JPH07227936A - Rubber laminated article and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a rubber laminated article, in which a silicone rubber if fully crosslinked and, at the same time, main rubber and the silicone rubber are strongly and laminatingly bonded together and onto the main rubber side of which neither surface tackiness nor bloom develops, and its manufacturing method. CONSTITUTION:A rubber laminated article 1 is provided by laminatingly bonding a main rubber 12 and a silicone rubber 11 to each other. The main rubber 12 includes DCP based EPDM, chlorinated polyethylene or their mixture. Further, the main rubber 12 and the silicone rubber 11 are thermally crosslinked and, at the same time, the bond area 10 between both the rubbers is crosslinkingly bonded. Furthermore, other additive rubber component is added to and mixed with the main rubber 12. The preferable additive rubber component is one or two or more selected from the group consisting of ENB based EPDM, IR (or isoprene rubber), NBF (or butadiene-acrylonitrile rubber) or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber laminated product in which a silicone rubber and another synthetic rubber are laminated by cross-linking and adhering at the joint surface, and a method for producing the same.

[0002]

2. Description of the Related Art Silicone rubber comprises polymers and monomers whose main chain molecules are mainly composed of oxygen-silicon bonds. For this reason, the main chain molecule has characteristics different from those of general synthetic rubbers and the like, which mainly consist of polymers and monomers composed of carbon-carbon bonds. As the above features,
In addition to heat resistance due to the large binding energy of the main chain molecule, cold resistance, oxidation stability, weather resistance, etc. can be mentioned. In addition to this, it has advantages over other materials such as transparency and low toxicity. For this reason, conventional silicone rubber is used for construction joints, gaskets, daily necessities, electric wires, hoses,
Widely used in automobile parts and so on.

However, silicone rubber has the following drawbacks. That is, the bond angle of the main chain molecule is wider than that of synthetic rubber and the molecular structure cannot be densely packed, so the mechanical strength is weak. Therefore, it is difficult to use it for members that require durability. Also, the silicone rubber polymer, which is the raw material for silicone rubber, is very expensive. For this reason, normally, another inexpensive and excellent synthetic rubber or the like and silicone rubber are laminated and used as the laminated rubber.

In producing the above-mentioned laminated rubber, first, a first uncrosslinked mixture is prepared by mixing a silicone rubber polymer with a crosslinking agent composed of an organic peroxide or a platinum compound and additives such as a reinforcing agent. A second uncrosslinked mixture is prepared by mixing a synthetic rubber component with additives such as a crosslinking agent and a reinforcing agent. Then, the above two kinds of uncrosslinked mixtures are filled in a molding die in two layers. Alternatively, a two-layer molded product is produced using a crosshead extruder or the like. Next, heat is applied to the mold or the two-layer molded product to cause a cross-linking reaction in each uncross-linked mixture, and at the same time, both are cross-linked and bonded at their joint surfaces to form a laminated rubber.

By the way, sulfur or organic peroxide is used as a cross-linking agent to be mixed with the synthetic rubber component.
However, it is difficult to use the organic peroxide for the above purpose. That is, the crosslinking reaction using the above organic peroxide is a radical reaction. Basically, the radicals generated from the organic peroxide simultaneously proceed with the decomposition reaction of the rubber polymer constituted by the bonding of some rubber molecules and the crosslinking reaction between the rubber molecules. However, in the presence of oxygen, the decomposition reaction predominates over the crosslinking reaction.

Therefore, in the synthetic rubber which uses an organic peroxide as a cross-linking agent and is cross-linked in the air, the cross-linking between rubber molecules is not sufficiently performed. Therefore, the surface of the synthetic rubber becomes a rubber paste, or bloom occurs, which causes a problem. The above-mentioned bloom means that the uncrosslinked component in the synthetic rubber becomes white powder and floats on the surface. The synthetic rubber in which the above phenomenon occurs does not become an elastic body and is semi-solid. Therefore, sulfur is used as the cross-linking agent.

[0007]

However, sulfur has the effect of inhibiting the crosslinking reaction of the silicone rubber polymer.
For this reason, if sulfur is added to the synthetic rubber side during the production of the synthetic rubber, the sulfur may migrate to the silicone rubber side during crosslinking, and the silicone rubber may not be sufficiently crosslinked. As a result, the silicone rubber may be insufficiently cross-linked, and the cross-linking adhesion between the main rubber, which is a synthetic rubber, and the silicone rubber may be insufficient.

