JP2001162722A - Polyamide/rubber composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide/rubber composite wherein a polyamide layer and a rubber layer are strongly and integrally bonded without interposing an adhesive between both layers. SOLUTION: A polyamide/rubber composite 2 is constituted of a polyamide layer 4 comprising a polyamide composition containing a maleic anhydride modified rubber and a rubber layer 6 which is formed by directly applying a rubber composition, which contains a diene type uncrosslinked rubber component, a phenol resin and sulfur or an uncrosslinked rubber component with an iodine value of 36 or less, double bond-containing silane or liquid modified polybutadiene and organic peroxide, to the polyamide layer 4 to vulcanize the rubber composition layer to bond the same to the polyamide layer 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide / rubber composite, and more particularly, to a polyamide / rubber composite comprising a polyamide layer and a rubber layer, which are firmly integrated without interposing an adhesive therebetween. The technology relates to a technology that can be joined to

[0002]

BACKGROUND ART Conventionally, a resin-rubber composite formed by integrally bonding a predetermined resin and rubber has been widely used in various fields. For example, a tubular resin and rubber have been used. In addition to resin-rubber composite hoses formed by laminating each other, resin hoses and rubber joints, or integrated composite products of rubber hoses and resin connectors, in recent years, attention has been paid to anti-vibration rubber that can advantageously reduce weight and cost. For example, a resin-rubber composite type vibration damping rubber in which a resin support member is attached to rubber instead of the conventional metal support member is such. In recent years, in electric appliances and the like that require waterproofness such as mobile phones, such a resin-rubber 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.

When manufacturing such a resin-rubber composite, generally, first, a resin layer of a desired shape is formed using a predetermined resin, and then a predetermined layer of the obtained resin layer is formed. After applying a suitable adhesive to the surface,
A method of molding an unvulcanized (uncrosslinked) rubber composition that provides a composite rubber layer on the adhesive-coated surface, and then vulcanizing and bonding the same, or vulcanizing the unvulcanized rubber composition in advance After applying an adhesive to a predetermined surface of the rubber layer formed by molding, a predetermined resin is molded on the application surface to form a resin layer of the composite, and at the same time, it is adhered to the rubber layer. The technique has been widely used since the resin layer and the rubber layer can be bonded to each other with a sufficient bonding force or adhesive force.

However, in such a method of forming a resin-rubber 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 in order to apply such an adhesive evenly on the surface of the resin layer, it is necessary to prepare the adhesive. In addition, it is necessary to pay close attention to the concentration of the adhesive component in the solvent, and it is necessary to strictly control the working conditions such as the working time and the working environment temperature in the coating process. A series of operations related to the application of the adhesive becomes extremely troublesome, and therefore, lowers productivity. There was a problem to have.

[0005] Therefore, in order to cope with such a problem, various methods for satisfactorily joining the resin layer and the rubber layer 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 comprising a resin layer formed by using a resin contained in a proportion of not less than% by weight, while compounding a double bond-containing silane and a peroxide vulcanizing agent with various rubber components ( A technique of forming a polyamide-rubber composite by bonding a rubber compound) to the previously obtained resin layer by pressure bonding and vulcanization bonding is disclosed. Japanese Patent Application Laid-Open No. 11-207875 discloses a method for producing a resin-rubber composite type vibration damping rubber, in which a specific uncrosslinked rubber component, a double bond-containing silane and an organic peroxide are prepared on a polyamide whose surface is alkali-treated. There is disclosed a method of forming a target vibration-proof rubber (resin-rubber composite) by vulcanizing and molding a rubber composition containing an oxide.

However, the present inventors have studied and found that any of the various composites formed according to the method described in the above-mentioned specification and publication can realize a certain degree of bonding force. However, it has been found that it is still not enough in practical use, and that there is still room for improvement.

[0008]

Under these circumstances, the present inventors have conducted intensive studies and as a result, have found that a polyamide layer is formed using a composition obtained by mixing various rubber materials modified with maleic anhydride with a predetermined polyamide. While being formed, as a rubber composition, a natural rubber, a diene-based raw rubber such as a synthetic rubber obtained by polymerization of a diolefin monomer such as butadiene or copolymerization of a diolefin monomer and another monomer, a phenol resin and For a composition in which sulfur is compounded together, or a raw rubber having a small number of double bonds, a silane compound containing an olefin double bond (double bond-containing silane) or liquid modified polybutadiene and an organic peroxide are used. Using any one of the compositions prepared by combining the above, the polyamide layer obtained directly is added directly to the obtained polyamide layer. Adhesive allowed, in the polyamide-rubber composite obtained by forming a rubber layer Te following, found that the those that with their polyamide layer and the rubber layer, could be secured together with a high bonding strength,
The present invention has been completed.

