JPH1081784A - Rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber composition capable of giving a rubber molded product excellent in vulcanization adhesivity to other dienic rubber compositions and not deteriorated in low air permeability. SOLUTION: This rubber composition is obtained by kneading at least one kind of low-air-permeable, functional group-vulcanizable rubber with a vulcanization agent capable of vulcanizing the functional group-vulcanizable rubber within a temperature range not vulcanizing the functional group-vulcanizable rubber, subsequently kneading the kneaded product with at least one kind of carbon- carbon double bond-vulcanizable rubber in an amount of 25-100 pts.wt. per 100 pts.wt. of the functional group-vulcanizable rubber, and simultaneously selectively vulcanizing the functional group-vulcanizable rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low air permeability functional group vulcanizable rubber (hereinafter also referred to as "functional group vulcanizable rubber").
And a rubber composition containing a carbon-carbon double bond vulcanizable rubber (hereinafter, also referred to as a "double bond vulcanizable rubber"), which is not inferior in low air permeability. And a rubber composition having excellent vulcanization adhesion with other diene rubber compositions.

[0002]

2. Description of the Related Art Conventionally, a rubber composition using a single rubber as a rubber component is required to bring out performances that cannot be obtained, and also to improve the processability of the obtained rubber composition and reduce the cost of raw materials. A technique of blending two or more rubbers has been used.

[0003] In the field of tires, low air permeability and vulcanization adhesion with other diene rubber compositions are required, especially for inner liners and cases.
A rubber composition obtained by blending two or more types of rubbers, which can impart low air permeability and another rubber, is used.

[0004] However, in order to further improve the low air permeability, the mixing ratio of the low air permeability rubber in the rubber composition comprising the low air permeability rubber and another rubber, for example, when the low air permeability rubber is a rubber component. When the amount is increased to 50% by weight or more, the vulcanization adhesion between the obtained rubber composition and another diene rubber composition is remarkably reduced.

[0005] On the other hand, Japanese Patent Application No. 8-121766 discloses a rubber composition comprising two or more types of rubbers of a functional group vulcanizable rubber and a double bond vulcanizable rubber. Discloses a technique for obtaining a rubber composition containing a functional group vulcanizable rubber selectively vulcanized, and vulcanizing the rubber composition after molding so that the double bond vulcanizable rubber is also vulcanized. As a result, a rubber molded product containing no unvulcanized rubber can be obtained.

[0006] In view of the above facts, the present inventors have
Using a specific rubber combination of a low-air permeability functional group vulcanizable rubber and a double bond vulcanizable rubber in a specific compounding ratio,
And a method for obtaining a rubber composition which is excellent in vulcanization adhesion with other diene rubber compositions and can provide a rubber molded product which is not inferior in low air permeability by employing the two-stage method. I arrived at.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a rubber composition which has excellent vulcanization adhesiveness with other diene rubber compositions and can provide a rubber molded product which is not inferior in low air permeability. To get things.

[0008]

According to the present invention, there is provided (a) at least one vulcanizable rubber having a low air permeability functional group and a curing agent capable of vulcanizing the functional group vulcanizable rubber. The kneaded material is kneaded in a temperature range where the vulcanizable rubber is not vulcanized.
While kneading 5 to 100 parts by weight of at least one carbon-carbon double bond vulcanizable rubber within a temperature range in which the functional group vulcanizable rubber can vulcanize, the functional group vulcanizable rubber is The present invention relates to a rubber composition obtained by selectively vulcanizing.

The functional groups of the vulcanizable rubber include a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an epoxy group, an acid anhydride group, a halogen atom (including a fluorine atom in a fluorine-based polymer), Ester groups, chlorosulfone groups, methylol groups, sulfonate groups and / or
Alternatively, it is preferably a nitrile group, and as the curing agent, an organic curing agent and / or an inorganic curing agent can be used.

The functional group vulcanizable rubber is preferably a bromide of isobutylene / p-methylstyrene copolymer rubber, chlorobutyl rubber and / or bromobutyl rubber.

