JP2001162723A - Rubber/polyamide composite and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a rubber/polyamide composite by strongly and integrally bonding and fixing a rubber layer and a polyamide layer without interposing an adhesive between both layers. SOLUTION: A rubber/polyamide composite is manufactured by molding a rubber composition containing at least a BR type rubber selected from butadiene rubber, a butadiene copolymer rubber and a modified butadiene rubber as a rubber component into a vulcanized molded article 4 having a desired shape and applying surface modifying treatment to the molded article and further bringing a predetermined polyamide 6 into contact with the treated surface 8 of the molded article 4 in a molten state to integrally bond and fix the same to the molded article.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-polyamide composite and a method for producing the same, and more particularly, to a method for firmly bonding a rubber and a polyamide constituting a rubber-polyamide composite without interposing an adhesive therebetween. The present invention relates to a technology that can be integrally joined and fixed.

[0002]

2. Description of the Related Art Conventionally, rubber-resin composites in which a predetermined rubber and a resin are integrally joined and fixed have been widely used in various fields. Rubber / resin composite hose formed by laminating resin and resin, rubber hose and resin connector,
Alternatively, in addition to an integrated composite product of a resin hose and a rubber joint, in recent years, attention has been paid to an anti-vibration rubber that can advantageously reduce the weight and cost, and instead of a conventional metal support member, a resin support is used. A rubber-resin composite type vibration damping rubber in which a member is attached to rubber is such. In recent years, in the case of electric appliances and the like that require waterproofness such as mobile phones, such a rubber-resin composite is also used as a housing part in which a plurality of resin members assembled together are sealed with a rubber member. It is used.

By the way, when manufacturing such a rubber-resin composite, generally, first, a resin molded article is formed as a resin portion of the composite using a predetermined resin, and then the obtained resin is obtained. After applying an appropriate adhesive to a predetermined surface of the resin molded product, an unvulcanized rubber composition that gives a rubber portion of the composite is formed on the adhesive applied surface,
Furthermore, after applying the adhesive to a predetermined surface of a vulcanized rubber as a rubber portion of a composite formed by vulcanization molding of an unvulcanized rubber composition in advance, or by applying a vulcanized adhesive thereto,
A method of forming a resin part of the composite by forming a predetermined resin on the coating surface and bonding the resin part to the vulcanized rubber at the same time, the rubber and the resin are mutually bonded with a sufficient bonding force or adhesive force. Because they can be joined and fixed, they have been widely used.

However, in such a method of forming a rubber-resin composite, since an organic solvent type is usually used as the adhesive, a gas of an organic solvent generated from the adhesive is used. The working environment is significantly degraded, thereby greatly impairing the safety of the worker, and the preparation of the adhesive is required to apply such an adhesive evenly on the surface of the resin molded article. In doing so, it is necessary to pay close attention to the concentration of the adhesive component in the solvent, and it is necessary to strictly control working conditions such as working time and working environment temperature in the coating process. Since a detailed management is required, a series of operations related to the application of the adhesive becomes extremely troublesome, and therefore, the productivity is reduced. There is a problem to Shorai.

[0005] Therefore, in order to cope with such a problem, various techniques for satisfactorily bonding rubber and resin without using an adhesive have been clarified.

[0006] For example, EP-A-344427 discloses that a thermoplastic resin containing an aliphatic polyamide in a proportion of 30% by weight or more and a rubber component containing a carboxyl group are added with a peroxide as a vulcanizing agent. A method has been proposed in which a rubber composition obtained by compounding a predetermined amount of a rubber is bonded to each other by vulcanization adhesion. Also, in Japanese Patent Application Laid-Open No.
A rubber composition obtained by forming a resin molded product using a resin contained in a proportion of not less than% by weight, while compounding a specific silane compound and a peroxide as a vulcanizing agent with various rubber components ( A technique for forming a rubber-polyamide composite by bonding a rubber compound) to a previously obtained resin molded product by pressure bonding and vulcanization bonding is disclosed. Furthermore, Japanese Patent Application Laid-Open No. 8-72203 discloses that while a predetermined resin is subjected to an appropriate surface modification treatment, an alkoxysilane compound is added to and blended with a predetermined rubber component on the treated surface. A method has been proposed in which an unvulcanized rubber composition is laminated and vulcanized to form a desired rubber / resin laminate.

However, the inventors of the present invention have studied and found that any of the methods described in the above-mentioned specifications and publications achieves a certain degree of bonding force in the obtained composite (laminated body). Although we can do it, we have found that it is still not enough in practical use.