Here, the present invention has been completed based on the above-mentioned findings, and the problem to be solved is that the polyamide layer and the rubber layer are firmly bonded without the use of an adhesive. An object of the present invention is to provide a polyamide-rubber composite which is integrally joined.

[0010]

According to the present invention, in order to solve such a problem, a polyamide layer comprising a polyamide composition containing a maleic anhydride-modified rubber, a diene-based uncrosslinked rubber component, a phenol resin, and sulfur are used. Vulcanization bonding directly on the polyamide layer using a rubber composition containing or an uncrosslinked rubber component having an iodine value of 36 or less and a rubber composition containing a double bond-containing silane or liquid modified polybutadiene and an organic peroxide. By doing so, the gist is a polyamide-rubber composite having the formed rubber layer.

That is, the polyamide according to the present invention
In the rubber composite, while the polyamide layer constituting it is formed of a polyamide composition containing a maleic anhydride-modified rubber, a rubber layer directly vulcanized and bonded to such a polyamide layer, Due to the great feature of being formed from the rubber composition according to or as described above, the polyamide layer and the rubber layer may cause, between the respective layers, a factor such as deterioration of the working environment during the production of the composite and decrease in productivity. Without any intervening adhesive
It is possible to firmly adhere to each other with a practically advantageous bonding force, therefore, in the polyamide-rubber composite of the present invention that can exhibit such excellent bonding properties, It can be advantageously used in various fields such as rubber vibration insulators, hoses, and housings for electric appliances.

According to a preferred embodiment of the polyamide-rubber composite according to the present invention, the polyamide composition for providing the polyamide layer contains the maleic anhydride-modified rubber in a proportion of 1 to 50% by weight. Preferably, the phenolic resin constituting the rubber composition is advantageously used in a proportion of 1 to 20 parts by weight based on 100 parts by weight of the diene-based uncrosslinked rubber component. Will be done. According to another preferred embodiment of the present invention, the double bond-containing silane contained in the rubber composition according to the present invention, advantageously,
In the rubber composition, the liquid modified polybutadiene is used in an uncrosslinked rubber component having an iodine value of 36 or less, while the rubber composition is used in a proportion of 2 to 10 parts by weight based on 100 parts by weight of the uncrosslinked rubber component having an iodine value of 36 or less. It is desirable to use the rubber component in an amount of 1 to 40 parts by weight based on 100 parts by weight of the rubber component. By adopting each of these embodiments, the desired physical properties can be sufficiently ensured in the polyamide layer or the rubber layer formed from the polyamide composition or the rubber composition, and the polyamide layer and the rubber can be used. At the bonding interface with the layer, advantages such as the above-mentioned excellent bonding properties can be more effectively exhibited.

According to another preferred embodiment of the polyamide-rubber composite of the present invention, the rubber composition, that is, a rubber composition containing the diene-based uncrosslinked rubber component, a phenol resin and sulfur is provided. As the substance, a substance further containing a methylene donor is advantageously employed.

According to still another preferred embodiment of the polyamide-rubber composite according to the present invention, the double bond-containing silane is vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris (2- Preferably, it is a silane compound selected from the group consisting of methoxyethoxy) silane, 3-methacryloxypropyl-trimethoxysilane and 3-methacryloxypropyl-triethoxysilane, and also another desirable embodiment of the present invention. According to one of the liquid-modified polybutadiene, epoxy-modified polybutadiene, epoxy resin-modified polybutadiene, acrylic acid-modified polybutadiene, methacrylic acid-modified polybutadiene, maleic acid-modified polybutadiene, maleic anhydride-modified polybutadiene,
And a liquid polymer selected from the group consisting of urethane-modified polybutadiene.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a basic structure of a polyamide-rubber composite according to the present invention as described above. In FIG. 1, the polyamide / rubber composite 2 has a laminated structure in which a polyamide layer 4 and a rubber layer 6 are integrally joined.
In the present invention, the polyamide layer 4 and the rubber layer 6
Are formed by using a specific polyamide composition and a rubber composition, respectively, and the rubber layer 6 is bonded to the polyamide layer 4 by vulcanization bonding.
Where they are integrated, they have exceptional features.