In view of the above problems, the present invention provides a rubber laminated product in which the silicone rubber is sufficiently crosslinked, the main rubber and the silicone rubber are firmly laminated and joined, and the main rubber is not sticky and bloom does not occur. It is intended to provide the manufacturing method.

[0009]

The present invention is a rubber laminated product obtained by laminating and bonding a main rubber and a silicone rubber, wherein the main rubber contains DCP EPDM, chlorinated polyethylene or a mixture of both, and The rubber laminate is characterized in that the rubber and the silicone rubber are each cross-linked with an organic peroxide, and the joint surfaces of the two are cross-linked.

Most notable in the present invention is that the main rubber contains DCP EPDM, chlorinated polyethylene, or a mixture of both. DCP EPD
M is an ethylene-propylene copolymer containing DCP (dicyclopentadiene) as the third component. The chlorinated polyethylene is a random chlorinated product produced by chlorine substitution reaction of polyethylene, and its structure is a three-component copolymer of ethylene, vinyl chloride and 1,2-dichloroethylene.

It is preferable to use the chlorinated polyethylene having a chlorine content of 25 to 45%. If the chlorine content is less than 25%, the properties are similar to those of polyethylene, and there is a possibility that the resin will not be an elastic body. If the content is more than 45%, the properties are similar to those of polyvinyl chloride, and there is a possibility that it will not become an elastic body.

To carry out the above-mentioned organic peroxide crosslinking and crosslinking adhesion, as will be described later, an organic peroxide crosslinking agent is applied to the main rubber, and an organic peroxide crosslinking agent or a platinum-based crosslinking agent is applied to the silicone rubber. Use agents. Examples of the organic peroxide crosslinking agent used for the silicone rubber include benzoyl peroxide, 1,1-diterebutylperoxy 3,3,5-trimethylcyclohexane, and dicumylperoxyside. Examples of the platinum-based crosslinking agent include chloroplatinic acid and alcohol-modified chloroplatinic acid. When the organic peroxide is cross-linked and the cross-linking is adhered, a normal pressure hot air heating furnace (H
AV), a fluidized bed heating furnace (LCM), a vulcanizer, etc. are preferably used.

It is preferable to add and mix other additive rubber components to the main rubber. Examples of the added rubber component include ENB EPDM, IR (isoprene rubber), NBR (butadiene acrylonitrile rubber),
SBR (styrene butadiene rubber), CSM (chlorosulfonated polyethylene), ACM (acrylic rubber), Q
One or more selected from the group of (silicone rubber), FKM (fluorine rubber) and U (urethane rubber). This improves the extrudability of the rubber laminate,
The advantage of faster cross-linking occurs.

Next, as the method for producing the rubber laminate, a first uncrosslinked mixture obtained by mixing the main rubber component, an organic peroxide crosslinking agent, and additives such as a reinforcing agent, and a silicone rubber polymer. And a second uncrosslinked mixture consisting of a silicone rubber cross-linking agent are laminated and molded into a desired shape to form a laminated molded article, and this laminated molded article is then crosslinked and crosslinked with organic peroxide in the presence of hot air. The method for producing a rubber laminated product is characterized in that the main rubber component comprises DCP EPDM, chlorinated polyethylene or a mixture of both.

Examples of the additives include a filler, a softening agent, a crosslinking accelerator, an acid acceptor, a defoaming agent, and a vulcanization aid, in addition to the reinforcing agent. The reinforcing agent and the filler improve the strength of the main rubber and serve as an extender. As the reinforcing agent and the filler, for example, carbon black, kaolin clay, talc, mica, calcium carbonate and silica are used. The softening agent is for facilitating kneading when mixing the rubber component and the additive. For example, paraffin oil is used.

The cross-linking accelerator acts together with the organic peroxide cross-linking agent to accelerate the cross-linking speed with a small amount. For example, stearic acid and triallyl isocyanurate are used. The acid acceptor is for trapping chlorine gas dissociated from the chlorinated polyethylene at the time of crosslinking so as not to evaporate. For example, magnesium oxide is used. The defoaming agent removes bubbles generated in the uncrosslinked mixture. For example, calcium oxide is used. The vulcanization aid is, for example, ethylene dimethacrylate,
1,3 butylene dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, triallyl trimellitate are used.

