WO2002022719A1

WO2002022719A1 - Process for producing vulcanized rubber/thermoplastic resin composite

Info

Publication number: WO2002022719A1
Application number: PCT/JP2000/006332
Authority: WO
Inventors: Atsushi Kazuno; Masashi Moriyama; Toshiya Tsujimoto
Original assignee: Toyo Tire & Rubber Co., Ltd.
Priority date: 2000-09-14
Filing date: 2000-09-14
Publication date: 2002-03-21

Abstract

A process for producing vulcanized rubber/thermoplastic resin composites which comprises using a mold having a cavity for vulcanized-rubber molding holding and a cavity for resin molding formation, placing a vulcanized rubber molding prepared beforehand in the cavity for vulcanized-rubber molding holding, and injecting a molten thermoplastic resin into the cavity for resin molding formation to form a resin molding, characterized by forming a vulcanizable adhesive layer (A) consisting mainly of chlorosulfonated polyethylene on that surface of the vulcanized rubber molding which is to be bonded to the thermoplastic resin, subsequently forming an adhesive layer (B) consisting mainly of a phenolic resin, and then injecting the thermoplastic resin. By the process, a vulcanized rubber/thermoplastic resin composite in which the vulcanized rubber molding has been tenaciously bonded to the thermoplastic resin can be produced with satisfactory productivity.

Description

Description Method for manufacturing vulcanized rubber / thermoplastic resin composite

The present invention relates to a method for producing a vulcanized rubber / thermoplastic resin composite, which is a composite in which a vulcanized rubber molded body and a resin molded body formed of a thermoplastic resin are bonded with high strength. Background art

Vulcanized rubber / thermoplastic resin composites, in which a vulcanized rubber molded body and a resin molded body formed of a high-rigidity resin material are integrated, are used in, for example, automotive suspensions, machine suspensions, and vibration isolation for building components. Or used for vibration damping members. As a method for producing such a vulcanized rubber-thermoplastic resin composite, for example, a technique described in Japanese Patent Publication No. 7-55510 is known.

According to the technology described in the above publication, the surface of a vulcanized rubber molded body is chlorinated, and the chlorinated surface is formed by vulcanization bonding mainly composed of a resin-type phenol resin and an aldehyde-modified polybutyl alcohol. A method for producing a vulcanized rubber / thermoplastic resin composite by forming an agent layer, disposing it in a mold, injecting a heated and melted thermoplastic resin (1), and the surface of a vulcanized rubber molded body A vulcanized adhesive layer containing chlorosulfonated polyethylene as the main component is formed on the surface of the vulcanized rubber. A method (2) for producing a resin composite is disclosed.

However, as in the above method (1), a method that requires chlorination treatment that affects the material itself of the vulcanized rubber molded article requires a crack when elasticity is applied to the rubber material. It is difficult to adopt because it may occur. In addition, the above-mentioned method (1) requires chlorination of the surface of the vulcanized rubber molded body before forming the adhesive layer, which requires a lot of time for the processing steps other than the formation of the adhesive layer, and thus the production is difficult. It is not preferable in terms of sex.

On the other hand, the above method (2) does not require the chlorination treatment as in the above method (1). However, after the vulcanized adhesive layer is formed, when the thermoplastic resin that has been heated and melted is injected and molded, the formed adhesive layer is washed away by the molten resin and stains are generated inside the mold. There is a problem to do. Such dirt is subjected to cleaning and the like. However, as the generation of dirt increases, the frequency of cleaning increases and productivity decreases. Also, the method (

2) In order to obtain sufficient adhesion, it is necessary to preheat the vulcanized rubber molded body at least at 120 ° C for about 30 minutes after forming the adhesive layer. It is not preferable in terms of productivity because a lot of time and equipment are required for processing steps other than forming.

Accordingly, an object of the present invention is to provide a vulcanized rubber formed by bonding a vulcanized rubber molded body and a thermoplastic resin with high strength to a thermoplastic resin composite, which affects the material itself of the vulcanized rubber molded body. It is an object of the present invention to provide a method which can be manufactured with high productivity without performing chlorination treatment or the like. Disclosure of the invention

The above object of the present invention can be achieved by the following method.