That is, in the polyamide-rubber composite 2 of the present invention, the polyamide layer 4 constituting the same is formed of a polyamide composition containing a maleic anhydride-modified rubber, while the rubber layer 6 However, in addition to the diene-based uncrosslinked rubber component as a base component, two essential components, specifically, a rubber composition containing sulfur and a phenolic resin, or an iodine value of 36 or less as a base component Using one of the rubber compositions containing an organic peroxide and a double bond-containing silane or a liquid-modified polybutadiene as an essential component together with the uncrosslinked rubber component having, on the polyamide layer 4 as described above. By being formed by direct vulcanization bonding, the polyamide layer 4 and the rubber layer 6 are integrally joined. In the bonding interface between such a polyamide layer 4 and the rubber layer 6, irrespective of the adhesive also does not use anything like, it is the high bonding property becomes to be secured satisfactorily.

Accordingly, in the polyamide / rubber composite 2 having such excellent bonding properties, the shape thereof is appropriately set, for example, by using a resin / rubber composite type vibration-isolating rubber or a resin / rubber. In addition to a composite hose, a resin hose and a rubber joint, or an integrated composite product of a rubber hose and a resin connector, it can be advantageously used as a waterproof housing part used for electric appliances such as mobile phones. .

Here, the polyamide layer 4 which is one of the constituent layers of the polyamide-rubber composite 2 according to the present invention is formed by injection molding and extrusion molding using a polyamide composition containing a maleic anhydride-modified rubber. And the like. In this case, the maleic anhydride-modified rubber added and contained in the polyamide composition giving the polyamide layer 4 is maleic anhydride. An appropriate material is selected from various rubber materials modified by graft polymerization using the anhydride of the above, and used alone or in combination of two or more. Needless to say, any of various known rubbery materials which can be modified with maleic anhydride can be advantageously used as a raw material for providing such a maleic anhydride-modified rubber.

In the present invention, the amount of the maleic anhydride-modified rubber used is such that the polyamide-rubber composite 2 can exhibit sufficient bonding properties.
Although it is appropriately set in consideration of the type of the modified rubber and the like, generally, the maleic anhydride-modified rubber is used so as to be 1 to 50% by weight of the total amount of the polyamide composition. Becomes However, if the amount used is too small, the bondability between the polyamide layer 4 made of such a polyamide composition and the rubber layer 6 will be significantly reduced, and conversely, if the amount used is too large, This is because, in addition to causing a decrease in the physical properties of the polyamide layer 4, the appearance of the polyamide layer 4 is greatly impaired.

The polyamide composition containing the maleic anhydride-modified rubber as described above can be uniformly mixed with the above-mentioned maleic anhydride-modified rubber by using a predetermined polyamide as a base component. The polyamide as a base component of such a polyamide composition may be any one of an appropriate one of various known polymers having an amide bond (—CONH—) as a repeating unit. Is a mixture of two or more of them.

The polymer employed 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.

In addition to the polyamide and the maleic anhydride-modified rubber, the polyamide composition according to the present invention may further include, if necessary, various known resin materials other than polyamide, and a polyamide resin. It is also possible to appropriately mix glass fiber or the like known as an additive, whereby various properties according to the type of such a compound are advantageously imparted to the polyamide layer 4. I can do it.

On the other hand, in the polyamide-rubber composite 2 according to the present invention, the rubber layer 6 integrally formed on the polyamide layer 4 made of the above-described polyamide composition is, as described above, a rubber according to the above or above. Provided in the composition.

The rubber composition for providing the rubber layer 6 contains an uncrosslinked diene rubber component as a base component, and the raw rubber used as such a diene rubber component is as follows. Natural rubber (N
In addition to R), it can be obtained by polymerization of a diolefin monomer having two olefin double bonds such as butadiene, isoprene, chloroprene or the like, or by copolymerization of such a diolefin monomer with a monomer copolymerizable therewith. Various synthetic rubbers such as butadiene rubber (BR) and acrylonitrile-butadiene rubber (NB
R), styrene-butadiene rubber (SBR), vinylpyridine-butadiene rubber (PBR), acrylate-butadiene rubber (ABR), chloroprene rubber (CR),
Nitrile / chloroprene rubber (NCR), styrene / chloroprene rubber (SCR), polyisoprene rubber (I
R), nitrile-isoprene rubber (NIR), styrene-isoprene rubber (SIR), butyl rubber (IIR), and the like. An appropriate rubber is selected from those raw rubbers and used alone or in combination.

