JP4603819B2 - Vulcanized adhesive body of rubber and resin member and method for producing the same - Google Patents

Description

  The present invention relates to a vulcanized bonded body of rubber and a resin member and a method for manufacturing the same.

  In rubber products, there are many composites of rubber and resin members. For example, an automotive cooler hose employs a composite structure in which a barrier layer of nylon or the like is bonded to the innermost layer of the hose in order to reduce loss due to refrigerant permeation.

In the fiber and rubber bonding technology, there are many known literatures and patents for treating fibers in advance with an adhesive or an RF compound (resorcin and formalin) (see, for example, Patent Documents 1 and 2). As far as the present applicant knows, there is no known document relating to directly bonding a resin member to rubber by vulcanizing with a predetermined rubber composition without treating it with an adhesive or the like.
JP-A-5-186926 JP-A-5-279934

In general, an adhesive is used as a method for vulcanizing and bonding the resin member and the rubber. However, according to the inventor's research, the following problems were found in the vulcanized indirect bonding method using an adhesive.
(1) Since the adhesive contains an organic solvent, it is subject to environmental / process restrictions.
(2) The adhesive itself and further an adhesive application step are required, resulting in an increase in cost.
(3) It is necessary to control the adhesive application state, and there is a possibility that adhesion failure may occur due to uneven coating.
(4) In order to obtain stable adhesion, surface treatment such as corona treatment on the surface of the resin member is required.

(5) Also, after applying an adhesive to the surface of the resin member and drying, the unvulcanized rubber is pasted and vulcanized to bond, but the adhesive is applied to the surface of the rubber and the resin is coated on it. Even if the members are bonded together and applied, they cannot be bonded. That is, after extruding the resin, the rubber can be coated, but after extruding the rubber, the resin member is coated and cannot be bonded. Actually, an automobile cooler hose has a structure in which an innermost layer is a resin, a rubber is provided on the innermost layer, a reinforcing fiber is provided thereon, and a jacket rubber is provided thereon.

  Such a rubber hose has a hose structure (sometimes referred to as “veneer structure”) by an indirect bonding method using an adhesive. That is, such a rubber hose is made by coating the resin on the mandrel, treating the resin surface, applying and drying the adhesive, extruding the intermediate rubber, knitting the reinforcing layer, extruding the outer rubber, and vulcanizing these. Manufactured by.

  An object of the present invention is to overcome the above-mentioned problems of the prior art, and a novel vulcanization adhesion technique (vulcanization direct adhesion technique) in which a rubber and a resin member are bonded without applying an adhesive. ) To develop.

The present invention relates to a rubber that can form a bond due to the interaction in the production of a vulcanized adhesive body comprising a rubber and a resin member, in which a bond due to the interaction is formed between the rubber and the resin member. A step of preparing a composition, a step of preparing a resin member having a functional group capable of forming a bond due to the interaction, and vulcanization in a state where the rubber composition and the resin member are brought into contact with each other. Including a step of forming a bond by the interaction with a resin member, wherein the rubber is made of a rubber composition containing a compound that becomes resorcin and a methylene donor, and the resin member is a resin in a molten state. The present invention relates to a method for producing a vulcanized adhesive body, which includes a step formed by being deposited on top.

  In the present invention, the rubber composition is vulcanized while being in contact with a predetermined resin member so as to form a bond by a predetermined interaction, whereby the rubber and the resin member exhibiting stable adhesion are added. This is based on the knowledge that a sulfur-bonded product can be obtained.

  Further, the present invention provides an extremely stable rubber by controlling the temperature of the resin or the elapsed time after the resin is deposited when the resin member is formed by depositing a molten resin on the rubber composition. This is based on the knowledge that adhesion between the resin member and the resin member can be obtained.

  The present inventor examined various bonding means in order to develop a new vulcanized direct bonding technique between a rubber and a resin member.

  As a result, when mixing / preparing the compounded rubber with a Banbury mixer or the like, the present inventor can vulcanize the rubber composition and the resin member together by kneading resorcin and hexamethylenetetramine at the same time. For example, it has been found that sufficient adhesion can be obtained between the rubber and the resin member without using an adhesive, and the present invention has been achieved.

  The reason why adhesion improves when compounding resorcin and methylene donor compounds such as hexamethylenetetramine is not fully elucidated, but is explained by the reaction and adhesion mechanism as shown in FIGS. Can do. FIG. 1 is a schematic diagram showing the formation reaction of RH polymer of resorcin (R) and hexamethylenetetramine (H). FIG. 2 is a schematic view showing an adhesion mechanism of the vulcanized adhesive body of the present invention.

  As shown in FIG. 1, an amine compound such as hexamethylenetetramine functions as a methylene donor to form a resorcin RH polymer. In FIG. 1, n is an integer such as 2, 3. And this RH polymer forms the coupling | bonding by interaction between rubber | gum and a resin member, as shown in FIG.