[0008]

Under such circumstances, the present inventors have conducted intensive studies and as a result, among rubber materials, a butadiene rubber, a copolymer rubber of butadiene and another monomer, or a modified product of a butadiene rubber (in the present specification). These rubber materials are collectively referred to as BR rubber)), a vulcanized rubber molded product is formed using a rubber composition containing a rubber component, and the obtained rubber molded product is After applying an appropriate surface modification treatment, by contacting a predetermined polyamide in a molten state with the treated surface of the rubber molded product, after the polyamide is cured, the polyamide and the rubber molded product Have been found to be able to be joined and fixed with a high joining force, and have completed the present invention.

Accordingly, the present invention has been completed on the basis of such knowledge, and an object of the present invention is to provide a rubber / polyamide in which rubber and polyamide are integrally joined and fixed. In the method of manufacturing the composite,
It is an object of the present invention to provide a method capable of firmly bonding and fixing rubber and polyamide to each other without interposing an adhesive between them. Another object of the present invention is to provide a rubber-polyamide composite which is firmly and integrally joined and fixed without any intervening member.

[0010]

According to the present invention, in order to solve the above-mentioned problems, a rubber composition containing at least a BR rubber composed of butadiene rubber, butadiene copolymer rubber, or modified butadiene rubber as a rubber component. After obtaining a vulcanized molded product having a desired shape, a surface modification treatment is performed, and a predetermined polyamide is brought into contact with the treated surface in a molten state to obtain the rubber and the polyamide. And a method for producing a rubber-polyamide composite characterized by integrally joining and fixing the same.

That is, the rubber according to the present invention
In the method for producing a polyamide composite, the rubber portion of the rubber-polyamide composite is prepared using a specific rubber composition, specifically, a rubber composition containing at least a BR rubber as a rubber component. The vulcanized molded article to be formed is formed in a desired shape, and after performing a surface modification treatment of the obtained vulcanized molded article, a polyamide in a molten state is coated on the treated surface of the vulcanized molded article. There is a great feature in that it is brought into contact, so that the polyamide and the vulcanized molded product (rubber) cured after such an operation can be practically used without any adhesive. They can be joined and fixed together with an advantageous degree of joining force. in short,
According to the method of the present invention, a rubber-polyamide composite in which rubber and polyamide are firmly and integrally joined and fixed can be advantageously and without causing a deterioration in working environment and a decrease in productivity. It can be easily manufactured.

According to a preferred embodiment of the method for producing a rubber-polyamide composite according to the present invention, as the butadiene copolymer rubber, SBR, NB
R, ABR, or PBR is advantageously used, or alternatively, the modified butadiene rubber includes epoxy or epoxy resin-modified polybutadiene, maleic or maleic anhydride-modified polybutadiene, acrylic or methacrylic acid-modified polybutadiene, or urethane-modified polybutadiene. Is desirable.

In another preferred embodiment of the production method according to the present invention, as the rubber component in the rubber composition, a rubber material other than the BR rubber is combined with the BR rubber. Will be used.
As a result, the properties and functions according to the type of rubber material to be combined with the BR rubber can be advantageously imparted to the rubber constituting the rubber-polyamide composite.

Further, according to another preferred embodiment of the method of the present invention, B comprising the butadiene rubber, butadiene copolymer rubber or modified butadiene rubber is used.
The R-based rubber is used in a proportion of 1% by weight or more of the total amount of the rubber component, whereby the effects of the present invention as described above can be more effectively exerted.

Further, according to a preferred embodiment of the method for producing a rubber / polyamide composite according to the present invention, the surface modification of the vulcanized molded article includes an ultraviolet irradiation treatment, a plasma discharge treatment, and a corona discharge treatment. Or plasma jet treatment, which makes it possible to perform such surface modification treatment more easily and more effectively. In the present invention, the ultraviolet irradiation treatment as the surface modification treatment is, advantageously,
It is desirable to use a low-pressure ultraviolet lamp having a peak wavelength of 300 nm or less, so that the processing efficiency and the processing effect can be greatly improved.

According to another preferred embodiment of the production method according to the present invention, the polyamide resin is injection-molded on the surface-modified surface of the vulcanized molded article, whereby the vulcanization is carried out. For the treated surface of sulfur molded products,
A technique for bringing the polyamide into contact is advantageously employed. According to the method of the present invention, the vulcanized molded product (rubber) can be pre-compressed at the same time as the injection molding of the polyamide. It can be used particularly advantageously in the production of rubber-resin composite products that require pre-compression for the purpose of improving durability, such as rubber, such as resin composite-type anti-vibration rubber.