Further, sulfur which is one of the components constituting the rubber composition together with the diene-based uncrosslinked rubber component,
Generally, the uncrosslinked rubber component is used in an appropriate amount according to the type of the raw rubber giving the component, etc.
Usually, as the amount of use, an amount of about 0.5 to 10 parts by weight with respect to 100 parts by weight of the diene-based uncrosslinked rubber component is advantageously employed. , An appropriate crosslinking density can be realized, and the bonding property between the rubber layer 6 and the polyamide layer 4 becomes good. In the present invention, as long as the amount of sulfur is within such a quantitative range, the method of adding and compounding the sulfur is not limited. For example, sulfur is added as a vulcanizing agent for a diene-based uncrosslinked rubber component, By mixing a known sulfur donor such as thiuram polysulfides or morpholine disulfide capable of dissociating and releasing active sulfur as a vulcanizing agent, sulfur can be added to the rubber composition. is there.

Further, as the essential components of the rubber composition according to the present invention, the diene-based uncrosslinked rubber component and the phenol resin used in combination with sulfur include phenols such as phenol, cresol, xylenol, and resorcinol; Formaldehyde, acetaldehyde,
A resin obtained by reacting with an aldehyde such as furfural or the like under an acid catalyst or an alkali catalyst, or a modified resin obtained by modifying them is intended, and specific examples thereof include: For example,
Phenol-formaldehyde resin, phenol-furfural resin, resorcin-formaldehyde resin and the like can be mentioned, and one or a plurality of mixtures thereof are used.

The phenol resin of this type is used in an appropriate amount according to the degree of bonding required for the polyamide-rubber composite 2 and the type of uncrosslinked rubber component to be combined. The phenol resin is used in an amount of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the diene-based uncrosslinked rubber. This is because if the amount of the phenol resin used is too small, the bondability of the finally obtained polyamide-rubber composite 2 is greatly reduced. This is because, in the rubber layer 6, the physical properties of the rubber, such as the hardness thereof being too high, are caused, or the cost is increased.

In the present invention, it is desirable to further compound various compounds conventionally known as methylene donors with the rubber composition having such a compounding composition. That is, such a methylene donor is capable of accelerating the crosslinking reaction in the phenol resin and exerting a function of curing the phenol resin. In the present invention, particularly, in preparing the rubber composition, novolak is used as the phenol resin. When a system resin is used, it is advantageously used.

Examples of such a methylene donor include hexamethylenetetramine, paraformaldehyde, and melamine-based resins, and one or a combination of two or more of them can be used. The amount of the phenol resin used is usually 1 part by weight of the phenol resin in the rubber composition.
The ratio is determined so as to be about 0.03 to 1 part by weight. However, if the amount is less than 0.03 parts by weight, the compounding effect cannot be sufficiently expected. On the other hand, if it exceeds 1 part by weight, the effect corresponding to it will be sufficient. This is because it cannot be obtained.

On the other hand, in the present invention, the rubber layer 6
The rubber composition used as a material for forming a base material contains an uncrosslinked rubber component having an iodine value of 36 or less (hereinafter, such a rubber component is referred to as a low iodine value uncrosslinked rubber component) as a base component. It is necessary to contain it. As a result of intensive studies by the present inventors, the iodine value was 3 as the base component of the rubber composition.
When a rubber component exceeding 6 (in other words, a rubber component containing a large number of double bonds) is used, the intended polyamide-rubber composite 2 cannot sufficiently achieve the desired bonding property, and as a result, This is because it has been found that problems such as a decrease in the durability of the composite 2 occur. The iodine value of the uncrosslinked rubber component is generally determined by adding an alcohol solution of iodine and mercury (II) chloride or a glacial acetic acid solution of iodine chloride to a chloroform or carbon tetrachloride solution of the uncrosslinked rubber component for a predetermined time. After standing, iodine remaining without reaction was titrated with a normal solution of sodium thiosulfate.
It can be obtained by using a known measuring method such as calculating the amount of absorbed iodine.