Next, the main rubber component will be described. In the main rubber component, for example, DCP EPDM
Is contained in an amount of 30 to 100% (weight%, the same applies hereinafter). Alternatively, 10 to 100% of chlorinated polyethylene is contained in the main rubber component. Alternatively, the main rubber component contains 30 to 70% of DCP EPDM and 30 to 70% of chlorinated polyethylene.

When the DCP EPDM is less than 30% in the main rubber component, or when the chlorinated polyethylene is 1%.
If it is less than 0%, as described above, the decomposition reaction of the rubber polymer is more dominant than the crosslinking reaction between rubber molecules, and the main rubber component may not be sufficiently crosslinked.

The content ratio of the DCP-based EPDM or the like may be appropriately selected depending on the use of the rubber laminated product. For example, if it is a rubber laminated product used as a flame retardant gasket, DCP EPDM 50%, chlorinated polyethylene 5
It is preferably made from a rubber component having a content ratio of 0%.

Next, it is preferable that another rubber component is added to the main rubber component. As a result, the Oshida moldability of the first uncrosslinked mixture is improved, and the crosslinking rate is increased. The added rubber component is preferably added and mixed in the main rubber component in an amount of 5 to 70%.

When the amount of the added rubber component is more than 70%, as described above, the decomposition reaction of the rubber polymer is more dominant than the crosslinking reaction between rubber molecules, and the main rubber may not be sufficiently crosslinked. On the other hand, if it is less than 5%, it is difficult to obtain the effect of addition. Examples of the added rubber component include ENB EPDM, IR (isoprene rubber), NBR (butadiene acrylonitrile rubber), S
BR (styrene butadiene rubber), CSM (chlorosulfonated polyethylene), ACM (acrylic rubber), Q
There is one kind or two or more kinds selected from the group of (silicone rubber), FKM (fluorine rubber) and U (urethane rubber).

Next, in carrying out organic peroxide crosslinking and crosslinking adhesion, the temperature is preferably 150 to 300.degree. If the temperature is lower than 150 ° C., the crosslinking rate becomes very slow, which may reduce the productivity. If the above temperature is higher than 300 ℃,
The rubber polymer may be decomposed by heat and the desired physical properties may not be obtained.

Next, as the organic peroxide crosslinking agent,
For example, 1,3 bis (tertiary butylperoxyisopropyl) benzene, 2,5 dimethyl 2,5 (tertiary butylperoxy) hexyne-3, dicumyl peroxide, 2,
4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,1-diterebutylperoxy 3,
3,5-Trimethylcyclohexane, 2,5-Dimethyl 2,5-dibenzoylperoxyhexane, n-Butyl 4,4-diterebutylperoxyvalerate, terebutylperoxybenzoate, diterebutylperoxydiisopropyl From the group of benzene, terebutylcumyl peroxide, 2,5-dimethyl 2,5-diterebutylperoxyhexane, diterebutylperoxide, 2,5-dimethyl 2,5-diterebutylperoxyhexyne 3 There are one or more selected.

The organic peroxide crosslinking agent is preferably added so that the amount of active oxygen is 0.005 to 0.02 mol with respect to 100 g of the rubber component. If the amount of active oxygen is less than 0.005 mol, the crosslinking between rubber molecules may be insufficient. If the amount is more than 0.02 mol, the elasticity may be lowered and the rubber may not be formed. There is also a problem that bloom is generated due to the residual organic peroxide crosslinking agent that is not used for crosslinking.

[0025]

FUNCTION AND EFFECT The rubber laminated product of the present invention is obtained by cross-linking the main rubber containing a specific rubber component and the silicone rubber with organic peroxide, and cross-linking the both at their joint surfaces. . The component of the specific main rubber is DCP EPDM, chlorinated polyethylene, or a mixture of both.

Therefore, in the cross-linking of the organic peroxide of the main rubber component, the cross-linking reaction between rubber molecules is more dominant than the above-mentioned decomposition reaction of the polymer. For this reason, the main rubber is in a good condition without surface stickiness and blooming. Further, the main rubber does not contain sulfur that hinders the crosslinking of the silicone rubber.

Therefore, in the cross-linking adhesion with the silicone rubber, sulfur migrates from the main rubber, and the disadvantage of the conventional method that the silicone rubber cannot be cross-linked sufficiently is eliminated. Therefore, excellent and strong cross-linking adhesion between the main rubber and the silicone rubber becomes possible. Further, according to the above manufacturing method, a rubber laminated product having excellent properties can be easily manufactured as described above.