That is, according to the present invention, a vulcanized rubber molded body prepared in advance is disposed in the vulcanized rubber molded body containing cavity of a mold having a vulcanized rubber molded body containing cavity and a resin molded body forming cavity. A method for producing a vulcanized rubber / thermoplastic resin composite, in which a thermoplastic resin is injected in a molten state into the resin molded body forming cavity to form a resin molded body,

A vulcanized adhesive layer (A) containing chlorosulfonated polyethylene as a main component is provided on the surface of the vulcanized rubber molded product that adheres to the thermoplastic resin, and then an adhesive layer (A) containing a phenol-based resin as a main component The method for producing a vulcanized rubber 'thermoplastic resin composite, wherein the thermoplastic resin is injected after B) is provided.

Further, the present invention provides the method for producing a vulcanized rubber / thermoplastic resin composite, wherein the thermoplastic resin is a fiber-reinforced thermoplastic resin containing inorganic fibers. Method, regarding.

The present invention also relates to a method for producing a vulcanized rubber-thermoplastic resin composite, comprising: forming a resin molded article; and further heating and holding the molded article at 100 ° C. or higher. Vulcanized rubber with a fi ^ method for thermoplastic resin composites.

In the production method of the present invention, the formation of the adhesive layer does not require a chlorination treatment or the like, which affects the material itself of the vulcanized rubber molded article. In addition, the vulcanized rubber / thermoplastic resin composite obtained by the method i of the present invention has the adhesive layer (B) next to the vulcanized adhesive layer (A). When pouring, the vulcanized adhesive layer (A), which tends to have high mold contamination, is prevented from flowing out. As a result, the frequency of cleaning the mold can be reduced, and productivity is improved. Further, the formation of the adhesive layer (B) can be performed in a shorter time than the preheating step in the above method (2), and from this point, productivity can be improved. Furthermore, the adhesive strength of the adhesive layer formed from the vulcanized adhesive layer (A) and the adhesive layer (B) is practically sufficient, and is a vulcanized rubber and thermoplastic resin having a stable strength. A complex is obtained. It is preferable that the thermoplastic resin is a fiber-reinforced thermoplastic resin containing inorganic fibers to increase the physical strength. In addition, it is preferable to provide a post-cure step because a stronger adhesive force can be obtained. BEST MODE FOR CARRYING OUT THE INVENTION

As the raw material rubber constituting the rubber molded product used in the present invention, those conventionally used for rubber molded products such as vibration-proof rubber can be used without limitation. Specifically, gen-based rubber ethylene propylene rubber (EPR, EPDM) such as nitrile rubber (NBR), styrene butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR) and other synthetic rubbers, including halogenated butyl rubbers such as brominated butyl rubber (Br-IIR), polyurethane rubber, ataryl rubber, fluorine rubber, silicone rubber, and chlorosulfonated polyethylene. And natural rubber and the like, and may be used alone or in combination of two or more.

If necessary, known rubber additives, such as antioxidants, waxes, coloring agents, fillers, softeners such as plasticizers and process oils, and tackifiers are added to the rubber material to form a rubber molded product. Manufactured. In addition, as a method for crosslinking the rubber raw material composition, a method using a known crosslinking agent such as an iodine paper or a peroxide crosslinker can be used without limitation. In the present invention, examples of the thermoplastic resin forming the resin molded body include general thermoplastic resins such as polyolefin such as polypropylene, polychlorinated vinyl, polyvinylidene chloride, acrylonitrile styrene resin (AS resin), ABS, and acrylic resin. Plasticization! ^{1 It} is called engineering plastics such as raw resin, polyamide, polycarbonate, polyester such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyester resin, and modified polyphenylene ether. Thermoplastic resin, polyphenylene sulfide, polyether ether ketone (PEEK), polyarylate, polysulfone, polyether sulfone, polyketone sulfide, polyesterimide, aromatic polyester, polyamino bismaleimide, triazine resin Examples of such resins include super engineering plastics. Since the resin molded body becomes a structural member, it is preferable to use a material having high bow and high rigidity.

A thermoplastic resin reinforcing material can be added to the above-mentioned thermoplastic resin in order to increase physical strength. As the thermoplastic resin reinforcing material, inorganic short fibers are preferable. Specific examples include glass fiber, potassium titanate whisker, whiskers such as zinc oxide and calcium sulfate, and wollastonite. These inorganic short fibers are kneaded and dispersed with a thermoplastic resin by applying a force-pulling agent treatment as necessary. The content of the thermoplastic resin reinforcing material (inorganic short fiber) is not particularly limited, but it is preferable to use a fiber-reinforced thermoplastic resin containing 20 to 75% by weight of the inorganic short fiber. In particular, it is preferable to use a fibrous strength thermoplastic resin containing 30 to 60% by weight.