  In the present invention, the vulcanized adhesive body of rubber and resin member can be obtained by direct adhesion without using an adhesive by vulcanization of a predetermined rubber composition and a predetermined resin member. This eliminates the problem of cost increase and environmental burden due to the above, and the vulcanized adhesive body can exhibit stable adhesiveness due to the bond formed by the interaction formed between the rubber and the resin member.

  Further, in the present invention, in the adhesion between the rubber and the resin member, it is possible to directly bond without using an adhesive. For example, the resin is extruded onto the extruded rubber surface to be vulcanized or bonded. It is possible to vulcanize and bond rubber by extruding the resin surface.

  The inventor of the present invention uses a resin in a vulcanized adhesive body having a structure including a rubber layer, a resin layer thereon, and a rubber layer thereon (sometimes referred to as a “barrier structure”), such as a rubber hose. It has been found that when the layer is formed by the deposition of a high temperature molten resin and a rubber layer, the resin layer may not adhere sufficiently to the rubber layer. When a molten resin is extruded onto the extruded inner tube rubber, the cross-linking reaction or the RH polymer formation reaction proceeds in a state of lack of simultaneity due to the heat quantity of the resin, which may cause poor adhesion.

  Based on this knowledge, the present inventor has studied means for obtaining sufficient adhesion between the rubber and the resin member even when the resin member is formed from a molten resin. As a result, the inventor controls the temperature of the resin and the elapsed time after resin deposition by clarifying the influence of the extrusion temperature of the resin and the elapsed time from resin deposition to vulcanization on the adhesion. It has become possible, and it has been found that extremely stable adhesion between a rubber and a resin member can be obtained without being influenced by various manufacturing processes, and the present invention has been completed.

  According to the present invention, a vulcanized adhesive body of rubber and resin member is obtained by vulcanization of a predetermined rubber composition and a predetermined resin member, and a bond is formed between the rubber and the resin member by interaction. Therefore, stable adhesiveness can be exhibited.

An embodiment for carrying out the present invention will be described.
(1) Rubber A rubber that is bonded to each other by an interaction without using a resin member and an adhesive. It consists of a rubber composition containing a compound that becomes resorcin and a methylene donor . A rubber composition containing resorcin and at least one of an amine compound serving as a methylene donor and a formaldehyde compound may be vulcanized. Such a rubber is not particularly limited, and can be made of various materials, and can be a member having various shapes, various structures, and the like, unless otherwise specified.

(2) Rubber composition A rubber composition can be vulcanized in contact with a predetermined resin member to form the rubber described above, and the rubber forms a bond by interaction with the resin member. can do.

  Such a rubber composition can be blended with various general-purpose polymers without particular limitation as a rubber component.

  For example, as a rubber component, nitrile butadiene rubber (hereinafter referred to as “NBR”), hydrogenated nitrile butadiene rubber (hereinafter referred to as “HNBR”), chlorinated butyl rubber (hereinafter referred to as “Cl-IIR”). And at least one polymer selected from the group consisting of halogenated butyl rubber such as brominated butyl rubber (hereinafter referred to as “Br-IIR”), regular butyl rubber (hereinafter simply referred to as “IIR”), and the like. Can be used.

  Resorcin can be contained in an amount of 1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. If the amount is less than 1 part by mass, the adhesive force may be reduced. If it exceeds 10 parts by mass, adhesion failure may occur.

  The amine compound serves as a methylene donor, and at least one amine compound selected from the group consisting of hexamethylenetetramine, hexamethylenediamine and the like can be used.

  Preferably, the amine compound is hexamethylenetetramine (hereinafter sometimes referred to as “HMTA”). There are few impediments to the environment, which is preferable for improving workability.

  The amine compound can be contained in an amount of 1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the rubber component. If the amount is less than 1 part by mass, the adhesive force may be reduced. If it exceeds 10 parts by mass, adhesion failure may occur.

  The formaldehyde compound can be selected from the group consisting of formalin, paraformaldehyde, trioxane and the like. The formaldehyde compound can be contained in an amount of 1 to 10 parts by mass, preferably 1 to 5 parts by mass, with respect to 100 parts by mass of the rubber component. If the amount is less than 1 part by mass, the adhesive force may be reduced. If it exceeds 10 parts by mass, adhesion failure may occur.

  Preferably, the rubber composition contains at least one of silica and a silane coupling agent. Even if the amine compound such as resorcin and hexamethylenetetramine alone is sufficient, the rubber and the resin member may be sufficiently bonded, but a stable bonding level and a range of resin types of adherends that can be bonded are widened.

  Silica can be blended in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the rubber component regardless of the particle size, pH, and the like.