Here, as the uncrosslinked rubber component having a low iodine value, various raw rubbers which can advantageously realize the above-mentioned iodine value, for example, ethylene / propylene rubber (EP)
M), ethylene-propylene-non-conjugated diene copolymer rubber (EPDM), and hydrogenated acrylonitrile-butadiene rubber (H-NBR) obtained by subjecting acrylonitrile-butadiene rubber to hydrogenation treatment. One or more of those having an iodine value of 36 or less, preferably 28 or less can be appropriately selected and used in consideration of the use of the polyamide-rubber composite 2 and the like. In particular, EPDM having such an iodine value is suitably used in that it has excellent physical properties after crosslinking.

The rubber composition containing such a specific uncrosslinked rubber component as a base component further contains an organic peroxide as an essential component. Generally, the organic peroxide is vulcanized. And organic peroxides such as benzoyl peroxide, dicumyl peroxide, and di-t.
-Butyl peroxide, t-butylcumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5 Di (benzoylperoxy) hexane, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxypropyl) benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxy Oxybenzene, 2,
4-dichlorobenzoyl peroxide, 1,1-di-
It has been conventionally used as a peroxide vulcanizing agent for elastomers such as t-butylperoxy-3,3,5-trimethylcyclohexane and n-butyl-4,4-di-t-butylperoxyvalerate. Are variously used advantageously. And among the above examples,
The use of dicumyl peroxide is particularly recommended because various physical properties or characteristics can be expressed in a good balance in the obtained rubber layer 6.

If the amount (combination amount) of this kind of organic peroxide is too small, the compression set in the rubber layer 6 becomes excessive, and the bonding between the rubber layer 6 and the polyamide layer 4 becomes too large. In general, the low iodine value of the uncrosslinked rubber component is 100
It is used so that the ratio is 1 part by weight or more based on parts by weight. On the other hand, as the upper limit of the amount of organic peroxide used,
Usually, the amount is about 10 parts by weight based on 100 parts by weight of the low iodine value uncrosslinked rubber component so that a decrease in bonding property and durability in the polyamide-rubber composite 2 can be advantageously prevented.

Further, in the rubber composition containing the low iodine value uncrosslinked rubber component, one of the double bond-containing silane and the liquid-modified polybutadiene may be used as an essential component together with the organic peroxide. Is compounded.

Incidentally, such a double bond-containing silane is intended to mean an organosilicon compound having an olefin double bond in its molecular structure, and specifically includes vinyltrimethoxysilane and vinyltriethoxysilane. And vinyl-tris (2-methoxyethoxy) silane, 3-methacryloxypropyl-trimethoxysilane, 3-methacryloxypropyl-triethoxysilane, and the like. Generally, one or more of them can be mentioned. Are used in combination. Among them, 3-methacryloxypropyl-trimethoxysilane is advantageously used as a suitable double bond-containing silane.

The amount of the silane containing a double bond is appropriately determined depending on the required degree of bonding, taking into account the type of the low iodine value uncrosslinked rubber component to be used and the like. However, generally, 2 to 100 parts by weight of the low iodine value uncrosslinked rubber component in the rubber composition,
The amount is set to 10 parts by weight, preferably 3 to 6 parts by weight. If the amount of the double bond-containing silane used is too small, the bonding property at the bonding interface between the rubber layer 6 and the polyamide layer 4 becomes insufficient, and if it is excessively large, Adversely affects the physical properties of the rubber layer 6 or the polyamide-rubber composite 2
This causes problems such as an increase in the manufacturing cost of the device.

On the other hand, as the liquid-modified polybutadiene, various known polymers obtained by modifying liquid polybutadiene using various methods conventionally known as a method for modifying a polymer compound can be advantageously used. Specific examples thereof include epoxy-modified polybutadiene, epoxy resin-modified polybutadiene, acrylic acid-modified polybutadiene, methacrylic acid-modified polybutadiene, maleic acid-modified polybutadiene, maleic anhydride-modified polybutadiene, and liquid substances such as urethane-modified polybutadiene. Those obtained by further modifying them, for example, semi-esterified or imidized liquid maleic anhydride-modified polybutadiene, aminated liquid epoxy-modified polybutadiene and the like can be mentioned.In the present invention,
One or a combination of a plurality of them is appropriately used.

In the liquid modified polybutadiene as described above, the type of the low iodine value uncrosslinked rubber component to be employed is taken into consideration so that the high bonding property aimed at by the present invention can be advantageously achieved. Usually, it is one of the low iodine value uncrosslinked rubber components.
It is used at a ratio of 1 to 40 parts by weight, preferably at a ratio of 2 to 20 parts by weight with respect to 00 parts by weight. Because the amount of the liquid modified polybutadiene is 1
When the amount is less than 10 parts by weight, the object of the present invention cannot be advantageously achieved, and in the rubber layer 6 composed of the composition containing it in an amount exceeding 40 parts by weight,
This is because the properties are unfavorable.