Among the above curing agents, polyamines, polycarboxylic acids or polyols are used as organic curing agents, and oxides, carbonates or hydroxides of divalent metals of Mg, Zn, Ca or Ba are used as inorganic curing agents. can give. Preferably, the organic curing agent is N, N'-diethylthiourea.

The kneading temperature range of the above (a) is 40-1.
00 ° C., and the kneading temperature range of (b) is 90 to 140 ° C.
And the kneading temperature of (a) is preferably lower than the kneading temperature of (b). Further, the kneading temperature range of (a) is 60 to 90 ° C., and the kneading temperature range of (b) Is 1
00 to 120 ° C., and the kneading temperature of (a) is (b)
Is preferably lower than the kneading temperature.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to (a) at least one vulcanizable rubber having a low air permeability and a curing agent capable of vulcanizing the functional group vulcanizable rubber. Kneading within the temperature range where the vulcanizable rubber does not vulcanize, (b) the resulting kneaded material,
25 to 10 based on 100 parts by weight of the functional group vulcanizable rubber
While kneading 0 parts by weight of at least one carbon-carbon double bond vulcanizable rubber within a temperature range in which the functional group vulcanizable rubber can be vulcanized, the functional group vulcanizable rubber is selectively kneaded. To a rubber composition obtained by vulcanization.

In the present invention, the functional group vulcanizable rubber and the double bond vulcanizable rubber can impart excellent low air permeability to a rubber molded product obtained from the rubber composition of the present invention. And, the functional group becomes a cross-linking point, the latter has an affinity with the diene rubber, and can impart excellent vulcanization adhesion to other diene rubbers to the rubber composition of the present invention. And a carbon-carbon double bond serves as a cross-linking point.

The functional group vulcanizable rubber may be any as long as the functional group can be a crosslinking point. It may have a carbon-carbon double bond, in which case the degree of unsaturation is preferably 50 or less, preferably 30 or less. It is preferably low unsaturated (high saturated) of 25 or less. In other words, the functional group vulcanizable rubber is one that cannot or cannot be vulcanized with sulfur.

The rubber (hereinafter, also referred to as "saturated rubber") before introducing the functional group of the low-air-permeable functional group vulcanizable rubber includes, for example, acrylonitrile-butadiene rubber (NBR), fluorine rubber, epichlorohydrin rubber, Butyl rubber, halogenated butyl rubber, isobutylene / p-
Brominated methyl styrene copolymer rubber, chloroprene rubber, ethylene / acrylate copolymer rubber, epoxidized natural rubber, ethylene-propylene-diene rubber (EPDM), etc., and air permeability of natural rubber (NR) Because it is lower than diene rubber such as
NBR, halogenated butyl rubber, bromide of isobutylene / p-methylstyrene copolymer rubber, chloroprene rubber, epoxidized natural rubber, and EPDM are preferred. These rubbers are blended with the double bond vulcanizable rubber after introducing the required functional groups.

A functional group is introduced into these saturated rubbers in order to enable vulcanization (crosslinking) with a curing agent other than sulfur, thereby obtaining a functional group vulcanizable rubber. However, for example, fluorine rubber, epichlorohydrin rubber, halogenated butyl rubber,
Chloroprene rubber, bromide of isobutylene / p-methylstyrene copolymer rubber, epoxidized natural rubber and N
In the case of BR, it is not always necessary to introduce a new functional group.

The functional group possessed by the functional group vulcanizable rubber may be any functional group capable of vulcanizing (crosslinking) the functional group vulcanizable rubber with a curing agent other than sulfur, such as a hydroxyl group and a carboxyl group. , Amino group, isocyanate group,
Examples include an epoxy group, an acid anhydride group, a halogen atom (including a fluorine atom in a fluorine-based polymer), an ester group, a chlorosulfone group, a methylol group, a sulfonate group and / or a nitrile group.

[0019]

Embedded image

And the like.

Of these, a halogen atom, an acid anhydride group, a carboxyl group, and an epoxy group are preferred from the viewpoint of prompt reaction.