Therefore, according to the present invention, a rubber laminated product in which the silicone rubber is sufficiently cross-linked, the main rubber and the silicone rubber are firmly laminated and joined, and the main rubber side is not sticky and bloom does not occur, and its production A method can be provided.

[0029]

【Example】

Example 1 A rubber laminate and a method for manufacturing a rubber laminate according to an example of the present invention will be described with reference to FIGS. 1 to 5. As shown in FIG. 1, the rubber laminated product 1 is formed by laminating and bonding a main rubber 12 and a silicone rubber 11. The main rubber 12 contains chlorinated polyethylene, and the main rubber 12 and the silicone rubber 11 are each crosslinked with an organic peroxide, and the joint surface 10 between them is crosslinked.

Next, a method for manufacturing the rubber laminated product 1 will be described. First, a first uncrosslinked mixture 120 prepared by mixing a main rubber component made of chlorinated polyethylene, an organic peroxide crosslinking agent, and additives such as a reinforcing agent, and a second composition formed of a silicone rubber polymer and a silicone rubber crosslinking agent. Two uncrosslinked mixtures 110 are prepared. Next, as shown in FIG.
This is put into the crosshead extruder 2. In the crosshead extruder 2, the first and second uncrosslinked mixtures 110 and 120 are laminated and molded into a desired shape to form a laminated molded product 13. Next, this laminated molded product 13 is introduced into the crosslinking device 3, and organic rubber is crosslinked and crosslinked in the presence of hot air to obtain the rubber laminated product 1. Finally, the rubber laminate 1 is cooled using the water cooling device 4. The same material as in Example 2 is used as the first uncrosslinked mixture 120 and the like.

Next, FIG. 3 shows the crosshead extruder 2. The crosshead extruder 2 has two material input ports 21 and 22 and an extrusion port 25. Material input port 2
The second uncrosslinked mixture 110 is charged from 1 and the first uncrosslinked mixture 120 is charged from the material charging port 22. Then, the first and second uncrosslinked mixtures 110 and 120 are continuously extruded from the extrusion port 25 into a laminated molded article 13 having a predetermined shape and extruded.

Next, FIG. 4 shows an HAV 31 (normal pressure hot air heating furnace) used as the crosslinking device 3. HAV above
Reference numeral 31 denotes an inlet 311 for introducing the laminated molded product 13, an outlet 312 for sending out the rubber laminated product 1 after completion of the organic peroxide crosslinking and crosslinking adhesion, and a crosslinking chamber 315 provided between the inlet 311 and the outlet 312. , The above-mentioned laminated molded product 12 at the inlet 3
Conveyor 314 for transporting from 11 to exit 312
And an outlet 313 for introducing hot air into the bridge chamber 315.

In the above HAV 31, first, the inlet 3
The laminated molded product 13 is introduced from 11. The laminated molded product 13 is placed on the conveyor 314 and passes above the outlet 313. The laminated molded product 13 is crosslinked and crosslinked with the organic peroxide by the hot air from the outlet 313. afterwards,
The crosslinked rubber laminate 1 is conveyed from the outlet 312.
The temperature of the hot air is maintained at about 220 ° C.
The crosslinking time is about 7 minutes.

Further, FIG. 5 shows an LCM 35 (fluidized bed heating furnace) used as the crosslinking device 3. LCM3 above
5 is an inlet 351 for introducing the laminated molded product 13 and an outlet 35 for sending out the rubber laminated product 1 in which the organic peroxide crosslinking is completed.
2, a bridging chamber 355 provided between the inlet 351 and the outlet 352, glass beads 356 filled in the bridging chamber 355, and an outlet 353 for introducing hot air for heating the glass beads 356. Become.

In the LCM 35, the laminated molded product 13 introduced from the inlet 351 passes through the glass beads 356. The glass beads 356 are heated by the hot air from the air outlet 353. Glass beads 3
The laminated molded product 13 is crosslinked by the conduction heat from 56 and sent to the outlet 352. The temperature of the hot air is 2
It is kept at about 20 ° C. Further, cooling water is constantly circulated in the water cooling device 4.

