JP6813352B2 - Vulcanized adhesive between polyamide resin member and rubber member and its manufacturing method - Google Patents

Description

The present invention relates to a vulcanized adhesive in which a polyamide-based resin member and a rubber member are bonded to each other during vulcanization molding of the rubber member, and a method for producing the same. The present invention also relates to a pneumatic tire provided with the vulcanized adhesive.

For example, it is known that a resin film is used as a gas barrier layer (that is, an inner liner) of a pneumatic tire, but a resin member such as a resin film generally has a problem of poor adhesiveness to a rubber member.

Patent Document 1 contains a resorcin-based formaldehyde condensate in the resin member and a melamine-formaldehyde-based resin in the rubber member in order to improve the adhesiveness between the thermoplastic polyester-based resin member and the rubber member. It is disclosed to let. However, it is a technique specialized for thermoplastic polyester-based resin members, and its application to polyamide-based resin members is not disclosed.

On the other hand, in Patent Document 2, in a laminate of a polyamide resin film and a layer of a rubber composition, a modified etherified methylol is added to the rubber composition together with a condensate of a phenolic compound such as cresol or resorcin and formaldehyde. It is disclosed to contain a methylene donor such as melamine. However, it has been found that when a condensate of a phenolic compound and formaldehyde is contained in the rubber composition together with the melamine derivative, the rubber member becomes hard and the durability of the obtained vulcanized adhesive is impaired.

Japanese Unexamined Patent Publication No. 2014-001270 Japanese Unexamined Patent Publication No. 2013-006387

An object of an embodiment of the present invention is to provide a vulcanized adhesive which can improve the adhesiveness between a polyamide resin member and a rubber member and also has durability.

The vulnerable adhesive according to an embodiment of the present invention is a vulture adhesive composed of a polyamide-based resin member and a rubber member vulture-bonded to the polyamide-based resin member, and is contained in the polyamide-based resin member. Containing a phenol compound and formaldehyde and / or a condensate of the phenol compound and formaldehyde, and containing a melamine derivative without containing the condensate of the phenol compound and formaldehyde in the rubber member. It is a thing.

The pneumatic tire according to the embodiment of the present invention includes the vulcanized adhesive in at least one portion selected from the group consisting of an inner liner portion, a sidewall portion, and a bead portion.

The method for producing a vulcanized adhesive according to an embodiment of the present invention includes a step of obtaining a polyamide resin member containing a condensate of a phenol compound and formaldehyde and / or a phenol compound and formaldehyde, and a rubber. Vulcanization in a state where the melamine derivative is added to the material forming the member and mixed, and the mixed material containing no condensate of a phenol compound and formaldehyde and the polyamide resin member are in contact with each other. It includes a step of obtaining a vulcanized adhesive composed of the polyamide-based resin member and the rubber member by performing molding.

According to this embodiment, it is possible to provide a vulcanized adhesive which can improve the adhesiveness between the polyamide resin member and the rubber member and also has excellent durability.

Hereinafter, matters related to the practice of the present invention will be described in detail.

The vulcanized adhesive according to the embodiment is composed of a polyamide-based resin member and a rubber member vulcanized and adhered to the resin member, and the rubber member does not contain a condensate of a phenol compound and formaldehyde. It contains a melamine derivative. By reacting the melamine derivative added in the rubber member with the polyamide-based resin of the resin member, the adhesive force between the resin member and the rubber member can be enhanced. More specifically, the terminal amino group in the polyamide in the resin member attacks the melamine derivative contained in the material forming the rubber member by nucleophilic attack, which causes a chemical bond, which causes the resin member and the rubber member to form a chemical bond. It develops the strong adhesive force of. Further, since the material forming the rubber member does not contain a condensate of a phenolic compound and formaldehyde, it is possible to prevent the rubber member from being cured by the reaction between the condensate and the melamine derivative, and the durability is high. Can be suppressed.

As the polyamide-based resin member, a member made of a polyamide-based resin or a polyamide-based thermoplastic elastomer is used.

As the polyamide resin, a polyamide resin or a mixture of a polyamide resin and a thermoplastic resin other than the polyamide resin is used.