The rubber composition having the above-mentioned compounding composition may further contain, if necessary, a known rubber compounding agent such as a vulcanizing agent, in addition to the above-mentioned various components. Accelerators, vulcanization accelerators, reinforcing agents such as carbon black, softeners such as oil, plasticizers, anti-aging agents, stabilizers, flame retardants, etc., are appropriately blended in the usual quantitative range. If you do, you can do nothing.

Using the rubber composition or the rubber composition prepared as described above, a rubber having a desired shape is formed on a predetermined surface of the polyamide layer 4 previously formed as described above. The desired polyamide-rubber composite 2 of the present invention is formed by forming the layer 6 and bonding it by vulcanization. In the formation of the rubber layer 6 and vulcanization bonding, for example, At the same time, an unvulcanized (uncrosslinked) rubber layer 6 made of a rubber composition is formed on the polyamide layer 4 by press vulcanization such as compression molding, transfer molding, and injection molding (injection vulcanization). In addition to the vulcanization method, after the rubber composition is molded into a desired shape by extrusion molding, calendering, or the like, the unvulcanized molded product is overlaid on the polyamide layer 4, and And allowed to press in accordance with the requirements,
After forming the unvulcanized rubber layer 6, the unvulcanized rubber layer 6
Vulcanization by direct vulcanization, indirect vulcanization, can vulcanization or the like is advantageously used. The vulcanization conditions such as temperature and time during vulcanization of the rubber composition (unvulcanized rubber layer 6) are appropriately set in consideration of the composition of the target rubber composition. .

Accordingly, in the polyamide-rubber composite 2 of the present invention thus obtained, the polyamide layer 4
The rubber layer 6 and the rubber layer 6 can be firmly fixed with a bonding force sufficient for practical use. Since it can be realized without interposing any adhesive at the interface, the polyamide /
In producing the rubber 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. You can enjoy the benefits that can be realized.

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

[0043]

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, in addition to the following examples, the present invention may be variously modified based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the above specific description.
It should be understood that modifications, improvements and the like can be made.

Example 1 A polyamide / rubber composite of Nos. 1 to 18 was prepared by integrally joining a polyamide layer and a rubber layer in the following manner. For each, a bondability test between the polyamide layer and the rubber layer was performed.

First, as shown in Tables 1 to 3 below, (A) ethylene-propylene-nonconjugated ethylene-propylene-modified with maleic anhydride as shown in the following Tables 1 to 3 Nylon 6 containing diene copolymer rubber (maleic anhydride-modified EPDM) (US: Zytel ST-811HS manufactured by Du Pont), (B) Nylon 66 containing maleic anhydride-modified EPDM (US: Zytel manufactured by Du Pont) ST-801HS) or (C) Nylon 6 (1013B manufactured by Ube Industries)
Rubber compositions for providing a rubber layer of the composite were prepared and prepared in various compounding compositions as shown in Tables 1 to 3 below.
In preparing the rubber composition, natural rubber (NR) or styrene-butadiene rubber (SBR), which is a diene-based raw rubber, was used as an uncrosslinked rubber component. Further, as the phenolic resin, (a) cashew-modified phenolic resin (Sumitomo Bakelite Co., Ltd. Sumilite Resin PR12686), (b) oil-modified phenolic resin (Sumitomo Bakelite Co., Ltd. Sumilite Resin PR13349),
Or (c) using a resorcinol-based phenol resin (Sumitomo Chemical Co., Ltd. Sumikanol 620), while using a melamine resin (Sumitomo Chemical Co., Ltd. Sumikanol 507A) as a methylene donor and sulfur as a vulcanizing agent. Using. In addition, CBS and MBTS in the table below
Indicates N-cyclohexyl-2-benzothiazolylsulfenamide and benzothiazolyl disulfide as vulcanization accelerators, respectively.

