JP2002220481A - Production method for composite of rubber and supporter, and its composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new production method for a composite of a rubber and a supporter, useful for a vibrationproof rubber, an isolating rubber and the like, and capable of easily obtaining, wherein the rubber and the supporter such as a metal are strongly adhered. SOLUTION: The composite of the rubber and the supporter is obtained by adhering the rubber and the supporter using glycidylperoxide, and this composite obtained is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber-support composite such as a rubber-metal composite.

[0002]

2. Description of the Related Art Anti-vibration rubber used for mounting an engine of an automobile or the like includes vibration-proofing performance for reducing engine vibration and accompanying noise, heat resistance to heat generated by the engine, and mechanically securing the engine. In addition to the supporting performance (strength) to support, strong adhesion to a vibration-proof rubber support such as a metal material is required.

[0003] Conventionally, adhesion between a vibration-isolating rubber and a support such as a metal is performed by applying an undercoating adhesive and an overcoating adhesive to a degreased metal and then directly vulcanizing the unvulcanized rubber on the metal. Have been done. However, in this method, since an organic solvent is used for applying the adhesive, there are problems in work safety, occupational health, and environment. It is conceivable to use an aqueous adhesive as the adhesive, but there is a disadvantage that drying takes longer than an organic solvent, which is economically disadvantageous. In addition, when these adhesives are used, there is also a problem that quality is deteriorated due to unevenness in film thickness when the adhesive is applied.

[0004] In order to solve these problems, a composite method of bonding rubber and metal without using an adhesive has been proposed. For example, a method is known in which degreased metal is plated with brass or galvanized, and a rubber composition containing an organic salt of cobalt such as cobalt naphthenate is used, and a method of directly vulcanizing and bonding the metal with sulfur is known. . However, this method has a problem that it is necessary to plate the metal, the operation becomes complicated, and the cost increases. It has also been proposed that a metal surface be treated with an alkali, and a rubber composition containing a silane coupling agent and an organic peroxide be vulcanized and molded to obtain a composite (Japanese Patent Application Laid-Open No. HEI 1-1990).
However, it is necessary to wash with water after alkali washing, and it is disadvantageous in terms of time and cost when further drying is considered.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in a rubber-support composite and to achieve good adhesion between rubber and metal by an easy method without using an adhesive. It is to provide a complex.

[0006]

Means for Solving the Problems The present inventors have found that, in a method for cross-linking and bonding a rubber composition, the use of glycidyl peroxide enables good adhesion between the rubber and the support. It was completed.

That is, the present invention provides: (1) a method for producing a rubber / support composite, wherein the rubber and the support are bonded using glycidyl peroxide. (2) The method for producing a rubber / support composite according to the above (1), wherein the rubber is an uncrosslinked rubber and the support is a metal.

(3) The glycidyl peroxide has the following general formula (1)

Embedded image (In the formula, n represents an integer of 1 or 2, R ₁ and R ₂ are lower alkyl groups having 1 to 3 carbon atoms, and R ₃ represents a hydrocarbon group having 1 to 10 carbon atoms when n is 1. And when n is 2, R ₃ represents a divalent C 1 to C 6 bridging group, and when the bridging group is a phenylene group or a cyclohexylene group, R ₃ is substituted with a C 1 to C ₃ alkyl group. (1) or (2), wherein the glycidyl peroxide is represented by the formula (1).

(4) When the glycidyl peroxide of the general formula (1) is n = 1 in the general formula (1), R is a phenyl group, a cyclohexyl group, a linear or branched alkyl having 1 to 5 carbon atoms. A phenyl group substituted by an alkyl group having 1 to 3 carbon atoms, and when n = 2, R is a glycidyl peroxide which is an ethylene group, an ethynylene group, an m- or p-phenylene group or a cyclohexylene group. A method for producing a rubber-support composite according to one of the above items (2) and (3). (5) The rubber according to the above (4), wherein the glycidyl peroxide is t-butyl glycidyl peroxide.
A method for producing a support composite. (6) A rubber-support composite in which a rubber and a support are bonded using glycidyl peroxide. (7) A rubber composition containing glycidyl peroxide. It is.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. According to the method of the present invention, in order to manufacture a rubber-support composite by bonding rubber and a support, a rubber composition containing glycidyl peroxide is usually closely adhered onto a support and crosslinked by a conventional method. I just need.

The glycidyl peroxide which can be used in the present invention is not particularly limited, but has a molecular weight of 133 to 42.
About 1 is preferable, and glycidyl peroxide represented by the general formula (1) is usually used. The glycidyl peroxide is known in Japanese Patent Application Laid-Open No. 5-97912 and the like.