On the other hand, in the present invention, vulcanization of a desired shape obtained using a rubber composition containing at least a BR-based rubber composed of butadiene rubber, butadiene copolymer rubber, or modified butadiene rubber as a rubber component. A rubber-polyamide composite is also characterized in that a predetermined polyamide is brought into contact with the surface-modified surface of the molded product in a molten state, and the rubber and the polyamide are integrally joined and fixed. , And its gist.

The rubber / polyamide composite according to the present invention has a structure in which rubber and polyamide are integrally joined and fixed. In the present invention, the rubber is composed of a rubber component. As a vulcanized molded product formed using a rubber composition containing at least a BR-based rubber, and the polyamide is provided on the surface-modified surface of such a vulcanized molded product (rubber). The rubber and polyamide are firmly joined and bonded to each other without any adhesive due to the remarkable characteristic of being brought into contact in the molten state and being joined and fixed.
It is possible that the product of the present invention can be advantageously used in various fields such as a vibration-proof rubber, a hose, and a housing for electric appliances. is there.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a basic laminated structure of a rubber / polyamide composite according to the present invention as described above. A vulcanized rubber molded body 4 formed of a rubber composition containing at least a BR rubber as a rubber component;
It is formed with a structure in which a polyamide molded body 6 made of a predetermined polyamide is integrally joined and fixed. And, in the present invention, such a method of forming the rubber-polyamide composite 2 has a great feature.

That is, in the present invention, (A) First, a vulcanized rubber having a desired shape is formed by a molding and vulcanizing operation using a rubber composition in which a BR rubber is compounded as an essential rubber component. A molded body 4 is formed, and (B)
After performing an appropriate surface modification treatment on the vulcanized rubber molded body 4 thus obtained, (C) the treated surface 8 of the modified vulcanized rubber molded body 4 is subjected to: The vulcanized rubber molded body 4 and the polyamide molded body 6 are brought into contact with each other in a molten state by forming a polyamide molded body 6 having a desired shape on the treated surface 8 by bringing the polyamide into contact with the molten state and curing the polyamide. Thus, the target rubber-polyamide composite 2 integrally bonded and fixed is formed.

The fixing mechanism between the vulcanized rubber molded article 4 and the polyamide molded article 6 according to the present invention has not yet been fully elucidated. A), (B),
If the desired rubber / polyamide composite 2 is formed by sequentially performing the operation of (C), the vulcanized rubber molded body 4 and the polyamide molded body 6 may be used with any adhesive. It is an undeniable fact that they can be firmly adhered to each other with a high bonding force. Therefore, in the rubber / polyamide composite 2 thus obtained relatively easily, its shape is appropriately adjusted. By setting to, for example, rubber-resin composite type anti-vibration rubber, rubber-resin composite hose, rubber hose-resin connector, resin hose-rubber joint integrated composite product, electric appliances such as mobile phones, etc. It can be used advantageously as a waterproof housing part or the like used for the above.

By the way, such a rubber according to the present invention
As described above, the vulcanized rubber molded body 4 constituting the polyamide composite 2 includes, as a rubber component, a BR rubber, that is, a butadiene rubber (BR), a butadiene copolymer rubber, or a modified butadiene rubber (modified BR). It is formed using a rubber composition obtained by blending at least one or more of them.

Here, of the BR rubber as an essential rubber component constituting such a rubber composition, BR includes polybutadiene formed by emulsion polymerization of butadiene, solution polymerization using a suitable catalyst, and the like. Various known substances such as liquid polybutadiene formed with an average molecular weight of 2000 to 4000 by anionic living polymerization or coordination polymerization are advantageously used. It should be noted that there is no problem if such a liquid BR has a functional group such as a carboxyl group, a hydroxyl group, or an allyl group at one or both ends, in addition to a polymer having no functional group at the polymer end.

On the other hand, the butadiene copolymer rubber is intended to mean various elastomers obtained by copolymerizing butadiene and a monomer copolymerizable with butadiene. Typical examples thereof include: Styrene-butadiene rubber (SBR), nitrile rubber (NBR), acrylate-butadiene rubber (ABR), pyridine-butadiene rubber (PBR), and the like. In addition, they may be either solid rubber or liquid rubber, and when they are liquid rubber, they may have no functional group at the polymer end, or may have one end or both ends. Even if the terminal has a functional group such as a carboxyl group, a hydroxyl group, a vinyl group, or an amino group, there is no problem.