Next, as shown in FIG. 2A, a rubber layer (12) having a disk shape of 36 mm in diameter × 6 mm in thickness as shown in FIG. 2A using the various polyamide compositions and rubber compositions prepared above. A substantially cylindrical polyamide-rubber composite in which a pair of polyamide layers (14, 14) having the same shape were integrally joined to the entire surface of both sides was prepared. Specifically, while using each polyamide composition, two substantially cylindrical polyamide layers each having a predetermined groove are formed by injection molding, while each rubber composition is used to form a disc-shaped unvulcanized resin. After the rubber layer is formed by extrusion molding, vulcanization conditions of 160 ° C. × 20 minutes are adopted, and the unvulcanized rubber layer is vulcanized and bonded to each of the previously obtained polyamide layers on both surfaces. Thereby, the desired polyamide-rubber composites (Nos. 1 to 18) were produced. Here, the polyamide-rubber composites according to Nos. 1 to 8 were formed according to the present invention.

Using each of the thus obtained polyamide-rubber composites, a bonding test was performed. In this bondability test, first, as shown in FIG. 2 (b), a pair of chucks (16, 16) provided in a tensile tester (Autograph manufactured by Toyo Seiki Co., Ltd.) Polyamide layer (14,1) in composite
After fixing each of 4), the upper chuck is moved at a rate of 5 min./min.
At a speed of 0 mm, the polyamide-rubber composite was displaced in a direction separating from the lower chuck at a speed of 0 mm (in the direction of the arrow) to apply a tensile force, and the tensile force [N] required at that time was measured. Then, the maximum value (F [N]) of the measured value is obtained, and the bonding force (T [MP
a)) by the following equation: T = F / A (where A [mm ² ] is
This is calculated according to the bonding area of one surface of the rubber layer with the polyamide layer), and the results are shown in Tables 1 to 3 below. This tension operation was performed until the rubber layer was broken or the polyamide layer and the rubber layer 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 the rubber layer" and "bonding between the polyamide layer and the rubber layer" caused by performing the tensile operation as described above. Percentage of “breakage in rubber layer” in the breakdown of polyamide-rubber composite due to “peeling at interface” [%]
For example, the fact that it is 100% can be understood that no peeling occurred at the bonding interface between the polyamide layer and the rubber layer.

[0048]

[0049]

[0050]

As is apparent from the results of Tables 1 to 3, each of the polyamide-rubber composites of Nos. 1 to 8 according to the present invention has a structure in which the polyamide layer and the rubber layer It can be seen that a high bonding force can be realized in the case of the above, and the polyamide layer and the rubber layer are very hard to be separated from each other. On the other hand, No. 9 ~
In the polyamide-rubber composite according to Example 18, unlike the rubber composition of the present invention, the rubber composition for providing a rubber layer contains a diene-based raw rubber and sulfur, but a phenol resin. Is not blended, or, as the polyamide composition forming the polyamide layer, the one containing no maleic anhydride-modified rubber is used, any of them, the polyamide layer and the rubber layer It can be seen that the bondability is extremely poor.

Example 2 Separately from the above-mentioned Example 1, polyamide-rubber composites according to Nos. 19 to 45 were produced, and each of them was subjected to a bonding test.

Specifically, first, as shown in Tables 4 to 7 below, the polyamide composition for providing the desired polyamide / rubber composite polyamide layer was the same as that used in Example 1 above. A similar polyamide composition (A),
While preparing (B) and (C), a rubber composition for providing a rubber layer of the composite was prepared and prepared according to various compounding compositions shown in Tables 4 to 7 below. In the preparation of such a rubber composition, as an uncrosslinked rubber component, the iodine value of ethylene / propylene /
Non-conjugated diene copolymer rubber (EPDM) or hydrogenated acrylonitrile-butadiene rubber (H-NBR) was used. Further, 3-methacryloxypropyl-trimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the double bond-containing silane, while epoxy-modified polybutadiene (Eporide PB3600 manufactured by Daicel Chemical Industries, Ltd.) is used as the liquid-modified polybutadiene. Maleic acid-modified polybutadiene (NISSO-PB BN-1 manufactured by Nippon Soda Co., Ltd.)
015) or methacrylic acid-modified polybutadiene (US:
Ricacryl 3500 manufactured by RICON RESINS) was used, and dicumyl peroxide, which is an organic peroxide, was further used as a vulcanizing agent.

Next, using the various polyamide compositions and rubber compositions prepared above, the vulcanization conditions at the time of vulcanization were set to 170 ° C. × 30 minutes in the same manner as in Example 1 except that FIG. Nos. 19 to 45 having a shape as shown in FIG.
Was prepared.