The method for introducing a functional group into the saturated rubber may be a commonly used method. For example, a hydroxyl group is introduced by using a so-called oxymercury which utilizes a slight double bond in the saturated rubber. There are a mercuration-demercury method or a hydroboration oxidation method, and a hydrolysis method when the saturated rubber contains a halogen. In order to introduce a carboxyl group, there is a method of oxidizing a primary alcohol with potassium permanganate or the like, or a carbonation method using a Grignard reagent. In order to introduce an amino group, there are a method of halogenating an alcoholic hydroxyl group and aminating the same, and a method of nitrifying and reducing a bromide of p-methylstyrene. In order to introduce an epoxy group, there is a method using formic acid and aqueous hydrogen peroxide.

The functional group has a role of imparting a crosslinking point to the saturated rubber to form a functional group vulcanizable rubber. The amount of the functional group may be appropriately selected depending on the application, but is usually 0.5 to 100 per 100 repeating units. There may be 50, preferably 1-10. In addition, even if the amount of the functional group is large, the crosslinking density can be controlled by the amount of the curing agent.

Commercially available low-air-permeability functional group vulcanizable rubbers include, for example, EXX manufactured by Exxon Chemical Co., Ltd.
PRO 90-10 (brominated isobutylene / p-methylstyrene copolymer rubber), bromobutyl 2222 (bromobutyl rubber) manufactured by Exxon Chemical Co., Ltd., chlorobutyl 1066 (chlorobutyl rubber) manufactured by Exxon Chemical Co., Ltd., Showa Denko Or neoprene WRT (chloroprene rubber) manufactured by DuPont, epoxidized natural rubber manufactured by Guthrie, Esplen EMA manufactured by Sumitomo Chemical Co., Ltd.
2752 (ethylene / acrylate copolymer rubber), Royal Tough 465 (maleated EPDM) manufactured by Uniroyal, and the like. These low-air-permeable functional group vulcanizable rubbers can be used in the present invention. .

The curing agent in the present invention is used to crosslink the functional group present in the functional group vulcanizable rubber between molecules and vulcanize the compound, and a compound that specifically reacts with the functional group is used. As the kneading ratio of the curing agent in the present invention,
0.1 to 3 parts by weight per 100 parts by weight of the functional group vulcanizable rubber
0 parts by weight, preferably 0.1 to 11 parts by weight. Further, as such a curing agent, an organic curing agent and an inorganic curing agent (excluding sulfur) may be used alone or in combination.

Examples of the organic curing agent include N, N'-diethylthiourea (EUR), N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine and
Polyamines such as 4'-diamino-diphenyl ether; polycarboxylic acids such as suberic acid, oxalic acid, succinic acid, adipic acid and maleic acid; polyols such as ethylene glycol and propylene glycol;
Polyisocyanates such as 4-tolylene diisocyanate and diphenylmethane-4,4'-diisocyanate; zinc diethyldithiocarbamate and dipentamethylenethiuram tetrasulfide;
When the functional group of the functional group vulcanizable rubber is, for example, a carboxyl group, a halogen atom, an acid anhydride group or a hydroxyl group, a polyamine is used; when the functional group is an amino group or an epoxy group, a polycarboxylic acid is used; It is preferable to use a polyol or polyisocyanate as a curing agent.

Examples of the inorganic curing agent include oxides, carbonates and hydroxides of divalent metals such as Mg, Zn, Ca and Ba. The functional group of the vulcanizable rubber is, for example, halogen. In the case of atoms, it is preferable to use these inorganic curing agents, but from the viewpoint of high reactivity, an oxide of Zn is particularly preferable.

The kneading ratio of the low-air-permeability functional group vulcanizable rubber and the organic curing agent is as follows: 0.1 to 10 parts by weight of the organic curing agent per 100 parts by weight of the functional group vulcanizable rubber; The amount is more preferably 0.1 to 3 parts by weight from the viewpoint of shortening and improvement of physical properties of rubber. Also,
As the kneading ratio of the functional group vulcanizable rubber and the inorganic curing agent, the inorganic cured product 1 to 100 parts by weight of the functional group vulcanizable rubber was used.
20 parts by weight, more preferably 1 to 8 parts by weight from the viewpoint of shortening the kneading time and improving the physical properties of rubber. These organic curing agents and inorganic curing agents can be used alone or in combination. When used in combination, they may be used within the range of the kneading ratio used alone.