Examples 2 to 12 Tables 1 to 12 below show examples of the present invention together with comparative examples.
This will be described with reference to Table 6. This example is a performance evaluation of Examples 2 to 12 and Comparative Examples C1 to C3 prepared from the first uncrosslinked mixture shown in Tables 1 to 3.

In the above Examples and Comparative Examples, the first rubber composition was mixed with the additive and the organic peroxide crosslinking agent or sulfur to prepare a first uncrosslinked mixture, which was laminated with the second uncrosslinked mixture. After molding, it is crosslinked and adhered with an organic peroxide crosslink or a sulfur crosslink, and a second uncrosslinked mixture to obtain a rubber laminate. The manufacturing method is similar to that of the first embodiment. The organic peroxide crosslinking device is HAV
To use. Among the above rubber components, chlorinated polyethylene and DCP EPDM are main rubber components, and ENB EPDM and isoprene rubber are additive rubber components.

A silicone polymer containing a polyorganosiloxane is used as the second uncrosslinked mixture, and benzoyl peroxide is used as the crosslinking agent.

The first uncrosslinked mixture will be described with reference to Tables 1 to 3. In addition, Tables 1 and 2 are component tables of the first uncrosslinked mixture according to the example, and Table 3 is a component table of the comparative example. In the table, DCP EPDM, ENB E
As PDM and isoprene rubber, JSR / EP75F and JSR / EP2 manufactured by Japan Synthetic Rubber Co., Ltd., respectively.
1, JSR / IR1200 was used. Also, as chlorinated polyethylene, Showa Denko Co., Ltd. Erasulene 4
01AE was used. The blending amount of these is shown by weight% in all rubber components.

Dicumyl peroxide was used as the organic peroxide. Additives are CaCO ₃ and talc as reinforcing agents / fillers, paraffin oil as a softening agent, stearic acid as a crosslinking accelerator, magnesium oxide as an acid acceptor, calcium oxide as a defoaming agent, and triallyl as a vulcanization aid. Isocyanurate was used. All of these compounding amounts are numerical values based on 100 parts by weight of the rubber component. The above acid acceptor was used only when chlorinated polyethylene was used in the rubber component.

The second embodiment will be described below. First,
Only chlorinated polyethylene is used as the rubber component. 3 parts by weight of the organic peroxide crosslinking agent is used with respect to 100 parts by weight of the rubber component. As for additives, 150 reinforcing agents / fillers, 50 softening agents, 1 crosslinking accelerator, 5 acid acceptors
The defoaming agent is 5 and the vulcanization aid is 2 parts by weight. The above materials are mixed to form an uncrosslinked mixture. The same applies to Examples 3 to 12 and Comparative Examples C1 to C3. In Comparative Example C3, sulfur is used as a crosslinking agent instead of the organic peroxide crosslinking agent. Therefore, no vulcanization aid is used.

Next, Tables 4 and 5 show the performance evaluations of the examples, and Table 6 shows the performance evaluations of the comparative examples. The above performance evaluation is based on the presence or absence of stickiness and bloom on the main rubber surface,
The cross-linking adhesive strength with silicone rubber was used. First,
Stickiness and bloom contact the surface of the rubber composition,
Visually observe and evaluate "Yes" or "No".

Next, the measurement of the cross-linking adhesive strength with silicone rubber will be described. In the above measurement, first, the first uncrosslinked mixture and the second uncrosslinked mixture are made into a laminated molded product having a thickness of 5 mm and a total thickness of 10 mm by a crosshead extruder. This is continuously crosslinked with HAV to obtain a test piece. Using a tensile tester specified in JISK6301,
Forcibly peel off the silicone rubber and the main rubber. The cross-linking adhesive strength is measured by observing the maximum weight at the time of peeling and the peeled state.

The performance evaluation will be described below. First, as shown in Tables 4 and 5, no stickiness or bloom is generated in the examples. on the other hand,
As shown in Table 6, in Comparative Examples C1 and C2, stickiness and bloom were confirmed on the surface. Regarding Comparative Example C3, neither stickiness nor bloom occurred.

Next, the adhesive strength with silicone rubber will be described. In the example, the main rubber and the silicone rubber are bonded at their joint surfaces, and the bonding strength is 20 to
It is in the range of 30. When a load exceeding the above adhesive strength is applied, the two do not separate and the rubber laminate itself is destroyed. Therefore, it can be seen that the adhesive strength between the two is sufficiently strong for practical use.