Examples of the polyamide resin include nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66 copolymer, nylon 6/66/610 copolymer, nylon MXD6, and nylon. Examples thereof include nylon resins (aliphatic polyamide resins) such as 6T and nylon 6 / 6T copolymers, and any one or a combination of two or more thereof may be used.

Examples of the thermoplastic resin other than the polyamide resin include ethylene-vinyl alcohol copolymer (EVOH), vinyl acetate (EVA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC) and the like. Polyvinyl resin; Polyester resin such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), polybutylene naphthalate (PBN); polyacrylonitrile (PAN), poly Polynitrile resins such as methacrylonitrile and acrylonitrile-styrene copolymer (AS); cellulose resins such as cellulose acetate and butyrate butyrate acetate; polyvinylidene chloride (PVDF), polyvinyl chloride (PVF), polychlorofluoroethylene ( Fluorine-based resins such as PCTFE); imide-based resins such as aromatic polyimide (PI) can be mentioned, and these may be used alone or in combination of two or more. When a mixture of the polyamide resin and a thermoplastic resin other than the polyamide resin is used, it is preferable that the polyamide resin is the main component, that is, 50% by mass or more of the resin component is the polyamide resin.

The polyamide-based thermoplastic elastomer may have (A) a sea-island structure in which rubber is dispersed in the above-mentioned polyamide-based resin (preferably polyamide resin), and (B) a hard segment made of polyamide and a soft segment exhibiting rubber elasticity. It may be a block copolymer composed of (C), or may have a sea-island structure in which rubber is dispersed in the block copolymer. Preferably, a polyamide-based thermoplastic elastomer in which rubber is dispersed in a polyamide resin is used.

In the above embodiments (A) and (C), examples of the rubber constituting the dispersed phase include various types of rubber that can be crosslinked (sulfurized), and examples thereof include natural rubber (NR) and epoxidized natural rubber (ENR). Diene rubbers such as isoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR), nitrile rubber (NBR) and their hydrogenated rubbers; ethylene propylene rubber (EPDM), maleic acid-modified ethylene propylene rubber, Olefin rubbers such as maleic acid-modified ethylene butylene rubber, butyl rubber (IIR), acrylic rubber (ACM); butyl halogenated rubber (for example, butyl brominated rubber (Br-IIR), chlorinated butyl rubber (Cl-IIR)), chloroprene rubber Examples thereof include halogen-containing rubbers such as (CR) and chlorosulfonated polyethylene, and any one or two or more of these can be combined. In one embodiment, the rubber constituting the dispersed phase is at least one selected from butadiene rubber (BR), butyl rubber (IIR), butyl halide rubber, nitrile rubber (NBR) and hydrogenated nitrile rubber (H-NBR). May be used.

In the above aspects (A) and (C), the compounding ratio of the polyamide resin and rubber (ratio as a polymer excluding additives) is not particularly limited, and for example, the mass ratio (polyamide resin / rubber). It may be 90/10 to 20/80, 60/40 to 25/75, or 50/50 to 30/70.

As a preferred embodiment, in the case of the sea-island structure of the above (A), the polyamide resin obtained by melt-kneading the polyamide resin and rubber together with a cross-linking agent and dynamically cross-linking (TPV) the rubber, the polyamide resin is in a continuous phase ( A dynamic crosslinked product having a rubber crosslinked product as a dispersed phase (domain phase) may be used as the matrix phase). Examples of the cross-linking agent include phenol resins such as alkylphenol-formaldehyde resin and brominated alkylphenol-formaldehyde resin. The dynamic crosslinked product can be produced, for example, by using various kneaders such as a twin-screw extruder, a screw extruder, a kneader, and a Banbury mixer.

The above-mentioned polyamide-based resin or polyamide-based thermoplastic elastomer forming the polyamide-based resin member requires various additives such as fillers, compatibilizers, plasticizers, softeners, processing aids, stabilizers, and antioxidants. It may be appropriately blended according to the above.