At this stage, other components such as a vulcanization accelerator such as stearic acid, a filler such as process oil and carbon black and an antioxidant are added to the vulcanization adhesiveness of the rubber composition of the present invention and the rubber. It may be added to such an extent that the low air permeability of the rubber molded product obtained from the composition is not reduced.

The kneading method (a) is preferably carried out in a temperature range where the functional group vulcanizable rubber is not vulcanized and the processability of the obtained rubber composition is not degraded, from the viewpoint of improving processability. Is preferably in the temperature range of 60 to 100 ° C., more preferably 40 to 90 ° C. in view of improvement in physical properties, and is preferably open roll in view of stabilizing physical properties, or in view of enhancing processability and workability. It is preferable to use a Banbury mixer.

Next, in the step (b), the kneaded product obtained in the step (a) and the double bond vulcanizable rubber are kneaded in a temperature range in which the functional group vulcanizable rubber can be vulcanized, The functional group vulcanizable rubber is selectively vulcanized.

The double bond vulcanizable rubber may be any one in which a carbon-carbon double bond serves as a crosslinking point. It may have a functional group. In that case, the content of the functional group is preferably small, and more preferably 0.1 to 5 per 100 repeating units. Further, the carbon-carbon double bond content is preferably higher, the degree of unsaturation of the double bond vulcanizable rubber is 50 or more,
It is preferably 70 or more, and particularly preferably 90 or more when it has a functional group.

The double bond vulcanizable rubber has an affinity for a diene rubber and imparts excellent vulcanization adhesion to the obtained rubber composition with another diene rubber composition. For example, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber (SB
R), diene rubbers such as NBR, etc., which can be used alone or in any combination, but from the viewpoint of improving mechanical strength, natural rubber, SBR, NB
It is preferable to use R, and it is particularly preferable to use natural rubber from the viewpoint of providing tackiness.

The kneading ratio of the kneaded product obtained in the above (a) and the double bond vulcanizable rubber is as follows.
25 to 100 parts by weight of a double bond vulcanizable rubber with respect to 0 parts by weight, preferably 25 to 100 parts by weight in terms of lowering air permeability.
The amount is preferably 50 to 100 parts by weight from the viewpoint of increasing the adhesive strength. A rubber composition obtained by kneading such a blend and selectively vulcanizing the functional group vulcanizable rubber is the rubber composition of the present invention. In addition, during the kneading accompanied by the selective vulcanization, other components such as a vulcanization accelerator such as stearic acid, a process oil, a filler, an antioxidant, and the like, the rubber composition of the present invention. May be blended within a range that does not lower the vulcanization adhesiveness of the rubber composition and does not lower the low air permeability of the rubber molded product obtained from the rubber composition.

In the above (b), only the functional group vulcanizable rubber in the blend of the functional group vulcanizable rubber and the double bond vulcanizable rubber is selectively vulcanized.

The selective vulcanization is carried out within a temperature range in which the functional group vulcanizable rubber starts to vulcanize and does not cause deterioration of the obtained rubber composition, for example, when natural rubber is used, preferably 90 to 140. C., from the viewpoint of shortening the kneading time, more preferably at a temperature of 100 to 120.degree.
This is achieved by kneading with the same means and method as the kneading. The temperature at the time of selective vulcanization in (b) is higher than the kneading temperature in (a). Further, it is preferable to knead in a Banbury mixer from the viewpoint of improving workability and workability.

The obtained rubber composition is a state in which an unvulcanized double bond vulcanizable rubber is used as a matrix and the vulcanized functional group vulcanizable rubber is uniformly present therein. .

The rubber composition of the present invention has excellent vulcanization adhesion with other diene rubber compositions, and is usually formed by a molding method such as roll or extrusion, and then finally subjected to double bonding. By vulcanizing the vulcanizable rubber, a rubber molded product having excellent low air permeability can be obtained.

For vulcanization of the double bond vulcanizable rubber, for example, sulfur, which is a vulcanizing agent for the double bond vulcanizable rubber, is added to a predetermined amount (for example, 0.5 to 2 PHR) of the rubber composition. For example, a vulcanization accelerator such as stearic acid and N-tert-butyl-2-benzothiazolylsulfenamide (NS), a filler such as process oil and carbon black, and an antioxidant are appropriately blended and kneaded. It may be performed by heating after molding.