As the adhesive used for forming the vulcanized adhesive layer (A), those containing chlorosulfonated polyethylene as a main component can be used without particular limitation, and commercially available products may be used. Usually, an adhesive dissolved in an appropriate solvent and added with necessary additives is used as the adhesive.

As the adhesive for forming the adhesive layer (B), those having a fuanol-based resin as a main component can be used without any particular limitation, and commercially available products may be used. Usually, an adhesive dissolved in an appropriate solvent and added with necessary additives is used as the adhesive. As phenolic resins, novolak phenolic resins obtained by reacting phenols and aldehydes in the presence of an acid catalyst, or phenols and aldehydes Any of the resol-type phenol resins obtained by reacting in the presence of a catalyst can be used, but the resole-type phenol resin is preferred. Examples of the phenols include phenol, cresol, xylenol, ethylphenol, isopropylphenol, tert-butylphenol, amylphenol / nonylphenol, nonylphenol, p-chlorophenol and p-phenol. ] -Valent phenol such as bromophenol

Phenols, divalent phenols such as resorcinol, catechol and hydroquinone, and trivalent or higher phenols such as pyrogallol. These phenols can be used alone or in combination of two or more. In particular, it is preferable to combine phenol and divalent phenols such as resorcinol. As formaldehydes, besides formalin, formaldehyde generating substances such as paraformaldehyde, trioxane and tetraoxane can also be used. As the acidic catalyst or the alkaline catalyst, a conventionally known one is used. The phenolic resin also includes modified products such as those in which the hydroxy group is a cyclic acetal derivative.

Examples of additives contained in the adhesive forming the vulcanized adhesive layer (A) and the adhesive layer (B) include polybutyl alcohol and its aldehyde modified product, a gen polymer, an epoxidized gen polymer, and a halogen. Polyolefin, aromatic nitroso compound, polymer imide compound, epoxy resin, phenol epoxy resin, polybutyl acetate, casein, melamine resin, urea resin, polyurethane and other organic components, titanium oxide, oxidized powder, magnesium oxide And inorganic components such as zinc oxide, calcium oxide, silicon oxide, metal oxides such as alumina, and other organic silanes.

In addition, the vulcanized adhesive layer (A) and the adhesive layer (B) may contain a coupling agent or may be treated with the coupling agent. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and the like.

The adhesive for forming the adhesive layer (B) is described in JP-A-Heisei 4-331324, JP-A-Heisei 4-234344, JP-T-Hei 8-502. Japanese Patent Publication No. 3107, Japanese Patent Publication No. 9-5100998, Japanese Patent Publication No. 10-5099-138, Japanese Unexamined Patent Publication No. 551-2 Those described in JP-A-9-449, JP-A-63-227675, JP-A-62-107975 and the like can be used.

In the method of the present invention, first, a vulcanized rubber molded body prepared in advance is placed in the vulcanized rubber molded body containing cavity of a mold having a vulcanized rubber molded body containing cavity and a resin molded body forming cavity. Set up. Then, a vulcanized adhesive layer (A) containing chlorosulfonated polyethylene as a main component is provided on the surface of the vulcanized rubber molded body that adheres to the thermoplastic resin.

The thickness of the vulcanized adhesive layer (A) is not limited as long as the required adhesive strength is exhibited, but is generally about 5 to 50; As a method for applying the adhesive, a known method such as brush coating, dipping, spray coating or the like can be used. In forming the vulcanized adhesive layer (A) on the surface of the vulcanized rubber molded body, the surface of the vulcanized rubber molded body forming the adhesive layer (A) may be subjected to plasma treatment, corona discharge treatment, or the like. Performing pre-processing is a preferred embodiment.

Next, on the vulcanized adhesive layer (A), an adhesive layer (B) containing a phenolic resin as a main component is provided. The thickness of the adhesive layer (B) is not limited as long as the required adhesive strength is exhibited, but is generally about 2 to 20 μm. As a method for applying the adhesive, a known method such as brush coating, tipping, and spray coating can be used.

Finally, a thermoplastic resin is injected in a molten state into the resin molded body forming cavity to form a resin molded body, thereby producing a vulcanized rubber-thermoplastic resin composite. When a thermoplastic resin is injection-molded, the mold temperature, the resin temperature, the injection pressure, and the like are appropriately adjusted according to the type of the thermoplastic resin.