  The type of silane coupling agent is not limited as long as it interacts with rubber. Preferably, 0.5-10 mass parts is mix | blended with respect to 100 mass parts of rubber components.

  Preferably, the rubber composition can contain at least one amine-based antioxidant. Specific examples of the amine-based anti-aging agent include general name: microwax [trade name: SUNNOC-W (manufactured by Ouchi Shinsei Chemical Co., Ltd.)] and general name: anti-aging 6C [trade name: NOCRAC- 6C (manufactured by Ouchi Shinsei Chemical Co., Ltd.)] and the like. Such an amine anti-aging agent can improve the weather resistance and workability (adhesion to a roll or the like) of rubber.

  Carbon black (hereinafter sometimes simply referred to as “C / B”) can be blended. Any type. Preferably, it is in the range of 10 to 100 parts by mass (can be freely selected for the purpose of adjusting physical properties and the like) with respect to 100 parts by mass of the rubber component.

  Oil, microwax, etc. can be blended. The type of oil is not limited as long as it is compatible with the polymer to be used. For example, the blending number is 0 to 50 parts by mass with respect to 100 parts by mass of the rubber component.

  A filler such as zinc oxide can be blended. Any type. 1-30 mass parts can be mix | blended with respect to 100 mass parts of rubber components.

（式中、Ｄはヘキサメチレンテトラミンやヘキサメチレンジアミン等のようなメチレンドナーとなる化合物を示し、ｎは括弧内の構成単位の繰り返し数を示す。）

によって形成されるが、一方、ＲＦ樹脂は、次の反応式ＩＩ：

（式中、ｍは括弧内の構成単位の繰り返し数を示す。）

によって形成され、ＲＦ樹脂では、反応式ＩＩで示すような生成物の−ＯＨ基の部分が−ＣＨ_２ＯＨ基になるものがあり、この−ＣＨ_２ＯＨ基が−Ｃ＝Ｃ−ポリマーの二重結合を攻撃することになるので、このような重合体とならないような配合がよい。 The rubber composition is a polymer of resorcin and a compound serving as a methylene donor (hereinafter simply referred to as “RD polymer”), for example, a polymer of resorcin and an amine compound (hereinafter simply referred to as “RA polymer” or “ RA resin ”) or a resin that exhibits similar performance (for example, an RF resin: a resin formed from resorcin and formalin) may be used. However, the RD polymer has the following reaction formula I:

(In the formula, D represents a compound serving as a methylene donor such as hexamethylenetetramine or hexamethylenediamine, and n represents the number of repeating structural units in parentheses.)

While the RF resin is formed by the following reaction formula II:

(In the formula, m represents the number of repeating structural units in parentheses.)

In some RF resins, the —OH group portion of the product as shown in Reaction Formula II becomes a —CH ₂ OH group, and this —CH ₂ OH group is converted to a —C═C—polymer. Since a heavy bond is attacked, a blending that does not form such a polymer is preferable.

  If the rubber composition needs to change the reaction rate of the RD polymer formation reaction or the structure of the RD polymer depending on the purpose of use, the structure of the production line, etc., use a catalyst such as acid or base. You can also.

  The rubber composition is prepared by kneading resorcin and an amine compound serving as a methylene donor separately and mixing them later when the progress of the formation reaction of the RA polymer is suppressed. At this time, resorcin can be kneaded with a less reactive compounding agent (sometimes referred to as “non-pro”), and therefore resorcin can be kneaded by raising the temperature to 150 to 160 ° C. or the like. An amine compound that serves as a methylene donor can be kneaded with a highly reactive compounding agent (sometimes referred to as “pro”), and therefore, an amine compound can be kneaded without applying heat at a low temperature of 110 ° C. or lower. preferable.

(3) Resin member The resin member of an adherend should just be a thing in which the coupling | bonding by interaction is formed between rubber | gum. A functional group capable of forming a hydrogen bond with the above vulcanized rubber or a functional group capable of dehydrogenation with the rubber can be provided on the surface. Examples of such a functional group include at least one group selected from the group consisting of a hydroxyl group (—OH), an amino group (—NH ₃ ), a carboxyl group (—COOH), and the like.

  Such a resin member can be made of various materials, shapes and the like without particular limitation as long as it has the above-described functional group.

  For example, the resin member can be made of various materials such as nylon 6 such as nylon 6, saponified ethylene vinyl acetate copolymer (hereinafter referred to as “EVOH”), and includes fibers, tubes, sheets, films, and layered materials. It can have various shapes such as objects.

(4) Vulcanization The rubber composition and the resin member are vulcanized in contact with each other, and can be bonded thereby. The vulcanization conditions are not particularly limited, and can be set to various temperatures, times, etc. in relation to the rubber composition.