In the above description, the modified BR includes
BR (polybutadiene) as described above using various techniques conventionally known as a method for modifying an elastomer.
Any of those modified can be employed, and specific examples thereof include epoxy or epoxy resin-modified polybutadiene, maleic acid or maleic anhydride-modified polybutadiene, acrylic acid or methacrylic acid-modified polybutadiene, and urethane-modified polybutadiene. In addition, elastomers obtained by further modifying them, for example, semi-esterified products and imidized products of maleic anhydride-modified polybutadiene, and aminated products of epoxy-modified polybutadiene can be given.

In the present invention, it is possible to use only the BR rubber as described above as the rubber component to be compounded in the rubber composition. However, the BR rubber and various other known rubbers can be used. There is no problem if the rubber composition is used as a rubber component by using a combination of the material and the rubber component, so that the characteristics and functions according to the type of the rubber material used together can be improved. In the vulcanized rubber molded article 4, it can be advantageously exhibited. For example, by using natural rubber (NR) as such a rubber material, the vulcanized rubber molded body 4
In addition, it is possible to effectively impart mechanical properties such as strength, durability fatigue properties, spring properties, and the like. In addition, by employing ethylene propylene rubber (EPR), the vulcanized rubber molded body 4 has excellent properties. It is possible to realize weather resistance, heat resistance, and the like.

When a combination of a BR rubber and another rubber material is employed as the rubber component in the rubber composition as described above, the combination ratio (blend ratio) of the combination is usually used. It is appropriately set in consideration of the rubber type and the like.
In the case of the R-based rubber and other rubber materials, the BR-based rubber is preferably the modified BR so that the ratio of the BR-based rubber is 1% by weight or more based on the total amount of the rubber component composed of the rubber. In this case, 2% by weight or more, and when the BR rubber is other than the modified BR, 5% by weight or more is used in combination. If the amount of BR rubber in the rubber component becomes too small,
This is because the effects of the present invention as described above cannot be sufficiently achieved.

Further, in the rubber composition according to the present invention, besides the rubber component, if necessary, various known rubber compounding agents such as a vulcanizing agent and a vulcanization accelerator,
Vulcanization accelerator, reinforcing agent such as carbon black, softener such as oil, plasticizer, anti-aging agent, stabilizer, flame retardant, etc.
Even if it is appropriately blended in the usual quantitative range, there is no problem at all. Among such compounding agents, as the vulcanizing agent, an appropriate vulcanizing agent is selected from various known vulcanizing agents depending on the type of the BR rubber or the like that provides the rubber component.
To be used, but generally, sulfur, peroxide,
Quinone dioxime, chlorine compounds, polyisocyanates and the like are used.

In the present invention, as the operation (A), an unvulcanized product of the rubber composition prepared as described above is used and molded into a desired shape. On the other hand, by vulcanizing, the vulcanized rubber molded body 4 is formed. As a method of molding and vulcanizing the rubber composition used in forming such a vulcanized rubber molded body 4, various methods used in general rubber processing can be appropriately employed. ,
After the rubber composition is molded by extrusion molding, calendering, or the like, the rubber composition is vulcanized by direct vulcanization, indirect vulcanization, can vulcanization, radiation vulcanization, or the like at a time or continuously. Methods, press vulcanization methods such as compression molding vulcanization, transfer molding vulcanization, and injection molding vulcanization are advantageously used. Further, vulcanization conditions such as temperature and time during vulcanization of the rubber composition are appropriately set in consideration of the composition of the target rubber composition and the like.

Next, in the present invention, the outer surface of the vulcanized rubber molded article 4 obtained above is subjected to a surface modification treatment in accordance with the operation (B).

Here, such a surface modification treatment is performed on at least the surface (8) of the vulcanized rubber molded body 4 with which the polyamide molded body 6 is brought into contact. Although various techniques generally used in modifying the surface of a polymer compound such as a resin can be advantageously performed, in the present invention, particularly, ultraviolet irradiation treatment, plasma discharge treatment, It is preferable to modify the surface of the vulcanized rubber molded body 4 by corona discharge treatment or plasma jet treatment, whereby a high modifying effect can be advantageously and easily obtained.