When injecting the thermoplastic resin in a molten state, the vulcanized rubber molded body is preheated at a temperature of about 100 to 150 ° C for about 100 to 300 minutes and placed in a mold. Alternatively, a molten thermoplastic resin can be injected. There is no need to preheat in terms of productivity. Further, it is more preferable not to preheat because the adhesive strength is high.

Further, a post-curing step of heating and holding at 100 ° C. or more after the formation of the resin molded article can be provided. It is preferable to provide a post-curing step of maintaining the caloric heat at 100 ° C. or more after the formation of the resin molded body so that a stronger adhesive force can be obtained. The vulcanized rubber 'thermoplastic resin composite obtained by the M¾ method of the present invention is, for example,

It is used for vibration isolating members and vibration damping members. A P-direction vibration member, a vibration damping member, and the like are usually interposed between high-rigidity structural members, and have an effect of preventing vibration of one structural member from being transmitted to another structural member. A structural member for attaching to each structural member is provided, at least one of which is a thermoplastic resin. Other structural members may be a metal material, or may be the same thermoplastic resin. It is preferable that both are made of a thermoplastic resin because the weight of the vibration isolating member can be further reduced.

FIG. 1 shows the shape of an adhesion test sample of a vulcanized rubber / thermoplastic resin composite used in the adhesion test in Examples. The adhesive sample 1 is composed of a resin molded body 3, an iron member 5, and a vulcanized rubber molded body 7. The adhesive surface a 1 -a 2 of the vulcanized rubber molded body 7 and the resin molded body 3 has a chlorosulfonated polyethylene as a main component on the side of the vulcanized rubber molded body 7 as shown in FIG. 2 in Example 1. The vulcanized adhesive layer (A) has an adhesive layer (B) mainly composed of a phenolic resin on the resin molded body 3 side.

The resin molded body 3 is composed of a screw portion 11, a flange portion 13, and an adhesive portion 14 having a predetermined area, and the iron member 5 has exactly the same dog. Example

Hereinafter, examples and the like that specifically show the configuration and effects of the present invention will be described.

Adhesive sample 1 shown in FIG. 1 was produced as follows.

1) A known vulcanizing adhesive suitable for bonding metal and rubber is applied to the bonding surface of the iron member 5 with rubber, and the raw rubber composition is supplied and heated by means such as press vulcanization or injection molding. -Vulcanizing under pressure to form a composite member in which the vulcanized rubber molded body 7 and the iron member 5 are integrated.

2) The vulcanized adhesive layer (A) and the adhesive layer (B) described in the examples or the vulcanized adhesive described in the comparative example are respectively formed on the a1-a2 surfaces of the vulcanized rubber molded body 7 of the composite member. After forming the layer (A) and disposing it in a predetermined mold, a thermoplastic resin containing inorganic short fibers is injection-molded. The adhesion test sample 1 is produced by shaping and molding the resin molded body 3.

(Preparation of vulcanized rubber molded body)

An unvulcanized rubber composition was prepared by a conventional method using the compounding composition shown in Table 1, and a vulcanized rubber molded article as an adhesive sample was prepared by injection molding into a predetermined shape by the above-described process. . table 1

(Measurement of adhesive strength)

The adhesive strength was measured using an Autograph DCS 500 (Shimadzu Corporation) using a resin mold for the adhesive sample, a jig having female threads that fit the threaded portion formed on the iron member, and a jig with each resin mold. The adhesive sample was attached by attaching a screw part of an iron member, and a tensile test was performed under the following conditions. Bow I tension measure: 2 Omm / min

vnttfe .: 2 3 C

Humidity: 6 5% RH

The adhesive strength T was determined by the following equation.

T (MP a) = (F / A) X 1 0 - 6

F: Maximum load (N), A: Adhesion area (m ² ).

Regarding the fracture mode, R100 (destruction of the vulcanized rubber material and good adhesion) when the proportion of the adhered rubber in the fractured surface is 100% is represented by R100, and R80 and the like when it is 80%. Therefore, the larger the value of R, the better the bonding performance. Practically, it can be used if it is R60 or more. The interface separation between the vulcanized rubber molded product and the resin molded product was expressed as RP.