  FIG. 3 is a graph showing the relationship between the minimum temperature and time required for bonding due to the interaction between the rubber and the resin member. As shown in FIG. 3, the contact surface between the rubber and the resin member has a relationship between the minimum temperature (T) and time (t) required until satisfactory adhesion is completed. In the vulcanization adhesion between the rubber and the resin member, vulcanization conditions can be set based on such experimental results.

  Preferably, for good adhesion between the rubber composition and the resin member, the temperature and time of vulcanization is a polymer of resorcin and a compound serving as a methylene donor (RD polymer, for example, RA polymer or RH polymer). Is set so that the formation reaction of rubber and the crosslinking reaction of rubber proceed simultaneously. In order to proceed the formation reaction of the RD polymer and the crosslinking reaction of the rubber simultaneously, it is preferable to control the start of the formation reaction of the RD polymer and the progress of the crosslinking reaction. For example, the rubber cross-linking reaction is started at the same time as the RD polymer forming reaction is started, or at least the rubber cross-linking reaction is started before the completion of the RD polymer forming reaction.

FIG. 4 is a graph showing the relationship between the RA polymer formation reaction and the rubber crosslinking reaction. As shown in FIG. 4, the RA polymer formation reaction (A) proceeds at room temperature once heat is applied at time t ₀ , but the rubber crosslinking reaction (B) is always heated after time t _1. It is necessary and the crosslinking reaction will stop unless heat is applied. Therefore, in order to proceed simultaneously with the RA polymer formation reaction (A) and the rubber crosslinking reaction (B), as shown in FIG. The rubber crosslinking reaction (B) is started, and the relationship between the RA polymer formation reaction (A) and the rubber crosslinking reaction (B) is set within a certain range such as the width C.

  In vulcanization, known vulcanization systems such as a vulcanizing agent, a vulcanization accelerator, and a vulcanization acceleration aid can be used. For example, at least one vulcanization system selected from the group consisting of sulfur, peroxide, zinc white and the like can be used.

  Sulfur does not matter. Preferably, 0.5-10 mass parts is used with respect to 100 mass parts of rubber components.

  The type of peroxide (hereinafter sometimes simply referred to as “PO”) is not limited. Preferably, 2.5-20 mass parts is used with respect to 100 mass parts of rubber components. Usually, the P.P. O. Is diluted to 40% concentration. O. A single amount is 1 to 8 parts by mass. P. O. Regarding the blending, there is no problem in the use of a co-crosslinking agent, a crosslinking aid and the like. If it is necessary to secure physical properties and other characteristics, the adhesiveness will be good even if the required number of parts is applied. For example, the co-crosslinking agent or the crosslinking aid can be used in an amount of 0 to 10 parts by mass with respect to 100 parts by mass of the rubber component.

  Various accelerators can be added. Any type. If necessary for securing physical properties and other characteristics, 0.1 to 10 parts by mass can be used per 100 parts by mass of the rubber component.

  The rubber composition and the resin member can be molded simultaneously with vulcanization or vulcanized simultaneously with molding. For example, in an automobile cooler hose, it is possible to adopt a structure of innermost layer rubber / resin / rubber / fiber / cover rubber. If the innermost layer is a resin, in order to secure sufficient sealing performance when caulking with the nipple, it depends largely on the application of the adhesive, but by using the innermost layer as rubber, the amount of adhesive required It can suppress, and it can be made to make a sealing performance secure and cost reduction.

(4-1) Formation and vulcanization of resin member The resin member can be formed by depositing a molten resin on the rubber composition. Thereafter, the rubber composition and the resin member are vulcanized as they are to obtain a vulcanized adhesive body of rubber and resin.

  The resin in the molten state is not particularly limited as long as a bond by interaction is formed between the rubber and the resin member, and may be one used for the above-described resin member. The molten state is obtained at a temperature near the melting point of the resin, and may be a temperature lower than the decomposition or alteration temperature of the resin. The rubber composition may be blended so as to form an RD polymer, an RA polymer, an RA resin, or a resin exhibiting similar performance as described above. The thickness of the molten resin is not particularly limited, and can be set to any thickness such as 10 μm to 1 mm.

  Preferably, the temperature of the molten resin and the elapsed time from the deposition to the vulcanization are controlled from the relationship between the type and material of the rubber composition and the type and material of the molten resin. By controlling the temperature and deposition time of the resin in this way, even if a molten resin is deposited on the rubber composition, the subsequent rubber crosslinking reaction can proceed simultaneously with the formation reaction of the RD polymer. And good adhesion between the rubber and the resin member can be obtained.