Incidentally, the ultraviolet irradiation treatment employed as such a surface modification treatment is performed by a mercury lamp,
It is carried out in the air or under a predetermined gas atmosphere such as a nitrogen gas using an ultraviolet irradiation device or an exposure device provided with a light source capable of emitting ultraviolet light such as a halogen lamp, an excimer lamp, and an excimer laser. Preferably, the vulcanized rubber molded body 4 is treated using an ultraviolet irradiation device (exposure device) equipped with a low-pressure ultraviolet lamp capable of emitting ultraviolet light having a peak wavelength of 300 nm or less. It is recommended. In general, it is well known that the lower the wavelength of ultraviolet light, the higher its energy becomes. Therefore, if processing is performed with ultraviolet light having a peak wavelength as described above, its processing efficiency and processing effect can be improved. Can be advantageously achieved. The processing conditions such as the processing time and temperature, the intensity of the ultraviolet light, the distance from the light source to the surface of the vulcanized rubber molded body 4 and the like in the ultraviolet irradiation treatment are determined according to the type of the light source. The degree of bonding required for the vulcanized rubber molded article 4 is appropriately set within a usual range, taking into account the compounding composition of the rubber composition constituting the vulcanized rubber molded article 4.

In the surface modification treatment of the vulcanized rubber molded body 4 by the plasma discharge treatment or corona discharge treatment, generally, an appropriate discharge treatment device is used to perform plasma discharge between the electrodes under a predetermined gas atmosphere. Alternatively, a method of modifying the outer surface of the vulcanized rubber molded article 4 by generating corona discharge is employed. In these discharge treatments, a discharge time and a power value (output) required for the discharge are used. The processing conditions, such as,
The degree of bonding required for the rubber / polyamide composite 2,
It is set appropriately in consideration of the composition of the rubber composition constituting the vulcanized rubber molded body 4, the type of gas used, and the like. As the gas used in such a discharge treatment, in the corona discharge treatment, since it can be performed under either atmospheric pressure or reduced pressure, other gases such as air, oxygen gas, and nitrogen gas are used. While an inert gas such as an argon gas can be used, the plasma discharge treatment is usually performed in a low-pressure atmosphere, so that a vacuum vessel is used as a discharge treatment device. After the pressure in the vacuum container is reduced using a device having electrodes inside the container, a predetermined gas is injected and filled in the container. Oxygen gas, nitrogen gas, inert gas, or the like is used as a gas to be filled in such a vacuum vessel.

Further, in the plasma jet treatment as the surface reforming treatment, a predetermined gas can be ionized and converted into plasma by using discharge or the like, and the plasma can be accelerated and jetted from a nozzle in a jet state. By using various known plasma jet processing apparatuses as described above, the plasma jet sprayed from the nozzle is sprayed on the surface of the vulcanized rubber molded body 4. Examples of the gas used in such plasma jet processing include air, oxygen gas, nitrogen gas, and inert gas. Among them, according to the type of the plasma jet processing apparatus used, etc. In addition to the plasma jet processing apparatus and the type of gas to be used, the degree of bonding required and the rubber constituting the vulcanized rubber molded body 4 are selected as appropriate processing conditions. It is set appropriately according to the composition of the composition and the like.

In the present invention, among those exemplified above, preferably, ultraviolet irradiation treatment, corona discharge treatment, or plasma jet treatment, which can be performed in air, is more preferably performed. It is desirable that the surface modification of the vulcanized rubber molded body 4 be performed by the treatment, so that the productivity can be significantly improved and the cost can be advantageously reduced.

On the other hand, the polyamide molded body 6 constituting the rubber / polyamide composite 2 according to the present invention is obtained by the operation (C).
Is formed by bringing a predetermined polyamide in a molten state into contact with the treated surface 8 of the vulcanized rubber molded article 4 modified as described above and curing the same. In the present invention, the polyamide that provides such a polyamide molded article 6 may be selected from various known polymers having an amide bond (—CONH—) as a repeating unit, depending on the use of the composite 2 as appropriate. Are selected and used alone or in combination.

The polymer used as the polyamide is, for example, hexamethylenediamine,
Decamethylenediamine, dodecamethylenediamine, 2,
2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, etc. Represented by aliphatic, alicyclic or aromatic diamines such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. A polymer obtained by polycondensation with a dibasic acid; a crystalline or non-crystalline polymer obtained by polycondensation of an aminocarboxylic acid such as 6-aminocaproic acid, 11-aminoundecanoic acid or 12-aminododecanoic acid; Polymers obtained by ring-opening polymerization of lactams such as caprolactam and ω-dodecalactam; copolymer polyamides and the like. Specific examples thereof include nylon 6, nylon 66, and nylon 61.
0, nylon 612, nylon 11, nylon 12,
Examples thereof include aromatic nylon and amorphous nylon. It is also possible to mix other known various resin materials with this kind of polyamide,
Further, glass fiber or the like conventionally known as an additive of polyamide can be appropriately blended with polyamide.