As the material forming the rubber member, various rubber compositions that are vulcanized and molded can be used, and are not particularly limited. In the rubber composition, as a rubber component (a polymer component that develops rubber elasticity by vulcanization), various vulcanizable rubbers are used, and the rubber constituting the dispersed phase described above is exemplified. Preferred are diene rubbers such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), nitrile rubber (NBR), and chloroprene rubber (CR). It can be used alone or in combination of two or more. In particular, in the case of tire applications, it is preferable to use NR, IR, BR, SBR or a blended rubber of two or more of these.

The rubber composition generally includes fillers such as carbon black and silica, silane coupling agents, oils, zinc oxide, stearic acid, antiaging agents, waxes, vulcanizing agents, vulcanization accelerators, and the like. Various additives used can be blended. The blending amount of the filler is not particularly limited, but can be, for example, 10 to 200 parts by mass with respect to 100 parts by mass of the rubber component, and more preferably 20 to 100 parts by mass. Examples of the vulcanizing agent include sulfur and sulfur-containing compounds, and the blending amount thereof is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. It is a mass part. Further, as the vulcanization accelerator, at least one of various vulcanization accelerators such as sulfenamide, thiuram, thiazole, and guanidine can be used, and the blending amount thereof is rubber. It is preferably 0.1 to 7 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the component.

In the present embodiment, the melamine derivative added to the material of the rubber member is a melamine-based compound having reactivity with the terminal amino group of polyamide, and examples thereof include a methylolated melamine compound obtained by methylolating melamine. Examples of the methylolated melamine compound include methylolated melamine, alkyl etherified methylol melamine in which some or all of the methylol groups are alkyl etherified (for example, methyl etherified or ethyl etherified), and these methylolated melamines. Examples thereof include a condensate of alkyl etherified methylol melamine. Specific examples include methylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine (that is, hexamethylol melamine hexamethyl ether), hexaethoxymethyl melamine, hexamethylol. Melamine pentamethyl ether, hexamethylol melamine tetramethyl ether, pentamethylol melamine pentamethyl ether, pentamethylol melamine tetramethyl ether, pentamethylol melamine trimethyl ether, tetramethylol melamine tetramethyl ether, tetramethylol melamine trimethyl ether, trimethylol melamine trimethyl ether , Trimethylol melamine dimethyl ether and the like, and any one or a combination of two or more of these can be used.

The blending amount of the melamine derivative is not particularly limited, but is preferably 0.3 to 20 parts by mass, more preferably 0.4 to 10 parts by mass with respect to 100 parts by mass of the rubber component in the rubber member. It may be 0.5 to 5 parts by mass.

In the present embodiment, the condensate of the phenolic compound and formaldehyde is not added to the material of the rubber member. Here, the phenolic compounds include, in addition to phenol, those in which one or more of the five hydrogen atoms bonded to the benzene ring of phenol are substituted with a hydroxyl group, an alkyl group and / or an acyl group. Examples of the condensate of the phenolic compound and formaldehyde include a cresol-formaldehyde condensate, a resorcin-formaldehyde condensate, and a modified resorcin-formaldehyde condensate modified with an epoxy compound.

As described above, in the present embodiment, the material of the rubber member does not contain the condensate of the phenolic compound and formaldehyde, but the phenolic compound and formaldehyde, and / or the phenolic compound are contained in the polyamide resin member. A condensate of formaldehyde and formaldehyde (hereinafter, these may be collectively referred to as a phenolic adhesive component) may be contained. By kneading these phenol-based adhesive components into the polyamide-based resin member, the adhesiveness between the polyamide-based resin member and the rubber member can be further enhanced.

In the phenolic adhesive component to be kneaded into the polyamide resin member, as the phenolic compound, in addition to phenol, one or more of the five hydrogen atoms bonded to the benzene ring of phenol are hydroxyl groups, alkyl groups and / or Examples thereof are those substituted with an acyl group, preferably resorcin or an alkyl derivative thereof. Therefore, the preferred phenolic adhesive component is a phenolic compound containing resorcin or an alkyl derivative thereof, formaldehyde, and / or a condensate thereof, and may be a modified product thereof.

