive useful for vulcanization adhesion between an organic peroxide vulcanized EPDM rubber composition and a metal treated with an adhesive for vulcanization adhesion between the rubber composition and metal. A composition for use is provided.

The present invention also provides a method for adhering an organic peroxide vulcanized EPDM rubber composition to a metal treated with an adhesive for vulcanization adhesion between the rubber composition and metal.

The present invention eliminates the need for the conventional work (tightening with ropes, fastening with bolts, etc.) to prevent the rubber composition from peeling off from the metal during unvulcanization, so productivity is significantly improved. .

[Brief explanation of the drawing]

Figures 1 and 2 show that when a sheet made of an organic peroxide vulcanized EPDM rubber composition is vulcanized and bonded to a metal core, the sheet is bonded to the metal core before vulcanization. FIG. 3 is a partially sectional side view showing a state of bolt tightening performed for the purpose of preventing peeling off from the holder. Explanation of symbols 1... core body, 2... rubber sheet, 3... side plate, 4... bolt, 5... hole FIG. FIG.2

Claims (5)

[Claims] (1) Adhesive used for vulcanization bonding between an organic peroxide vulcanized ethylene/propylene/diene ternary copolymer rubber composition and a metal treated with an adhesive for vulcanization bonding between the rubber composition and metal. 60 to 90 parts by weight of ethylene-propylene-diene ternary copolymer rubber and 40 to 40 parts by weight of butyl rubber.
It contains 5 to 20 parts by weight of a halogenated alkylphenol resin, or 5 to 20 parts by weight of an alkylphenol resin and a halogen donor, based on 100 parts by weight of raw material rubber consisting of 10 parts by weight, and further contains an organic peroxide-based vulcanizing agent. An adhesive rubber composition comprising: (2) Adhesive used for vulcanization adhesion between an organic peroxide vulcanized ethylene/propylene/diene ternary copolymer rubber composition and a metal treated with an adhesive for vulcanization adhesion between the rubber composition and metal. 100 parts by weight of raw material rubber consisting of 60 to 90 parts by weight of ethylene-propylene-diene ternary copolymer rubber and 40 to 10 parts by weight of butyl rubber, as solid contents.
5 to 5 parts by weight of halogenated alkylphenol resin
It is characterized by containing 50 parts by weight or 5 to 50 parts by weight of an alkylphenol resin and a halogen donor, further containing an organic peroxide-based vulcanizing agent, and having a solid content of 10 to 25% by weight. Cement composition for adhesion. (3) When vulcanizing and adhering an organic peroxide vulcanized ethylene/propylene/diene ternary copolymer rubber composition to a metal treated with an adhesive for vulcanizing the rubber composition and metal, Between the vulcanized organic peroxide vulcanized ethylene/propylene/diene ternary copolymer rubber composition and the metal treated with an adhesive for vulcanization adhesion between the rubber composition and metal, claim 1 An adhesion method characterized by performing vulcanization adhesion after disposing the adhesive rubber composition described in . (4) When vulcanizing and adhering an organic peroxide vulcanized ethylene/propylene/diene ternary copolymer rubber composition to a metal treated with an adhesive for vulcanizing the rubber composition and metal, Between the vulcanized organic peroxide vulcanized ethylene/propylene/diene ternary copolymer rubber composition and the metal treated with an adhesive for vulcanization adhesion between the rubber composition and metal, as claimed in claim 2, An adhesion method characterized by performing vulcanization adhesion after disposing the adhesive cement composition described in . (5) When vulcanizing and adhering an organic peroxide vulcanized ethylene/propylene/diene ternary copolymer rubber composition to a metal treated with an adhesive for vulcanizing the rubber composition and metal, A rubber composition between an organic peroxide vulcanized ethylene-propylene-diene terpolymer rubber composition and a metal treated with an adhesive for vulcanization adhesion between the rubber composition and metal. An adhesive characterized in that the rubber composition for adhesive according to claim 1 is disposed on the side, and the cement composition for adhesive according to claim 2 is disposed on the metal side, and then vulcanization bonding is performed. Method.