Then, using such a polyamide,
When forming the polyamide molded body 6 having a desired shape, for example, the polyamide melted by heating is injected or extruded onto the treated surface 8 of the vulcanized rubber molded body 4 to be in a molten state. Polyamide is applied to the treated surface 8
In addition to the method of molding into a desired shape while contacting with, first, using the above polyamide, after forming a polyamide molded article having substantially the same shape as the intended polyamide molded body 6, by using various molding techniques, At least the surface of the obtained polyamide molded article which is brought into contact with the vulcanized rubber molded article 4 is heated and melted, and the molded article is superimposed on the treated surface 8 of the vulcanized rubber molded article 4. It can be carried out by using a method of pressing in response.
Therefore, after such a molding operation, the polyamide (molded product) is cured by cooling to form the desired polyamide molded product 6, and thus the polyamide molded product 6 and the vulcanized rubber molded product 4 are formed. Is integrally bonded and fixed, thereby forming the rubber-polyamide composite 2.

In the present invention, among the above-described techniques for forming the polyamide molded article 6, the use of a technique of injection-molding a polyamide on the treated surface 8 of the vulcanized rubber molded article 4 is particularly recommended. is there. Like this,
If injection molding is used to form the polyamide molded body 6, the molten polyamide can be brought into contact with the treated surface 8 of the vulcanized rubber molded body 4, and at the same time, the polyamide can be molded. Vulcanized rubber molding 4
There is an advantage that pre-compression can also be applied to the rubber, and therefore, in such a method, a rubber-resin composite type vibration isolator that requires pre-compression to increase the durability of the rubber is required. In the production of the rubber / polyamide composite (2) as a rubber or the like, it can be particularly suitably adopted.

Accordingly, in the rubber / polyamide composite 2 obtained as described above, the vulcanized rubber molded body 4 and the polyamide molded body 6 are firmly joined together with a bonding force sufficient for practical use. It is something that could be fixed,
Such a bonding property can be achieved without any adhesive at the bonding interface between the vulcanized rubber molded body 4 and the polyamide molded body 6. In the production of the polyamide composite 2, it is possible to effectively prevent or eliminate the deterioration of the working environment and the impairment of the worker's safety, and the favorable productivity is also improved. It can be realized.

The rubber / polyamide composite according to the present invention is by no means limited to the shape shown in FIG. 1, and the rubber (vulcanized rubber molded product) constituting the composite may be used according to the application. 4) and polyamide (polyamide molded body 6) can be formed in various shapes by appropriately setting the shapes. Therefore, in the product of the present invention, the rubber and the rubber exemplified above are used. It can be advantageously used as various types of rubber-resin composite products including resin composite-type anti-vibration rubber.

[0042]

EXAMPLES Hereinafter, some examples of the present invention will be described to clarify the present invention more specifically. However, the present invention imposes some restrictions by the description of such examples. It goes without saying that you don't receive anything. In addition, the present invention, in addition to the following examples, in addition to the above specific description, various modifications based on the knowledge of those skilled in the art, unless departing from the spirit of the present invention,
It should be understood that modifications, improvements and the like can be made.

First, unvulcanized rubber compositions (Nos. 1 to 18) were prepared and prepared according to the various compounding compositions shown in Tables 1 to 3 below. In preparing such a rubber composition, a butadiene rubber (B
R), natural rubber (NR), nitrile rubber (NBR), styrene-butadiene rubber (SBR), epoxy-modified polybutadiene (Eporide P manufactured by Daicel Chemical Industries, Ltd.)
B3600), maleic acid-modified polybutadiene (NISSO-PB BN-1015, manufactured by Nippon Soda Co., Ltd.), methacrylic acid-modified polybutadiene (Ricacryl 350, manufactured by RICON RESINS, USA)
0) or ethylene propylene diene three-dimensional copolymer rubber (EPDM). Also, as the vulcanizing agent, sulfur,
Or using dicumyl peroxide as a peroxide,
As a vulcanization accelerator, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), benzothiazolyl disulfide (MBTS), tetramethylthiuram disulfide (TMTD), and 2-mercaptobenzothiazole (MBT) were used. Furthermore, zinc white and stearic acid were used as vulcanization accelerators. Furthermore, carbon black, aroma oil or paraffin oil, and dioctyl phthalate (DOP) were used as a reinforcing agent, a softening agent, and a plasticizer, respectively.

Next, in order to conduct a bondability test between the rubber and the polyamide, the various rubber compositions (No.
Rubber / polyamide composites corresponding to 1) to 18) were produced.