FIG. 5 is a graph showing the relationship between the temperature change and time of the molten resin and rubber composition. In Figure 5, using a resin in a molten state (temperature T _R), a rubber composition was coated, after a lapse of time t _x, showing how to start vulcanization. As shown in FIG. 5, the resin may reach room temperature (RT) after elapse of time t _x , and the rubber crosslinking reaction does not proceed at room temperature. The formation reaction of the RD polymer proceeds gradually even at room temperature, but hardly proceeds in a short time. Therefore, when vulcanization (T _V temperature) is started after the elapse of time t _x , the good relationship between the rubber and the resin can be obtained as long as the principle of simultaneous progress of the RD polymer formation reaction and the rubber crosslinking reaction is not destroyed. Adhesion is obtained.

  FIG. 6 is a cross-sectional view showing an example of a vulcanization process between a molten resin and a rubber composition, (a) is a cross-sectional view of the rubber composition, and (b) is a molten state on the rubber composition. It is sectional drawing which shows a mode that this resin is deposited, (c) is sectional drawing of the rubber composition of the state which coat | covered resin, (d) is the coating | coated state of the state which coat | covered the rubber composition further on resin. It is sectional drawing of a vulcanizate. As shown in FIGS. 6 (a) to 6 (d), a molten resin 2 is deposited on the first rubber composition 1 formed from various unvulcanized rubbers, and the rubber composition 1 is formed. Cover with Resin 2 Thereafter, for example, after 5 minutes, a second-layer rubber composition 3 formed from various unvulcanized rubbers is further deposited on the resin 2 to produce a vulcanized material 4. Is vulcanized and molded by press vulcanization at 150 ° C. for 50 minutes, for example.

  The vulcanization of the resin and the rubber composition as described above can be performed in a continuous line or a discontinuous line (offline). For example, in a continuous line, the following steps: extrusion of the lower layer rubber composition, resin coating, adhesive application or adhesive coating, upper layer rubber composition extrusion, resin (vulcanizing resin) coating and vulcanization. Sulfuration can be carried out continuously. In such a continuous line, it is possible to make the elapsed time from resin coating to vulcanization within 5 minutes. The discontinuous line is used to perform each process individually, and the time taken between the processes may be 24 hours or more.

  FIG. 7 is a perspective view of an example of a vulcanized adhesive body of rubber and resin. In FIG. 7, the vulcanized adhesive body 5 has a pipe shape, and includes an inner tube rubber 6, a resin layer 7 on the outer periphery of the inner tube rubber 6, and an outer rubber layer 8 on the outer periphery of the resin layer 7. At least the inner tube rubber 6 out of the inner tube rubber 6 and the outer cover rubber 8 forms a bond by interaction with the resin layer 7. When a hose having such a barrier structure is produced, when the resin is coated on the inner tube rubber, it is necessary to raise the temperature of the resin to the melting point or higher and to cover the rubber while the resin is in a molten state. In this case, adhesion failure may occur depending on the temperature of the resin and the elapsed time after resin coating, but the effect of the extrusion temperature of the resin and the elapsed time after coating on the adhesion between the rubber and the resin is clarified. By doing so, it is possible to sufficiently bond the rubber and the resin, and it is possible to ensure the adhesion between the rubber and the resin in various production lines.

  The vulcanized adhesive can improve the weather resistance by providing a weather resistant layer at least on the outermost layer. The weather resistant layer may be a jacket rubber layer. The outer rubber layer can be obtained by RH blending of HNBR rubber (blending of resorcin and hexamethylenetetramine). In the case of the hose having the above-mentioned barrier structure, NBR rubber or HNBR / NBR mixed rubber is mixed with RH, and this is used as an adhesive rubber layer, which is coated with a rubber-rubber-coated outer rubber to improve weather resistance. can do. The structure of such a hose is an inner tube rubber (RH) -resin-adhesive rubber layer-weather-resistant outer rubber. In the case of the hose having the barrier structure, the weather resistance can also be improved by a method in which an adhesive is applied on the resin and a weather-resistant outer rubber layer is coated thereon. The structure of such a hose is an inner tube rubber (RH) -resin-adhesive-weather-resistant outer rubber.

(5) Bonding by interaction It is formed between the rubber of the vulcanized adhesive and the resin member. Such bonds include, but are not limited to, various types of bonds. For example, such a bond is a physical bond such as an entanglement between molecular chains, or a chemical bond such as a bridge, a hydrogen bond, or a coordinate bond, and is composed of at least one of these bonds.

  In particular, the bond by interaction can include crosslinking with a rubber mediated by an RH polymer as shown in FIG. 2 and hydrogen bonding with a resin. For example, the RH polymer is crosslinked with a rubber such as nitrile butadiene rubber (NBR) or hydrogenated nitrile butadiene rubber (HNBR) by peroxide (PO) or the like, or entangles molecular chains, and Hydrogen bonds with functional groups capable of forming hydrogen bonds on the surface of a resin member made of nylon or ethylene vinyl acetate copolymer saponified product (EVOH).

  When silica or a silane coupling agent is added, stable adhesion between the rubber and the resin member can be obtained by hydrogen bonding or dehydration condensation reaction as shown in FIG.