The amount of the phenolic adhesive component blended into the polyamide resin member is not particularly limited, and is, for example, 0. 0 parts by mass with respect to 100 parts by mass of the polymer component (including the polymer component of the rubber forming the dispersed phase) forming the resin member. It is preferably 5 to 20 parts by mass, more preferably 1 to 10 parts by mass, and may be 2 to 5 parts by mass.

Examples of the polyamide-based resin member include, in addition to the resin film, members having various shapes such as a sheet shape and a plate shape, and are not particularly limited. Regarding the resin film which is a preferred embodiment, the term film is not only a film having a small thickness (for example, 0.01 mm or more and less than 0.2 mm), which is often called a film, but also a film having a large thickness, which is generally called a sheet or the like. (For example, 0.2 to 5 mm, typically 0.2 to 0.5 mm) shall also be included. The thickness of the resin film is preferably 0.02 to 1.0 mm, more preferably 0.05 to 0.5 mm, and further preferably 0.3 mm or less.

The rubber member is bonded (that is, vulcanized and bonded) to the polyamide-based resin member during its vulcanization molding, and its shape and the like are not particularly limited as long as it has an adhesive interface with the polyamide-based resin member. .. Further, the rubber member is not limited to an independent member, and may be a surface rubber layer or the like that is attached to the surface of another unvulcanized rubber member in an unvulcanized state. For example, it may be a tie rubber layer arranged between the inner liner and the carcass ply. When a plurality of rubber layers are integrally provided, the surface rubber layer in contact with the polyamide resin member may be used as the rubber member, and the melamine derivative may be blended only in the surface rubber layer.

Next, a method for manufacturing a vulcanized adhesive composed of a polyamide-based resin member and a rubber member will be described.

First, when producing a polyamide-based resin member, a polyamide-based resin or a polyamide-based thermoplastic elastomer may be used and molded into a predetermined shape. At that time, the above-mentioned phenol-based adhesive component may be added and kneaded into the polyamide-based resin or the polyamide-based thermoplastic elastomer.

When the polyamide-based resin member is composed of a dynamically cross-linked product, pellets of the dynamically cross-linked product are obtained by melt-kneading the polyamide-based resin and rubber together with a cross-linking agent using a twin-screw extruder. As a method of filming the obtained pellets, for example, a method of filming a normal thermoplastic resin such as extrusion molding or calender molding can be used. For example, a resin film can be obtained by extruding the pellets of the above-mentioned dynamically crosslinked product using a twin-screw extruder or a single-screw extruder.

When the phenolic adhesive component is kneaded into the polyamide resin member, the addition time may be the same as the addition of the rubber as the dispersed phase, or may be before or after. It is preferably added after dynamic cross-linking, whereby the effect of improving the adhesiveness can be further enhanced at the time of vulcanization adhesion with the rubber member described later.

In the method for producing a vulcanized adhesive, a material forming a rubber member, that is, a rubber composition is also prepared. At that time, the rubber composition is obtained by adding and mixing the melamine derivative without adding the condensate of the phenolic compound and formaldehyde into the rubber composition. The rubber composition can be produced by kneading according to a conventional method using a commonly used mixer such as a Banbury mixer, a kneader, or a roll. Since the melamine derivative decomposes under high temperature conditions to release formaldehyde, when mixing the materials of the rubber member, for example, kneading is preferably performed at 110 ° C. or lower, more preferably 100 ° C. or lower.

A rubber composition that does not contain a condensate of a phenolic compound and formaldehyde thus obtained is used as a material for forming a rubber member, and vulcanization molding is performed in a state where the material and the polyamide-based resin member are in contact with each other. By performing the above, a vulcanized adhesive is obtained. The vulcanization molding method is not particularly limited, and for example, the polyamide resin member and the above material (that is, the unvulcanized rubber member) are molded into a predetermined shape so as to be in contact with each other and composited. The composite may be vulcanized in a molding die, or the composite may be vulcanized by press processing. Alternatively, for example, the polyamide-based resin member may be set in the injection molding mold, the above material may be injected into the injection molding mold, and vulcanization molding may be performed integrally with the polyamide-based resin member. The vulcanization temperature is also not particularly limited, and may be, for example, 140 to 200 ° C., and may be set to a temperature lower than the melting point of the polyamide-based resin or the polyamide-based thermoplastic elastomer constituting the polyamide-based resin member.