Specifically, first, the vulcanized molded rubber which gives the rubber portion of each rubber / polyamide composite was prepared as No. 1 to 18
Each of the unvulcanized rubber compositions is introduced into a mold having a predetermined disk shape, and is press-vulcanized to obtain a diameter: 36 mmφ and a thickness: 6 mm.
And was formed in the shape of a disk. In the press vulcanization, vulcanization conditions include Nos. 9 to 14 and 16
For the rubber compositions of Nos. To 18, the conditions of 170 ° C. × 30 minutes are adopted, while for the other rubber compositions,
The condition of 160 ° C. × 20 minutes was adopted.

Next, each of the obtained vulcanized molded rubbers (No.
1 to 18) were subjected to a surface modification treatment according to any of the following treatment methods a, b, and c as shown in Tables 1 to 3 below.

Treatment method a: UV irradiation treatment Using an ultraviolet irradiation device (photo surface processor manufactured by Sen Engineering Co., Ltd.) equipped with a low-pressure ultraviolet lamp having a peak wavelength of 254 nm, a distance of 2 cm from the lamp in the irradiation device After the vulcanized molded rubber to be treated was placed at the position, the ultraviolet irradiation treatment was performed for 3 minutes in an air atmosphere.

Processing method b: Parallel plate electrode (diameter: 150 m) in a vacuum vessel made of plasma discharge treated glass
(mφ, distance between electrodes: 55 mm) using a plasma discharge treatment apparatus (manufactured by ITF Japan) at a position substantially at the center between the electrodes in the vacuum vessel. After placing the vulcanized rubber, the inside of the vacuum vessel is depressurized, and the inside pressure of the vessel is reduced to about 6 by injecting and filling argon gas into the vessel.
In the state of 7 Pa, frequency: 13.56 MH
z and power: 100 W processing conditions, 1 minute,
A plasma discharge treatment was performed.

Treatment method c: Corona discharge treatment Using a corona discharge treatment apparatus (manufactured by TANTEC, Denmark) having a wire electrode having a distance between electrodes of 10 mm, treatment is performed at a position substantially at the center between the electrodes of the treatment apparatus. In a state where the vulcanized molded rubber as the object was placed, the rubber was subjected to a corona discharge treatment for one minute under an air atmosphere under the conditions of an output of 850 W.

Nylon 66 (2020GC6 manufactured by Ube Industries, Ltd.) as a polyamide is melted on the vulcanized molded rubber of Nos. 1 to 18 which has been subjected to the surface modification treatment as described above, and injection molded. As shown in FIG.
A pair of polyamides (14, 14) having the same shape with respect to the entire both surfaces of the rubber (12) as shown in FIG.
Were integrally joined and fixed to produce a substantially cylindrical rubber / polyamide composite (Nos. 1 to 18). here,
The rubber-polyamide composites according to Nos. 1 to 7 and 9 to 17 were produced according to the present invention.

Using the various rubber-polyamide composites thus obtained, a bonding test was performed. In this joining test, first, as shown in FIG. 2B, a tensile tester (Autograph manufactured by Toyo Seiki Co., Ltd.)
Rubber and a pair of chucks (16, 16)
The polyamide portion (14,1) in the polyamide composite
After fixing 4), by displacing the upper chuck at a speed of 50 mm per minute in a direction (in the direction of an arrow in the drawing) separating the upper chuck at a normal temperature while fixing the lower chuck in position. A tensile force is applied to the rubber-polyamide composite, the tensile force [N] required at that time is measured, and the maximum value (F)
[N]), and from that, the joining force (T [MPa])
Was calculated in accordance with the following equation: T = F / A (where A [mm ² ] is the bonding area with the polyamide on one surface of the rubber), and the results are shown in Tables 1 to 3 below.
This tensile operation was performed until the rubber was broken or the rubber and the polyamide were separated at the joint interface. Further, in Tables 1 to 3 below, the destruction states shown together with the bonding force are “breakage in rubber” and “peeling at the bonding interface between rubber and polyamide” caused by performing the above-described tensile operation. It shows the percentage [%] of the "rupture in rubber" in the destruction of the rubber-polyamide composite by the above method. For example, 100% indicates that the fracture at the bonding interface between the rubber and the polyamide. It can be understood that no peeling occurred.

[0052]

[0053]

[0054]

As is clear from the results of Tables 1 to 3, in each of the rubber / polyamide composites of Nos. 1 to 7 and 9 to 17 according to the present invention, any of the rubber and polyamide composites It can be seen that a high bonding force can be realized between them and that the rubber and the polyamide are very difficult to peel off from each other. In contrast, N
In the rubber / polyamide composites according to No. 8 and No. 18, both rubbers and polyamide composites are formed from a rubber composition containing no BR rubber. It can be seen that the bondability with the film is extremely poor.