[0012]

Embedded image

(Wherein n, R ₁ , R ₂ and R ₃ have the same meanings as described above), and can be easily synthesized by reacting with a hydroperoxide represented by the formula:

As examples of the glycidyl peroxide represented by the general formula (1), when n = 1, t-butyl glycidyl peroxide, t-amyl glycidyl peroxide, t-hexyl glycidyl peroxide,
1,1,2-trimethylpropyl glycidyl peroxide, 1,1,2,2-tetramethylpropyl glycidyl peroxide, cumyl glycidyl peroxide,
m-Isopropylcumylglycidyl peroxide and the like. When n = 2, 2,4-dimethyl-2,
4-bis (glycidylperoxy) hexane, 2,4-
Dimethyl-2,4-bis (glycidylperoxy) hexyne-3, p-bis (1-methyl-1-glycidylperoxyethyl) benzene, m-bis (1-methyl-1-)
(Glycidyl peroxyethyl) benzene and the like.

The use amount of these glycidyl peroxides is 0.5% or more (mass%: hereinafter the same unless otherwise specified), usually 1% or more, preferably 2% or more, based on the whole rubber composition. It is preferably at least 3%, and the upper limit is at most 20%, depending on the hardness of the target rubber.
Preferably it is 10% or less. 4% to 8 at the moment
% Is considered optimal.

The glycidyl peroxide can be used in combination with another organic peroxide. As peroxides that can be used in combination, for example, dicumyl peroxide, di-t-butyl peroxide, 2,4-dimethyl 2,4-
Dialkyl peroxides such as bis (t-butylperoxy) hexane; diacyl peroxides such as dibenzoyl peroxide and di (4-methylbenzoyl) peroxide; 1,1-bis (t-butylperoxy) 3 Peroxyketals such as 2,3,5-trimethylcyclohexane, peresters such as tert-butylperoxybenzoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxy-2-ethylhexyl carbonate, etc. Percarbonates. When these are used in combination, the amount used is 0.5% to 1% based on the whole rubber composition of the present invention.
It is about 0%.

The rubber used in the present invention may be either natural rubber (NR) or synthetic rubber, and an uncrosslinked rubber is usually used as the rubber to be adhered to the support. As synthetic rubber, ethylene-propylene rubber (EPM),
Ethylene-propylene-non-conjugated diene copolymer rubber (E
Olefin rubber such as PDM), butadiene rubber (B
R), chloroprene rubber (CR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (H-NBR), and the like. In these, E
Olefin rubber such as PDM and EPM and H-NBR are suitable for use as a vibration-proof rubber-metal composite.

The non-conjugated diene component contained in EPDM is
For example, 1,4-pentadiene, 1,5-hexadiene,
2,5-dimethyl-1,5-hexadiene and 1,4-
Octadiene and cyclic dienes such as 1,4-cyclohexadiene, cyclooctadiene and dicyclopentadiene, for example, 5-ethylidene-2-norbornene,
Alkenyl norbornene, such as butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene. Among the above-mentioned dienes, dicyclopentadiene, 5-ethylidene-2-norbornene and the like are preferable. H-NBR is
Acrylonitrile-butadiene rubber (NBR) obtained by polymerizing butadiene and acrylonitrile has been subjected to a hydrogenation treatment. EPD among the above synthetic rubbers
M can be particularly preferably used.

The rubber used in the present invention includes, in addition to the rubber component of the rubber polymer or natural rubber, a reinforcing agent such as carbon black, a co-crosslinking agent, which has been conventionally used as an additive for rubber. It may contain a crosslinking aid, a softening agent, a processing aid, an antioxidant, a filler, a silane coupling agent, and the like, and usually contains these rubber additives.

The rubber composition containing glycidyl peroxide of the present invention may be produced by any method, but is usually prepared from the rubber component of the rubber polymer or natural rubber and the rubber additive. It is preferably obtained by additionally mixing glycidyl peroxide and, if necessary, another organic peroxide with a rubber prepared by a conventional method. That is, after preliminarily mixing the rubber polymer of the rubber or the rubber component of the natural rubber and the additives, kneading is performed at 80 to 140 ° C. for several minutes. The obtained kneaded material is further mixed with glycidyl peroxide and, if necessary, another organic peroxide using a roll, and kneaded at a roll temperature of 40 to 70 ° C. for 5 to 30 minutes to obtain a rubber composition. Can be obtained.

The support used in the composite of the present invention is not particularly limited, and is not particularly limited as long as it is suitable as a support for a rubber composite, such as metal, plastic, stone, and wood. Usually, metal is most widely used and used as a metal-rubber composite. The metal for the support is not limited, but specific examples of metals suitable for use as a vibration-proof rubber-metal composite include iron, aluminum, and alloys thereof. Examples of the alloy include a steel material (carbon steel, stainless steel, etc.), an aluminum alloy, and the like.

Adhesion between the rubber composition containing glycidyl peroxide and the support is achieved by bringing the rubber composition containing glycidyl peroxide into close contact with the support and then crosslinking the rubber composition. . When the support is a metal, on a metal that has been subjected to normal degreasing treatment, preferably a preformed rubber composition is compression-molded, extrusion-molded, transfer-molded, extruded by injection molding or the like, and pressed into contact.
After that, it is crosslinked by heating. The crosslinking temperature is usually 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 135 ° C.
Above, it is usually 200 ° C. or lower, preferably 180 ° C. or lower. The crosslinking time is usually at least 1 minute, preferably at least 3 minutes, usually at most 90 minutes, preferably at most 60 minutes, more preferably at most 40 minutes. Even when the support is made of a material other than metal, the rubber composition and the support can be bonded in the same manner as in the case of the metal. The thus obtained rubber-support composite of the present invention can be used for weather strips, gaskets, sealing materials, seismic isolation rubbers and the like.