The rubber composition of the present invention can be used in a wide variety of applications, and is particularly preferably used for tire inner liners, cases, tubes, gas hoses and the like.

In the present invention, as the composition and kneading conditions of the rubber composition, for example, the following can be preferably mentioned.

(Example 1) Low-air permeability functional group vulcanizable rubber (EXXPRO 90-10) 100 parts by weight Organic curing agent (EUR) 0.1 to 1 part by weight Inorganic curing agent (ZnO) 1 to 5 parts by weight Double bond vulcanizable rubber (natural rubber) 25 to 100 parts by weight Kneading temperature of step (a) 45 to 85 ° C Kneading time of step (a) 3 to 6 minutes Selective vulcanization temperature of step (b) 100 to 100 120 ° C. Selective vulcanization time of step (b) 4 to 10 minutes This rubber composition is advantageous in that a rubber molded product having good low air permeability and vulcanization adhesive properties can be obtained. is there.

(Example 2) Low-air permeability functional group vulcanizable rubber (epoxidized natural rubber) 100 parts by weight Organic curing agent (EUR) 0.1 to 3 parts by weight Inorganic curing agent (ZnO) 1 to 3 parts by weight Double bond vulcanizable rubber (natural rubber) 25 to 100 parts by weight Kneading temperature of step (a) 45 to 75 ° C Kneading time of step (a) 3 to 6 minutes Selective vulcanization temperature of step (b) 100 to 120 ° C. Selective vulcanization time of step (b) 4 to 10 minutes This rubber composition can obtain a rubber molded product having not only good low air permeability and vulcanization adhesiveness but also high hardness. This is advantageous in that it can be performed.

(Example 3) Low-air-permeable functional group vulcanizable rubber (halogenated butyl rubber) 100 parts by weight Organic curing agent (EUR) 0.1 to 2 parts by weight Inorganic curing agent (ZnO) 1 to 5 parts by weight II Heavy bond vulcanizable rubber (natural rubber) 25 to 100 parts by weight Kneading temperature of step (a) 48 to 85 ° C Kneading time of step (a) 3 to 10 minutes Selective vulcanization temperature of step (b) 100 to 120 C. Selective vulcanization time of step (b) 4 to 10 minutes This rubber composition is advantageous in that it has low air permeability.

(Example 4) Low-air-permeability functional group vulcanizable rubber (maleated EPDM) 100 parts by weight Organic curing agent (4,4'-diamino-diphenyl ether) 0.5 to 3 parts by weight Inorganic curing agent (ZnO) 1 to 5 parts by weight Double bond vulcanizable rubber (natural rubber) 25 to 100 parts by weight Kneading temperature of step (a) 45 to 80 ° C Kneading time of step (a) 2 to 4 minutes Selection of step (b) Typical vulcanization temperature 100 to 120 ° C. Selective vulcanization time of step (b) 2 to 8 minutes This rubber composition is advantageous in that it imparts weather resistance in addition to low air permeability.

(Example 5) 100 parts by weight of a low air permeability functional group vulcanizable rubber (NBR containing a carboxyl group) Organic curing agent (4,4'-diamino-diphenyl ether) 0.5 to 3 parts by weight Inorganic curing agent ( ZnO) 1 to 5 parts by weight Double bond vulcanizable rubber (natural rubber) 25 to 100 parts by weight Kneading temperature of step (a) 40 to 80 ° C Kneading time of step (a) 2 to 4 minutes of step (b) Selective vulcanization temperature 100 to 120 ° C. Selective vulcanization time of step (b) 2 to 8 minutes This rubber composition is advantageous in that it has low air permeability.

[0047]

EXAMPLES Next, the method for producing the rubber composition of the present invention will be described more specifically based on examples, but the present invention is not limited to these.