[0056]

As is apparent from the above description, in the method for producing a rubber-polyamide composite according to the present invention,
The rubber and the polyamide can exhibit the characteristic that they can be fixed to each other with a practically effective high joining force without interposing any adhesive between them, and therefore, According to such a method of the present invention, a rubber / polyamide composite in which rubber and polyamide are firmly and integrally joined and fixed can be advantageously and easily manufactured.

In the rubber / polyamide composite according to the present invention, excellent bonding properties can be realized at the bonding interface between the rubber and the polyamide. It can be advantageously used in various fields such as vibration-proof rubber, hoses, and housings for electric appliances.

[Brief description of the drawings]

FIG. 1 is an explanatory sectional view showing the configuration of a basic laminated structure of a rubber / polyamide composite according to the present invention.

FIG. 2A is a cross-sectional explanatory view showing a rubber / polyamide composite produced in an example, and FIG.
It is sectional explanatory drawing which shows the state which fixed the rubber / polyamide composite shown to (a) to the chuck | zipper of the tensile tester used in the Example.

[Explanation of symbols]

 2 Rubber / polyamide composite 4 Vulcanized rubber molded body 6 Polyamide molded body 8 Treated surface

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/00 306 C08J 7/00 306 C08L 9/02 C08L 9/02 (72) Inventor Hiroaki Ito Aichi 3-1, Higashi 3-chome, Komaki City Tokai Rubber Industries Co., Ltd. (72) Inventor Takehiko Taguchi 1-chome, Higashi 3-chome, Komaki City, Aichi Prefecture F-term (reference) 4F070 AA06 AA07 AA08 AA09 AB02 AB03 AB05 AC04 AC05 AC13 AC40 AC43 AC50 AC56 AC65 AC94 AE01 AE02 AE08 GA06 GB07 GC02 4F073 AA01 BA04 BA29 BB02 CA01 CA21 CA45 4F100 AK07A AK07J AK24A AK25A AK25J AK27A AK27J AK29A AK29A02A01A03A02A05A02A01A03A01 JK06 YY00A 4J002 AC021 AC031 AC071 AC081 AC111 CL012 CL032 CL052 DA046 EK006 ES016 FD146 FD157 G L00 GT00

Claims (9)

[Claims] 1. A B component comprising butadiene rubber, butadiene copolymer rubber or modified butadiene rubber as a rubber component.
Using a rubber composition containing at least an R-based rubber, a vulcanized molded product having a desired shape is obtained, and then subjected to a surface modification treatment. A method for producing a rubber-polyamide composite, wherein the rubber and the polyamide are integrally joined and fixed by contacting each other. 2. The method according to claim 1, wherein the butadiene copolymer rubber is SBR,
The method for producing a rubber-polyamide composite according to claim 1, which is NBR, ABR, or PBR. 3. The polybutadiene modified with epoxy or epoxy resin, polybutadiene modified with maleic acid or maleic anhydride, polybutadiene modified with acrylic acid or methacrylic acid, or polybutadiene modified with urethane or polybutadiene. A method for producing a rubber-polyamide composite of the present invention. 4. The rubber component in the rubber composition according to claim 1, wherein a rubber material other than the BR rubber is used in combination with the BR rubber. A method for producing a rubber-polyamide composite of the present invention. 5. A BR rubber comprising the butadiene rubber, butadiene copolymer rubber, or modified butadiene rubber,
The method for producing a rubber-polyamide composite according to any one of claims 1 to 4, wherein the rubber-polyamide composite is used in a proportion of 1% by weight or more of the total amount of the rubber component. 6. The method according to claim 1, wherein the surface modifying treatment is an ultraviolet irradiation treatment,
The method for producing a rubber-polyamide composite according to any one of claims 1 to 5, wherein the method is a plasma discharge treatment, a corona discharge treatment, or a plasma jet treatment. 7. The method for producing a rubber-polyamide composite according to claim 6, wherein the ultraviolet irradiation treatment is performed using a low-pressure ultraviolet lamp having a peak wavelength of 300 nm or less. 8. The method for producing a rubber / polyamide composite according to claim 1, wherein the polyamide is injection-molded on the surface of the vulcanized molded article which has been subjected to a surface modification treatment. 9. B comprising a butadiene rubber, a butadiene copolymer rubber or a modified butadiene rubber as a rubber component
A predetermined polyamide is brought into contact with the surface-modified surface of a vulcanized molded article having a desired shape obtained by using a rubber composition containing at least an R-based rubber in a molten state, and the rubber and the polyamide are combined. A rubber-polyamide composite, which is integrally joined and fixed.