The present invention will be described in more detail based on examples.
(Examples 1-3)
In order to verify the effect of addition of the silica or silane coupling agent, the rubber composition and the resin member having the composition shown in Table 1 are vulcanized to produce vulcanized adhesive bodies (Examples 1 to 3).

  As shown in Table 1, the amounts of resorcin and hexamethylenetetramine (hereinafter simply referred to as “RH”) added to the rubber composition were 3 parts by mass and 100 parts by mass, respectively, of the rubber component. 2 parts by mass.

  The addition amount of the silica and the silane coupling agent in the rubber composition is 15 parts by mass and 5 parts by mass with respect to 100 parts by mass of the rubber component, respectively. In Example 1, only silica is added, in Example 2, only the silane coupling agent is added, and in Example 3, both are added.

  Sulfur as a vulcanization system is added to the rubber composition in an amount of 2.3 parts by mass with respect to 100 parts by mass of the rubber component.

  As a resin member, a resin layer (a 0.10 mm thick film made of nylon 6) is used, and the resin layer is sandwiched between two rubber sheets (each 1 mm thick) of the rubber composition and vulcanized. (Vulcanization conditions: 150 ° C. × 50 minutes).

(Examples 4 to 6)
In order to verify the influence of the vulcanization system, the type of polymer and the blend, the rubber composition and the resin member having the composition shown in Table 1 were vulcanized to produce vulcanized adhesive bodies (Examples 4 to 6). To do.

  Example 4 is the same as Example 3 except that in Example 3, the vulcanized sulfur is changed to peroxide (8 parts by mass with respect to 100 parts by mass of the rubber component) and no accelerator is used. . Examples 5 and 6 are the same as Example 4 except that, in Example 4, the NBR of the rubber component is changed to HNBR and NBR / HNBR (ratio: 50/50), respectively.

(Examples 7 to 10)
In order to verify the adhesion with EVOH, the rubber composition and the resin member having the composition shown in Table 1 are vulcanized to produce vulcanized adhesive bodies (Examples 7 to 10).

  Examples 7, 8, 9 and 10 are the same as Examples 3, 4, 5 and 6 except that the resin layer is changed to a film made of EVOH in Examples 3, 4, 5 and 6, respectively.

(Examples 11 to 16)
In order to verify the adhesiveness between various butyl rubbers and various resin members, the rubber composition and resin member having the composition shown in Table 1 are vulcanized to produce vulcanized adhesive bodies (Examples 11 to 16).

  In Examples 11, 12 and 13, in Example 7, the rubber component NBR was changed to chlorinated butyl rubber (Cl-IIR: Example 11), brominated butyl rubber (Br-IIR: Example 12) and regular butyl rubber (IIR), respectively. : Change to Example 13), change sulfur of vulcanization system to zinc white (mainly 5 parts by mass of zinc oxide), change sulfur to 0.5 parts by mass (Example 13), and 1 part by mass of accelerator (implementation) Example 11 and 12) and 2 parts by mass (Example 13), except for changing to Example 7. Examples 14, 15, and 16 are the same as Examples 11, 12, and 13 except that the resin layer is changed to a film made of nylon 6 in Examples 11, 12, and 13, respectively.

(Examples 17 to 20)
In order to verify the effect of improving the weather resistance of the amine-based anti-aging agent in the NBR and HNBR-based blends, the rubber composition and the resin member having the blends shown in Table 1 are vulcanized to give a vulcanized adhesive (implemented) Examples 17-20) are prepared.

  As an amine-based anti-aging agent, a general name: microwax [trade name: SUNNOC-W (manufactured by Ouchi Shinsei Chemical Co., Ltd.)] and a general name: anti-aging 6C [brand name: NOCRAC-6C (Ouchi Shinsei Chemical Industry) 1) and a 1: 1 formulation.

  In Examples 17 and 18, an amine-based anti-aging agent (Example 17: 3 parts by mass of microwax and Example 18: 3 parts by mass of aging 6C) was added to the rubber composition in Examples 3 and 4, respectively. These are the same as in Examples 3 and 4. Example 19 is the same as Example 17 except that the rubber component in Example 17 is changed from NBR to NBR / HNBR (ratio 50/50). Example 20 is the same as Example 19 except that the vulcanization system in Example 19 is changed to peroxide in the same manner as in Example 18.