Production Examples 1 to 7 First, kneaded products were obtained by kneading using a roll at the mixing ratio and conditions shown in Table 1 to obtain the kneaded products A to G according to the step (a) of the present invention. In addition, low air permeability functional group vulcanizable rubber 1
EXXPRO 90- manufactured by Exxon Chemical Co., Ltd.
10 (brominated isobutylene / p-methylstyrene copolymer rubber), low air permeable functional group As the vulcanizable rubber 2, bromobutyl 2222 (bromobutyl rubber) manufactured by Exxon Chemical Co., Ltd., low air permeable functional group The vulcanizable rubber 3 is chlorobutyl 1066 (chlorobutyl rubber) manufactured by Exxon Chemical Co., Ltd. The low air permeable functional group vulcanizable rubber 4 is Royal Tough 465 (maleinated EPDM) manufactured by Uniroyal, low air The permeable functional group vulcanizable rubber 5 is DN631 (carboxyl group-containing NBR) manufactured by Zeon Corporation, and the low air permeable functional group vulcanizable rubber 6 is ENR50 (epoxidized natural rubber) manufactured by Guthrie. As the low-air-permeability functional group vulcanizable rubber 7, Neoprene WRT (chloroprene) manufactured by Showa Denko KK was used.

The curing agent 1 is EUR (N, N'-diethylthiourea) manufactured by Ouchi Shinko Chemical Co., Ltd., the curing agent 2 is 4,4'-diamino-diphenyl ether, and the curing agent 3 is ZnO was used.

Comparative Production Example 1 A vulcanized kneaded material H was obtained in the same manner as in Production Example 1 (kneaded material A) except that the kneading temperature was 100 ° C., which is the vulcanization temperature.

[0051]

[Table 1]

Examples 1 to 16 The kneaded products A to G obtained in Production Examples 1 to 7 were mixed at a mixing ratio shown in Table 2 with a Banbury mixer at 100 ° C. for 8 hours.
The rubber compositions 1 to 16 of the present invention were obtained by kneading and selective vulcanization according to the step (b) of the present invention in minutes. The double bond vulcanizable rubber was a natural rubber. Diamond black H manufactured by Mitsubishi Chemical Corporation was used as carbon black, and mineral oil manufactured by Japan Energy Co., Ltd. was used as mineral oil.

[Evaluation Method] Air Permeability In order to evaluate the air permeability of the rubber molded product comprising the rubber composition of the present invention, each of the obtained rubber compositions 1 to 16 was evaluated as follows.
5 parts by weight of ZnO, 1 part by weight of stearic acid, 2 parts by weight of sulfur, and 1 part by weight of NS with respect to 00 parts by weight, and kneaded using a roll, and a double bond vulcanizable rubber which has not been vulcanized yet. Vulcanization pressure of 100 using a hydraulic press
Vulcanization molding was performed under the conditions of kgf / cm ² , a vulcanization temperature of 150 ° C., and a vulcanization time of 40 minutes to obtain rubber molded products 1 to 16 as rubber sheets having a thickness of about 1 mm.

The air permeability of the rubber molded products 1 to 16 was determined by AS
According to the test method of TM D-1434-75M,
Gas permeability measuring device (GTR manufactured by Toyo Seiki Seisaku-sho, Ltd.)
It measured at the temperature of 20 degreeC using TESTER M-C1). Table 2 shows the results.

Vulcanization Adhesion In order to evaluate the vulcanization adhesion of the rubber composition of the present invention to other diene rubber compositions, first, the above rubber compositions 1 to 16 were rolled into a 2 mm thick sheet. , Thickness 2mm,
Rubber sheets 1 to 16 having a width of 80 mm and a length of 150 mm were prepared. In addition, a rubber sheet having a width of 80 mm and a length of 150 mm is formed from a blend of natural rubber and butadiene rubber having a weight ratio of 40:60 (including carbon black, sulfur and a vulcanization accelerator) by using a roll to form a sheet having a thickness of 2 mm. To obtain a diene rubber sheet. After each of the obtained rubber sheets 1 to 16 was vulcanized and bonded to a sheet made of a diene rubber composition, the peel strength (adhesive strength) was measured. The higher the peel strength, the better the vulcanization adhesion.