On the other hand, in the laminated products of Comparative Examples C1 and C2, the surface of the main rubber was rubber-like and the main rubber and the silicone rubber were not cross-linked at the joint surface. Further, in Comparative Example C3, the silicone rubber was in an uncrosslinked state, and similarly, crosslink adhesion was not performed. That is, a rubber laminated product could not be obtained in the comparative example. Therefore, the adhesive strength could not be measured.

As is known from the above, the rubber laminated product of the present invention is a rubber laminated product obtained by laminating and joining a main rubber containing a specific rubber component and a silicone rubber. The main rubber and the silicone rubber are each crosslinked with an organic peroxide, and are further crosslinked and bonded at their joint surfaces. The specific rubber component is DCP EPDM, chlorinated polyethylene, or a mixture of both. The rubber component allows sulfur-free crosslinking of the main rubber under hot air with organic peroxides. In this case, the cross-linking reaction between rubber molecules is predominant over the decomposition reaction of the rubber polymer described above, and a good main rubber without surface stickiness and bloom can be obtained.

Further, there is no sulfur which hinders the crosslinking reaction of the silicone rubber in the main rubber. Therefore, good cross-linking adhesion between the main rubber and the silicone rubber is possible, and a rubber laminated product composed of both is obtained. As described above, according to this example, it is possible to obtain a rubber laminated product in which the main rubber and the silicone rubber are firmly laminated and joined, and the main rubber side is not sticky and bloom does not occur, and a manufacturing method thereof. Further, since the rubber laminated product of this example does not use sulfur, it does not cause a problem such as discoloration even if it comes into contact with the coated plate. For this reason, it is suitable for use in exterior parts, etc., where design is especially required.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

[Table 6]

Example 13 Performance evaluation of Example 13 according to the present invention and Comparative Examples C4 to C7 will be described with reference to Table 7. The above performances are tensile strength, hardness and weather resistance. This example is a rubber laminated product produced by the method shown in Example 1. As the main rubber, the same rubber as in Example 4 is used. As the silicone rubber, YE3 manufactured by Toshiba Silicone Co., Ltd.
Use 465U.

Comparative Example 4 is a molded product using only silicone rubber. The same silicone rubber as in this embodiment is used as the silicone rubber. Comparative Example 5 below is a molded product using chloroprene rubber and ENB EPDM, respectively. In Comparative Example 7, chlorosulfonated polyethylene was laminated and molded on chloroprene. The preparation of the comparative example is performed according to the method shown in Example 1.
In all of the present examples and comparative examples, titanium oxide is added in the state of an uncrosslinked mixture to adjust the surface of the present examples and comparative examples after crosslinking to be white.

The above-mentioned tensile strength is based on JISK6301, with respect to the molded product obtained by No. 3 dumbbell,
It is measured by performing a punching tensile test. The hardness is measured according to JIS K6301 by using a JIS-A type hardness meter. From the above strength and hardness measurements, it can be seen whether or not the molded product has excellent mechanical strength. The weather resistance is obtained by exposing the molded product to a sunshine weather meter for 3000 hours.
After that, check the surface condition of the molded product by contact and visual inspection.

Next, the performance evaluation of this embodiment and the comparative example will be described. Comparative Example 7 and this Example are excellent in tensile strength. Regarding hardness, Comparative Example 7
And this example is excellent. Regarding the weather resistance, this example and comparative example 4 are excellent. This shows that the rubber laminated product of this example overcomes the weakness of the mechanical strength, which is the drawback of silicone rubber. This is especially clear when compared with Comparative Example 4 which is composed of a silicone rubber alone.

Further, in this embodiment, since the silicone rubber is laminated on the surface, good weather resistance results are obtained. Other than Comparative Example 4 made of only silicone rubber, problems such as discoloration occur. Therefore, this example is superior in weather resistance to the other comparative examples.

In addition, since the present embodiment has a laminated structure, the amount of expensive silicone rubber polymer used can be greatly reduced. Therefore, it can be used as a substitute for silicone rubber moldings, which is cheap and has superior characteristics. In particular, this example is excellent in mechanical strength, and therefore, it is most suitable as a rubber component material to be used outdoors or in a portion exposed to the outside. It should be noted that, as the above-mentioned use examples, building joint seals, gaskets, weather strips for automobiles, etc. can be considered.