(Adhesion test)
About the vulcanized adhesive body of each Example, the adhesiveness of rubber | gum and a resin layer is tested. The results are shown in Table 2.
Adhesion is performed by a commonly used adhesion test method. JIS-K-6256 5 (see JIS Handbook 2000, p.315-p.318): Conforms to the peel test of fabric and vulcanized rubber. This is performed in order to measure the peel strength between the sheet and the rubber attached to the resin sheet. 5.2 There are no changes in the testing machine. For 5.3 specimens, there is no change to 5.3.1. 5.3.2a) Cutting is carried out parallel to the direction of the rubber and resin sheet. b) c) is not necessary. For 5.3.3, do this with n = 3. As for the 5.4 test method, there is no particular change up to ~ 5.7 record. However, in this test, the adhesive strength is too strong to measure the adhesive strength. The rubber breaks. The types of peeling damage as an evaluation are R: the state of destruction of the rubber layer is ◎, and RT: peeling between the rubber and the resin when there is no adhesive is x. In addition, in evaluation of adhesiveness of Table 2, a numerical value shows the ratio with rubber | gum in%. With rubber, when the rubber and the adherend are peeled off, the rubber destruction area is expressed numerically by the following formula with respect to the total area of contact between the rubber and the adherend.
% With rubber = (rubber destruction area / total area where rubber and adherend contact) × 100
In the above formula, rubber breakage is a state where the rubber part breaks rather than the adhesive interface when the rubber and adherend are forcibly peeled off when the adhesion between the rubber and the adherend is very strong. . Interfacial fracture is a state in which when the adhesion between the rubber and the adherend is not so strong, the rubber portion is not broken and breakage occurs at the bonding interface. Total area of contact between the rubber and the adherend = rubber destruction area + interface destruction area.

(Weather resistance test)
The vulcanized adhesive of each example is tested for weather resistance. The results are shown in Table 4. The static ozone test is carried out at an ozone concentration of 40 pphm and an exposure time of 50 h at an extension rate of 40% and 0 to 20%, respectively. ◎: No crack, ○: microcrack, and x: cut.

  As shown in Tables 2 and 3, each of the vulcanized adhesives of each example has good adhesiveness. By adding silica (Examples 1 and 3 to 20) or adding a silane coupling agent (Examples 2 to 20), superior adhesion can be obtained as compared with the case of not adding (Example 2 or Example 1). .

  Excellent adhesion is obtained with NBR, HNBR and NBR / HNBR, any polymer type and blend (Examples 4-6). Adhesiveness with EVOH (Examples 7 to 10) is also good. The adhesiveness (Examples 11 to 16) between various butyl rubbers and resin members is also good. The weather resistance is also improved by the amine-based anti-aging agent (Examples 17 to 20).

(Examples 21 to 38)
A molten resin (EVOH) is deposited on the rubber composition and vulcanized. The vulcanized adhesive as shown in FIG. 7 is obtained by changing the temperature (T _R ) of the resin in the molten state as shown in FIGS. 5 and 6 and the elapsed time (t _X ) from after the resin deposition to before vulcanization. Get.

  Examples 21 to 25 are cases where the temperature of the molten resin is set to the same temperature (190 ° C.) as the melting point of the resin, 5 minutes after the resin deposition (Example 21), 30 minutes after (implementation) Example 22), vulcanization is carried out after 60 minutes (Example 23), after 2 hours (Example 24) and after 6 hours (Example 25). In each of Examples 21 to 25, as the composition of the rubber composition, each of NBR-based compounding (AC098R), HNBR-based compounding, and HNBR / NBR-based compounding was used, each of which was a compound (hexamethylenetetramine) serving as resorcin and methylene donor. ), Silica and silane coupling agent. Typically, the formulations of Examples 4, 5, and 6 are used for the NBR-based formulation, the HNBR-based formulation, and the HNBR / NBR-based formulation, respectively.

  Specifically, an inner tube rubber composition (the above rubber composition) is injection-molded on a mandrel (core), and a resin (EVOH) heated to a melting point or higher (190 to 240 ° C.) is almost equal to its melting point temperature. It is deposited on the inner tube rubber composition at the same temperature (190 ° C.). For the resin deposition, a deposition means as shown in FIG. 8 is adopted. FIG. 8 is a perspective view showing an example of a deposition method in which a molten resin is deposited on rubber. As shown in FIG. 8, the core 10 penetrates the resin film 9, and the resin layer 11 is coated on the inner tube rubber composition. Thereafter, in consideration of weather resistance, a rubber composition for an outer coat (HNBR-based RH blend) is further injection-molded on a resin to obtain a vulcanized product. The material to be vulcanized is vulcanized after each lapse of time from the deposition of the resin. The obtained vulcanized adhesive was subjected to the same adhesion test as in Example 1 and the results are shown in Table 4.

  Examples 26 to 31 are the same as Examples 21 to 25 except that the temperature of the molten resin is about 10 ° C. above the melting point of the resin (200 ° C.) in Examples 21 to 25. 5 minutes after application of the resin (Example 26), 30 minutes (Example 27), 60 minutes (Example 28), 2 hours (Example 29), 6 hours (Example 30) and Vulcanization is carried out after 12 hours (Example 31). The results are shown in Table 5.