The use of the vulcanized adhesive thus obtained is not particularly limited. Preferably, it is used for various pneumatic tires such as automobiles and motorcycles. When used for a pneumatic tire, for example, a resin film as a polyamide-based resin member may be vulcanized and bonded to a rubber layer (rubber member) on the inner surface side of the tire as an inner liner.

Further, the resin film can be preferably used for a portion other than the inner liner. For example, the resin film may be laminated with a layer of a rubber member constituting the sidewall, thereby reducing the weight by thinning the sidewall. May be good. In that case, for example, a vulcanized adhesive composed of a resin sheet on the outer surface side and a vulcanized rubber on the inner surface may be formed.

Further, it can be used as a polyamide-based resin member other than the resin film, and for example, it can be used as a relatively hard member constituting a bead filler or a bead core in a bead portion. In that case, for example, a vulcanized adhesive composed of a polyamide-based resin member constituting the core together with a metal material and vulcanized rubber surrounding the core may be formed.

The method for producing such a pneumatic tire is not particularly limited, and a green tire is produced by a known method using a polyamide-based resin member such as the above resin film, and the produced green tire is vulcanized and molded in a mold. Therefore, the pneumatic tire according to one embodiment is obtained.

According to this embodiment, sufficient adhesion between the polyamide resin member and the rubber member can be realized only by adding a chemical for adhesion at the time of kneading the material forming the rubber member. Therefore, the adhesiveness can be improved without subjecting the polyamide-based resin member or rubber member to a surface treatment with an adhesive liquid or the like in advance.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. Examples 1 and 2 are reference examples.

[Material used]
Details of each material shown in Table 1 below used in Examples and Comparative Examples are as shown below.

-Nylon resin: Nylon 6/66 copolymer, DSM "Novamid 2020J"
・ Compatibility agent: "Bond First E" manufactured by Sumitomo Chemical Co., Ltd.
・ BR: "UBEPOL BR150L" manufactured by Ube Industries, Ltd.
-Crosslinking agent: Brominated alkylphenol-formaldehyde resin, "Tackiroll 250-III" manufactured by Taoka Chemical Co., Ltd.
・ NR: RSS # 3
・ SBR: "JSR1502" manufactured by JSR Corporation
-Carbon black: "Showa Black N-330T" manufactured by Cabot Japan Co., Ltd.
-Stearic acid: "Lunac S-20" manufactured by Kao Corporation
-Zinc oxide: "Zinc Oxide No. 3" manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Sulfur: "Powdered sulfur" manufactured by Tsurumi Chemical Industry Co., Ltd.
-Vulcanization accelerator: "Noxeller NS-P" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
-Melamine derivative: Hexamethoxymethylmelamine, "Silets 963L" manufactured by Cytec Industries, Ltd.
-Resorcin condensate: modified resorcin-formaldehyde resin, "Sumicanol 620" manufactured by Taoka Chemical Co., Ltd.

[Preparation and evaluation of vulcanized adhesive]
A dynamic crosslinked product was prepared according to the formulation (parts by mass) shown in Table 1 below. Specifically, a dry blend of nylon resin and a compatibilizer and rubber pellets made by masterbatching rubber and a cross-linking agent are melted by a twin-screw extruder (manufactured by Plastic Engineering Laboratory) set at 220 ° C. By kneading, it was dynamically crosslinked and pelletized. The obtained pellets were molded into a resin film having a width of 14 cm and a thickness of 0.2 mm using a single-screw extruder.

In Example 3, a resorcinol condensate as a phenolic adhesive component was added to the pellets obtained by dynamic cross-linking using a twin-screw extruder, and melt-kneaded to obtain pellets. A film was formed using pellets by a uniaxial extruder.