(Dirt of mold)

Number of shots of vulcanized rubber / thermoplastic resin composites until mold cleaning is required due to mold contamination due to the production of vulcanized rubber 'thermoplastic resin composites (adhesion test samples) (number of times) It was expressed by.

Example 1 ^

Using a mold having a cavity for accommodating a vulcanized rubber molded body that has been previously bonded and molded with an iron member and a cavity for forming a resin molded body, the above-mentioned 1) is placed in a cavity for accommodating a vulcanized rubber molded body. The obtained vulcanized rubber molded body sample was placed, and a thermoplastic resin was injection-molded in a molten state to prepare an adhesion test sample.

The thermoplastic resin used was nylon 1.6, 6 with 50% by weight of glass fiber chop strand kneaded and added.

The injection molding conditions for the thermoplastic resin were a mold temperature of 100 ° C, a resin temperature of 285 ° C, and an injection pressure of 16 OMPa.

At the time of injection molding, a vulcanized adhesive (A) (manufactured by Lord Co., Ltd., Chemloc 25X) having a dry film thickness was applied to the bonding surface of the vulcanized rubber molded product with the thermoplastic resin on the surface to be bonded. The coating is dried to a thickness of 15 m, dried, and then dried. Then, an adhesive layer (B) (made by Lord Co., Ltd., Chemrock 205) having a phenolic resin as a main component is dried to a thickness of 8 mm. m, and dried. Preheating of rubber molded body Did not do.

Example 2

The adhesion test sample prepared in Example 1 was subjected to post-curing (post-heating) at 120 ° C. for 60 minutes after injection molding of the resin molded part to obtain an adhesion test sample.

An adhesion test sample was prepared in the same manner as in Example 1 except that the adhesive layer (B) was not provided. However, pre-heating was performed at 120 ° C. for 30 minutes before placing the composite member having the rubber molded body in the mold.

Comparative Example 2

An adhesion test sample was prepared in the same manner as in Example 1 except that the adhesive layer (B) was not provided. The preheating of the rubber molded body was not performed in the same manner as in Example 1.

Table 2 summarizes the results of the adhesion test and the evaluation of the stain on the mold.

Table 2

From the results shown in Table 2, in the example, the cleaning process was performed until the cleaning operation was necessary for the mold contamination. The number of shots (number of times) was much higher than that of the comparative example, indicating that the productivity was excellent. The results of the adhesion test show that the obtained vulcanized rubber / thermoplastic resin composite has a vulcanized rubber molded article highly adhered to the thermoplastic resin molded article. Further, in the embodiment, the preheating operation is not particularly required, and the productivity is also good in this respect. On the other hand, in the comparative example, the mold dirt is poor and the productivity is poor. Furthermore, in Comparative Example 1, a preheating operation was required to obtain a desired adhesive strength, and the productivity was also poor in this respect. In Comparative Example 2, it was recognized that the desired bonded bow could not be obtained if the preheating operation was omitted.

Industrial applicability

INDUSTRIAL APPLICABILITY The present invention is useful as a method for producing a vulcanized rubber-thermoplastic resin composite in which a vulcanized rubber molded article and a thermoplastic resin are bonded at a high strength, and the productivity of the vulcanized rubber-thermoplastic resin composite is improved. Can be manufactured well. Therefore, the present invention has high industrial applicability.

Claims

The scope of the claims

1. A vulcanized rubber molded body prepared in advance is disposed in the vulcanized rubber molded body accommodating cavity of a mold having a vulcanized rubber molded body containing cavity and a resin molded body forming cavity, and the resin molding is performed. A method for producing a vulcanized rubber-thermoplastic resin composite, in which a thermoplastic resin is injected in a molten state into a body forming cavity to form a resin molded body,

A vulcanized adhesive layer (A) containing chlorosulfonated polyethylene as a main component is provided on the surface of the vulcanized rubber molded product that adheres to the thermoplastic resin, and then an adhesive layer (A) containing a phenol-based resin as a main component The method for producing a vulcanized rubber-thermoplastic resin composite, comprising injecting the thermoplastic resin after providing B).

2. The method for producing a vulcanized rubber / thermoplastic resin composite according to claim 1, wherein the thermoplastic resin is a fibrous strength thermoplastic resin containing inorganic fibers.

3. After forming the resin molded body, heat it further at 100 ° C or more! (The method for observing a vulcanized rubber / thermoplastic resin composite according to claim 1 or 2 having a post-cure step for stunning.