  Examples 32-38 are the same as Examples 21-25, except that the temperature of the molten resin in Examples 21-25 is about 20 ° C. above the melting point of the resin (210 ° C.). 5 minutes after application of the resin (Example 32), 30 minutes (Example 33), 60 minutes (Example 34), 2 hours (Example 35), 6 hours (Example 36), Vulcanization is carried out 12 hours later (Example 37) and 24 hours later (Example 38). The results are shown in Table 6.

  As shown in Tables 4 to 6, when the temperature of the molten resin is substantially the same as the melting point of the resin (Examples 21 to 25), good adhesion can be obtained by vulcanization within 6 hours after deposition. However, after 12 hours or 24 hours have elapsed, the heat is lowered, and there is a tendency for adhesion failure (x) in which the rubber and the resin do not adhere at all. When the temperature of the molten resin is about 10 ° C. above the melting point of the resin (Examples 26 to 31), there is no problem if vulcanized by 12 hours after deposition, but the heat drops after 24 hours. For this reason, adhesion failure (Δ) of less than 80% to 60% or more with rubber tends to occur. When the temperature of the molten resin is about 20 ° C. above the melting point of the resin (Examples 32-38), good adhesion can be obtained even after 24 hours, which significantly shortens the time required for adhesion. It seems that the bonding is completed in a few minutes. Therefore, in a high temperature resin such as 210 ° C. or more, the bonding by the interaction of the adhesive surfaces is completed in a short time, and the vulcanization of the rubber in other parts can be left for a while or anytime. Adhesion failure does not occur.

  Although the above-mentioned embodiment is an off-line process, when it is performed in a continuous line, the inner tube rubber and the resin layer are directly applied at a temperature near the melting point such as 190 ° C. or at a decomposition temperature such as 240 ° C. It is possible to obtain adhesion. Moreover, although the above-mentioned Example may differ from said suitable temperature conditions and adhesive performance depending on the mixing | blending content resulting from the difference in the slow speed of RH polymer formation reaction, all are preliminary experiments. By confirming with the above, it is possible to control the temperature of the molten resin and the elapsed time from the time of deposition to the time of vulcanization, and it is possible to achieve good adhesion between the rubber and the resin member.

  In Examples 21 to 38, when the molten resin is changed to nylon or the like and a vulcanized adhesive body is obtained in the same manner, the same result as in the above EVOH is obtained.

It is a schematic diagram of an example which shows the formation reaction of the RH polymer of resorcinol (R) and hexamethylenetetramine (H). It is a schematic diagram of an example which shows the adhesion mechanism of the vulcanized adhesive body of this invention. It is a graph which shows the relationship between the minimum temperature required for the coupling | bonding by interaction with rubber | gum and a resin member, and time. It is a graph which shows the relationship between the formation reaction of RA polymer, and the crosslinking reaction of rubber. It is a graph which shows the relationship between the temperature change of resin and a rubber composition of a molten state, and time. It is sectional drawing which shows the vulcanization | cure process of one example of resin and a rubber composition of a molten state, (a) is sectional drawing of a rubber composition, (b) is resin in a molten state on a rubber composition. It is sectional drawing which shows a mode to make it adhere, (c) is sectional drawing of the rubber composition of the state which coat | covered resin, (d) is a vulcanizate of the state which coat | covered the rubber composition further on resin. FIG. It is a perspective view of the vulcanization adhesion object of rubber and resin of one example. It is a perspective view which shows one example of the deposition method which deposits the resin of a molten state on rubber | gum.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,3 Rubber composition 2 Resin 4 Vulcanized material 5 Vulcanized adhesive body 6 Inner tube rubber 7, 11 Resin layer 8 Outer rubber layer 9 Resin film 10 Core

Claims (3)

  In manufacturing a vulcanized adhesive body comprising a rubber and a resin member, and a bond by interaction is formed between the rubber and the resin member, a rubber composition capable of forming a bond by the interaction is prepared. A step of preparing a resin member having a functional group capable of forming a bond due to the interaction, and vulcanization in a state where the rubber composition and the resin member are in contact with each other. Including a step of forming a bond by the interaction therebetween, wherein the rubber is made of a rubber composition containing a compound that becomes resorcin and a methylene donor, and the resin member deposits a molten resin on the rubber composition A process for producing a vulcanized adhesive body comprising a step of forming a vulcanized adhesive body. Method for producing a vulcanization bonding body according to claim 1, wherein the compound serving as the methylene donor is at least one amine compound and formaldehyde compound. The method according to claim 1 or 2 wherein the vulcanization body characterized in that it comprises a step of advancing a crosslinking reaction of the polymer forming reaction and the rubber composition of the compound serving as the methylene donor and the resorcinol simultaneously .

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