An unvulcanized rubber member was prepared according to the formulation (parts by mass) shown in Table 1 below. Specifically, after sufficiently mixing each material except the vulcanization agent (sulfur and vulcanization accelerator) and the melamine derivative using a Banbury mixer, the temperature of the rubber material inside is kept below 100 ° C. As described above, the vulcanizing agent and the melamine derivative were added while slowly mixing, and the kneading was continued for a while. Then, the kneaded product was taken out, molded into a sheet having a thickness of 0.3 mm with a cold roll, and then cut into a predetermined size.

The obtained unvulcanized rubber member having a thickness of 0.3 mm was used as a tie rubber layer and attached to the surface of the unvulcanized topping rubber layer of Carcasply. Each sample of a resin film having a thickness of 0.2 mm was superposed on a tie rubber layer attached to a carcass ply, and press vulcanization was carried out at a press temperature of 160 ° C., a press time of 20 minutes, and a press pressure of 30 kg / cm ^2. And glued together. The adhesiveness of the obtained vulcanized adhesive was evaluated.

The resin film having a thickness of 0.2 mm obtained above and the unvulcanized rubber member having a thickness of 0.3 mm are superposed, and the press temperature = 160 ° C., the press time = 20 minutes, and the press pressure = 30 kg / cm ² Press vulcanization was carried out at the site to bond and integrate. The durability of the obtained vulcanized adhesive was evaluated.

[Evaluation method]
The following methods for evaluating adhesiveness and durability are as follows.

-Adhesiveness: The vulcanized adhesive for adhesiveness evaluation prepared above was cut into strips with a width of 25 mm and a length of 16 cm, and a 180-degree peeling test was conducted at a peeling speed of 50 mm / min to obtain adhesive strength (N). / 25 mm) was measured.

-Durability: Performed in a manner similar to JIS K6270. Specifically, the vulcanized adhesive for durability evaluation prepared above was punched in the orientation direction (extrusion direction) with dumbbell No. 3 to prepare a test piece. The test piece was sandwiched between chucks at a distance of 3 cm and repeatedly stretched by 50% at a frequency of 5 Hz (test temperature: −20 ° C.). The number of test pieces was 10, and 50% elongation was repeated 100,000 times. When the test is performed, the resin film and the rubber member are broken, or the resin film and the rubber member are peeled off. The number of films that broke or peeled after the test was examined. The smaller the number of broken or peeled pieces, the better the low temperature durability.

As shown in Table 1, in Comparative Example 1 in which the melamine derivative was not blended in the rubber member, it did not adhere to the resin film. Therefore, the durability test could not be carried out, and it was indicated as "-" in Table 1. On the other hand, in Comparative Examples 2 and 3, the adhesiveness between the resin film and the rubber member was improved by blending the melamine derivative in the rubber member, but the durability was inferior because the resorcin condensate was also blended in the rubber member. Was there. On the other hand, in Examples 1 to 3 in which the melamine derivative was blended without blending the resorcinol condensate in the rubber member, the adhesiveness between the resin film and the rubber member was remarkably improved, and the durability was also excellent. It was.

Although some embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments, omissions, replacements, changes, etc. thereof are included in the scope and gist of the invention, as well as in the scope of the invention described in the claims and the equivalent scope thereof.

Claims (3)

A sulfide adhesive body composed of a polyamide-based resin member and a rubber member vulture-bonded to the polyamide-based resin member. In the polyamide-based resin member, a phenol compound, formaldehyde, and / or phenols A vulverable adhesive containing a condensate of a compound and formaldehyde and containing a melamine derivative without containing a condensate of a phenolic compound and formaldehyde in the rubber member. A pneumatic tire comprising the vulcanized adhesive according to claim 1 in at least one location selected from the group consisting of an inner liner portion, a sidewall portion, and a bead portion. A step of obtaining a polyamide-based resin member containing a phenolic compound and formaldehyde, and / or a condensate of a phenolic compound and formaldehyde, and
The process of adding and mixing melamine derivatives into the material that makes up the rubber member,
By performing vulcanization molding in a state where the mixed material containing no condensate of a phenol compound and formaldehyde and the polyamide resin member are in contact with each other, the polyamide resin member and the rubber member are formed. The process of obtaining a vulcanized adhesive and
A method for producing a vulcanized adhesive, including.