In order to prepare a peel strength measurement sample, as shown in FIG. 1, a rubber sheet 1 and a diene rubber sheet 2 are brought into close contact with each other, and a mylar sheet 4 and a thick weave 5 are formed so that peeling starts at the interface. Insert the insertion member and
The adhesive was vulcanized at 60 ° C. for 30 minutes under a pressure of 100 kgf / cm ² . Reference numeral 3 denotes a top warp, which is used to reinforce the rubber sheet so as not to be broken during peeling, and is usually unvulcanized. 1m thick in the present invention
m, a width of 80 mm, a length of 150 mm, and a rubber-based polyester resin were used. Mylar sheet 4
Is to prevent the rubber sheet 1 and the diene-based rubber sheet 2 from adhering over the entire surface during vulcanization,
Any material having a melting point of 180 ° C. or more may be used. In the present invention, a material having a thickness of 0.05 mm, a width of 80 mm and a length of 40 mm and made of polyethylene terephthalate was used.
The thick weave 5 is inserted to start peeling at the bonding interface. In the present invention, the one having a thickness of 0.5 mm, a width of 80 mm, and a length of 80 mm made of a nylon resin is used.

The peel strength measurement sample obtained as described above was peeled at a speed of 50 mm / min, and the peel strength was measured using a tensile tester manufactured by Intesco Corporation. Table 2 shows the results.

[0058]

[Table 2]

Comparative Examples 1 to 19 Using the Banbury mixer at the compounding ratios shown in Table 3, 10
Comparative rubber composition 1 was kneaded at 0 ° C. for 8 minutes.
19, and evaluation was performed in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 20 Kneading was performed in the same manner as in Comparative Example 1 except that the kneaded material H (kneading temperature 100 ° C.) obtained in Comparative Production Example 1 was used and the mixing ratio shown in Table 3 was used. The kneaded material H vulcanized in the components was not uniformly dispersed, and a rubber composition could not be obtained.

[0061]

[Table 3]

From Tables 2 and 3, the rubber composition of the present invention has excellent vulcanization adhesiveness, and
It can be seen that the rubber molded products 1 to 16 obtained from No. 6 are not inferior in low air permeability as compared with the comparative rubber molded products 1 to 19 obtained from the comparative rubber compositions 1 to 19.

[0063]

The rubber composition of the present invention has excellent vulcanization adhesiveness with other diene rubber compositions, and a rubber molded product which is not inferior in low air permeability according to the rubber composition. Can be.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a sample manufactured for measuring peel strength.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Rubber sheet 2 Diene rubber sheet 3 Top anti 4 Mylar sheet 5 Thick weave

Claims (7)

[Claims] 1. A method according to claim 1, wherein (a) at least one vulcanizable rubber having a low air permeability and a curing agent capable of vulcanizing the vulcanizable rubber, the vulcanizable rubber being vulcanized. (B) 25 to 100 parts by weight of at least one carbon-carbon double bond vulcanizable material based on 100 parts by weight of the functional group vulcanizable rubber. A rubber composition obtained by selectively vulcanizing the functional group vulcanizable rubber while kneading the rubber within a temperature range in which the functional group vulcanizable rubber can vulcanize. 2. The functional group of the vulcanizable rubber has a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an epoxy group, a halogen atom (including a fluorine atom in a fluoropolymer), an acid anhydride group, The rubber composition according to claim 1, which is an ester group, a chlorosulfone group, a methylol group, a sulfonate group and / or a nitrile group. 3. The method of claim 1, wherein the functional group vulcanizable rubber is isobutylene /
The rubber composition according to claim 1, which is a bromide of a p-methylstyrene copolymer rubber. 4. The rubber composition according to claim 1, wherein the functional group vulcanizable rubber is chlorobutyl rubber and / or bromobutyl rubber. 5. The rubber composition according to claim 1, wherein the curing agent is a divalent metal oxide, carbonate or hydroxide of Mg, Zn, Ca or Ba. 6. The rubber composition according to claim 1, wherein the curing agent is N, N'-diethylthiourea. 7. The kneading temperature range of (a) is from 40 to 10.
The rubber composition according to claim 1, which is 0 ° C, the kneading temperature range of (b) is 90 to 140 ° C, and the kneading temperature of (a) is lower than the kneading temperature of (b).