[0023]

The present invention will be described below with reference to examples and comparative examples, but these are only for illustration and do not limit the present invention. In Examples and Comparative Examples, “parts” represents parts by mass. The adhesion test was performed according to JIS K6031 by a 90 ° peel test. That is, a bonded sample of rubber and metal was peeled off at a rate of 50 ± 2.5 mm / min by applying a tensile load, and the adhesive strength was measured. The results are tabulated.

Embodiment 1 FIG. After the natural rubber (NR) component is kneaded with an open roll, it is kneaded with the following composition to prepare a rubber composition containing glycidyl peroxide, and hot-plate pressed on a degreased 140 ° C. steel plate. The crosslinking was carried out for an optimum crosslinking time (30 minutes) determined by a curast meter to prepare a rubber / steel plate composite.

NR 100 Stearic acid 2 Zinc oxide 5 Dibenzothiazyl disulfide 1 Sulfur 2.5 TBGPO 5

Comparative Example 1 The TBGPO of Example 1 is replaced with DCP
The evaluation was performed in the same manner except that the above was replaced.

Example 2 An ethylene-propylene-non-conjugated diene copolymer polymer (EPDM) (uncrosslinked product) was kneaded with an open roll, kneaded with the following composition, and a rubber composition containing glycidyl peroxide. The product was prepared and degreased at 160 ° C
Hot-pressed on the steel plate of Example 1 and subjected to crosslinking for an optimum crosslinking time (30 minutes) determined with a curast meter to produce a rubber-steel plate composite.

EPDM 100 Stearic acid 2 Zinc oxide 5 2-Mercaptobenzothiazole 0.5 Tetramethylthiuram disulfide 0.5 Sulfur 2.5 TBGPO 5

Comparative Example 2 Evaluation was made in the same manner as in Example 2 except that TBGPO was changed to DCP.

Table 1 Adhesion Test Results Example 1 Comparative Example 1 Example 2 Comparative Example 2 Adhesive Strength (kgf / cm) 1.05 0.09 3.04 No Adhesion

Notes (1) In Examples 1 and 2, the rubber was broken before peeling occurred. (2) Raw material used NR: natural rubber (trade name: SMR CV-60) EPDM: ethylene-propylene-non-conjugated diene copolymer polymer (trade name: ethylene-propylene-terpolymer EP-24 Nippon Synthetic Rubber Co., Ltd.) TBGPO: t-butyl glycidyl peroxide (Title: Kayabutyl EP Neat, manufactured by Kayaku Akzo Co., Ltd.) DCP: Dicumyl peroxide (trade name: Kayakumil D, manufactured by Kayaku Akzo Co., Ltd.) Commercial reagents were used.

[0032]

According to the method for producing a rubber-support composite of the present invention, the rubber-support composite of the present invention can be strongly bonded to a support such as rubber and metal only by crosslinking. It is particularly useful for anti-vibration rubber, seismic isolation rubber, and the like.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hiromichi Ohara 78F term of 436, Oji, Ube City, Yamaguchi Prefecture 3D035 CA05 4F071 AA10B AB06B AC08A AF19 AF58 AH07 AH19 CA01 CA07 CD03 CD07 4F100 AB01B AB03 AH02A AN00A AN01 AT00B BA02 BA07 EJ052 GB32 JB15A JH02 4J002 AC011 AC031 AC071 AC081 BB151 EK006 FD146 GM00

Claims (7)

[Claims] 1. A method for producing a rubber-support composite, comprising bonding a rubber and a support using glycidyl peroxide. 2. The method according to claim 1, wherein the rubber is an uncrosslinked rubber and the support is a metal. 3. Glycidyl peroxide is represented by the following general formula (1). (In the formula, n represents an integer of 1 or 2, R ₁ and R ₂ are lower alkyl groups having 1 to 3 carbon atoms, and R ₃ represents a hydrocarbon group having 1 to 10 carbon atoms when n is 1. And when n is 2, R ₃ represents a divalent C 1 to C 6 bridging group. When the bridging group is a phenylene group or a cyclohexylene group, R ₃ is substituted with a C 1 to C ₃ alkyl group. 3. The method for producing a rubber-support composite according to claim 1, wherein the glycidyl peroxide is represented by the following formula: 4. When the glycidyl peroxide of the general formula (1) is n = 1 in the general formula (1), R is a phenyl group,
A cyclohexyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group substituted by an alkyl group having 1 to 3 carbon atoms, and when n = 2, R is an ethylene group;
4. The method for producing a rubber-support composite according to claim 2, wherein the glycidyl peroxide is an ethynylene group, an m- or p-phenylene group, or a cyclohexylene group. 5. The method according to claim 4, wherein the glycidyl peroxide is t-butyl glycidyl peroxide. 6. A rubber / support composite wherein the rubber and the support are bonded using glycidyl peroxide. 7. A rubber composition containing glycidyl peroxide.