[0061]

[Table 7]

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a rubber laminated product in Example 1.

FIG. 2 is an explanatory view of a method for manufacturing a rubber laminated product in Example 1.

FIG. 3 is a perspective view of a crosshead extruder according to the first exemplary embodiment.

FIG. 4 is a cross-sectional view of the atmospheric hot air heating furnace according to the first embodiment.

FIG. 5 is a sectional view of a fluidized bed heating furnace in Example 1.

[Explanation of symbols]

 1. ． ． Rubber laminated product, 11. ． ． Silicone rubber, 110. ． ． Second uncrosslinked mixture, 12. ． ． Main rubber, 120. ． ． First uncrosslinked mixture, 13. ． ． Laminated moldings,

Claims (12)

[Claims] 1. A rubber laminated product obtained by laminating and bonding a main rubber and a silicone rubber, wherein the main rubber contains DCP EPDM, chlorinated polyethylene or a mixture of both.
Also, a rubber laminated product characterized in that the main rubber and the silicone rubber are each crosslinked with an organic peroxide, and the joint surfaces of both are crosslinked. 2. The rubber as claimed in claim 1, wherein
A rubber laminated product characterized in that other added rubber components are added and mixed. 3. The additive rubber component according to claim 2, wherein the added rubber component is ENB EPDM, IR (isoprene rubber), NB.
It is selected from the group of R (butadiene acrylonitrile rubber), SBR (styrene butadiene rubber), CSM (chlorosulfonated polyethylene), ACM (acrylic rubber), Q (silicone rubber), FKM (fluorine rubber), U (urethane rubber). A rubber laminated product characterized by being one or more. 4. A first uncrosslinked mixture obtained by mixing a main rubber component, an organic peroxide crosslinking agent, and additives such as a reinforcing agent,
A silicone rubber polymer and a second uncrosslinked mixture of a silicone rubber crosslinking agent are laminated and molded into a desired shape to form a laminated molded article, which is then crosslinked with an organic peroxide in the presence of hot air. And a method of cross-linking adhesion, wherein the main rubber component contains DCP EPDM, chlorinated polyethylene, or a mixture of both. 5. The DCP-based EPD according to claim 4.
A method for producing a rubber laminated product, wherein M is contained in the rubber component in an amount of 30 to 100% (% by weight, the same applies hereinafter). 6. The method for producing a rubber laminate according to claim 4, wherein the rubber component contains 10 to 100% of chlorinated polyethylene. 7. The method for producing a rubber laminate according to claim 4, wherein the rubber component contains 30 to 70% of DCP EPDM and 30 to 70% of chlorinated polyethylene. 8. The method for producing a rubber laminate according to claim 4, wherein the main rubber component is further mixed with another additive rubber component. 9. The method for producing a rubber laminate according to claim 4, wherein the added rubber component is added and mixed in the main rubber component in an amount of 5 to 70%. 10. The additive rubber component according to claim 8 or 9, wherein the added rubber component is ENB EPDM, IR (isoprene rubber), NBR (butadiene acrylonitrile rubber), or S.
BR (styrene butadiene rubber), CSM (chlorosulfonated polyethylene), ACM (acrylic rubber), Q
(Silicone rubber), FKM (fluorine rubber), U (urethane rubber) is one or more selected from the group, and a method for producing a rubber laminated product. 11. The temperature of organic peroxide crosslinking and crosslinking adhesion according to claim 4 to 9 or 10, is 150 to 300 ° C.
And a method for producing a rubber laminated product. 12. The organic peroxide crosslinking agent according to claim 4, wherein the organic peroxide crosslinking agent is 1,3 bis (tertiary butylperoxyisopropyl) benzene, 2,5 dimethyl 2,5.
(Tert-Butylperoxy) hexyne-3, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,1-diterebutylbutyloxy 3,3,5-trimethylcyclohexane,
2,5-Dimethyl 2,5-dibenzoylperoxyhexane, n-butyl 4,4-diterebutylperoxyvalerate, terebutylperoxybenzoate, diterebutylperoxydiisopropylbenzene, terebutylcumyl peroxide , 2,5-Dimethyl-2,5-diterebutylperoxyhexane, diterebutylperoxide, 2,5-dimethyl2,5-diterebutylperoxyhexyne 3, one or more kinds selected from the group And a method for producing a rubber laminated product.