Each of the thus obtained polyamide / rubber composites was subjected to the same bonding test as in Example 1 above, and the results (bonding strength and breaking state [%]) were shown in Tables 4 to 4 below. 7 is also shown. Here, the polyamide-rubber composites of No. 19 to No. 30 are formed according to the present invention.

[0056]

[0057]

[0058]

[0059]

As is clear from the results of Tables 4 to 7, in the polyamide-rubber composites of Nos. 19 to 30 according to the present invention, in any of them, the polyamide layer and the rubber layer have a high bonding strength. It was recognized that the layers were adhered to each other with a force, so that the layers were extremely difficult to be separated from each other. On the other hand, in each of the polyamide-rubber composites according to Nos. 31 to 45, a rubber component having an iodine value too high is blended in a rubber composition for providing a rubber layer, or an iodine value of 36 or less. Although the rubber component and the organic peroxide are blended, neither the double bond-containing silane nor the liquid-modified polybutadiene is blended, or the polyamide layer has no maleic anhydride-modified rubber at all. Since it is formed of a polyamide composition that does not contain any of them, any of them is inferior in bonding property between the polyamide layer and the rubber layer as compared with those of the examples of the present invention. I understand.

[0061]

As is apparent from the above description, in the polyamide-rubber composite according to the present invention, the polyamide layer and the rubber layer constituting the composite are formed with no adhesive interposed between them. In spite of the fact that it is not, it can be firmly and integrally fixed with an excellent bonding force. Therefore, such a product of the present invention is a vibration-proof rubber, a hose, a housing for electric appliances. In various fields such as
It can be used to advantage.

[Brief description of the drawings]

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

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

[Explanation of Signs] 2 Polyamide-rubber composite 4 Polyamide layer 6 Rubber layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroaki Ito 3-1-1 Higashi Higashi Komaki City, Aichi Prefecture (72) Inventor Takehiko Taguchi 3-1-1 Higashi Higashi Komaki City, Aichi Prefecture Tokai Rubber Industry Co., Ltd. F term (reference) 4F100 AA01B AA36B AH02B AK02B AK28B AK29B AK33B AK46A AK48 AK75 AL06B AL07A AN00A AN00B BA02 GB90 JH02 JK06 YY00A YY00B

Claims (8)

[Claims] 1. A polyamide layer comprising a polyamide composition containing a maleic anhydride-modified rubber, a rubber composition containing a diene-based uncrosslinked rubber component, a phenolic resin and sulfur, or an uncrosslinked rubber component having an iodine value of 36 or less. Using a rubber composition containing a double bond-containing silane or a liquid-modified polybutadiene and an organic peroxide, a polyamide-rubber composite having a rubber layer formed by directly vulcanizing and bonding on the polyamide layer body. 2. The polyamide-rubber composite according to claim 1, wherein the polyamide composition contains the maleic anhydride-modified rubber at a ratio of 1 to 50% by weight. 3. The polyamide-rubber composite according to claim 1, wherein the phenol resin is used in a proportion of 1 to 20 parts by weight based on 100 parts by weight of the diene-based uncrosslinked rubber component. 4. The polyamide rubber according to claim 1, wherein the rubber composition containing a diene-based uncrosslinked rubber component, a phenol resin and sulfur further contains a methylene donor. Complex. 5. The method according to claim 1, wherein the silane containing a double bond is vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-
The polyamide according to claim 1 or 2, wherein the polyamide is a silane compound selected from the group consisting of tris (2-methoxyethoxy) silane, 3-methacryloxypropyl-trimethoxysilane, and 3-methacryloxypropyl-triethoxysilane. -Rubber composite. 6. The double bond-containing silane is added in an amount of 2 parts by weight per 100 parts by weight of the uncrosslinked rubber component having an iodine value of 36 or less.
The polyamide-rubber composite according to claim 1, used in a ratio of from 10 to 10 parts by weight. 7. The liquid-modified polybutadiene is selected from the group consisting of epoxy-modified polybutadiene, epoxy resin-modified polybutadiene, acrylic acid-modified polybutadiene, methacrylic acid-modified polybutadiene, maleic acid-modified polybutadiene, maleic anhydride-modified polybutadiene, and urethane-modified polybutadiene. The polyamide-rubber composite according to claim 1 or 2, which is a liquid polymer obtained. 8. The liquid modified polybutadiene is used in a proportion of 1 to 40 parts by weight based on 100 parts by weight of the uncrosslinked rubber component having an iodine value of 36 or less.
The polyamide-rubber composite according to claim 2 or claim 7.