JP5746959B2 - Fluororubber composition and composite seal member using the same - Google Patents

Description

  The present invention relates to a fluororubber composition used as a sealing material in various industrial fields and a composite seal member using the same, and more particularly to a fluororubber composition excellent in hot water resistance and a composite seal member using the same.

  Conventionally, so-called sealing materials such as gaskets and packings used in various industrial fields are generally provided to the market as composite sealing members in which rubber is vulcanized and bonded to a base such as metal or resin. .

  Such a composite seal member is required to have various characteristics according to the use environment, and one of the required characteristics is hot water resistance.

  When considering a sealing material having hot water resistance, the first rubber material to be used is fluororubber. This is because fluororubber has a very high heat resistance compared to other rubbers.

  Fluororubbers are roughly classified into two types, those capable of polyol crosslinking and those capable of peroxide crosslinking, and those that are more resistant to heat are peroxide-crosslinkable fluorine rubbers. It is said.

  Then, when vulcanized and bonded to a metal member (or resin member) using a peroxide-crosslinkable fluororubber, it is preferable to interpose a silane-based adhesive in order to improve adhesiveness and the like. .

  However, it is generally said that silane-based adhesives do not have sufficient hot water resistance. For this reason, composite seal members made of peroxide-crosslinkable fluororubber and metal members (or resin members) that are joined via the adhesive are less active in environments where heat resistance is required. I couldn't say that. For this reason, the use in an environment where hot water resistance is required mainly uses a fluorine-crosslinkable fluororubber and an epoxy adhesive which has good compatibility with the rubber and good hot water resistance. This is the current situation.

JP 2010-202804 A

  However, in the case of using a polyol-crosslinkable fluororubber, it cannot be said that the hot water resistance of the rubber itself is sufficient, and a new fluororubber composition with improved hot water resistance and a composite seal member using the same Suggestion is desired. Of course, it is also required to have an appropriate rubber hardness and elasticity and to have a good sealing property.

  The present invention has been invented under such circumstances, and its purpose is not only to provide good sealing properties but also to have sufficient durability in hot water (so-called hot water resistance is excellent). An object is to provide a fluororubber composition and a composite seal member using the same.

That is, the present invention is a fluororubber composition that is used by being bonded to a metal member or a resin member via an adhesive layer, and the fluororubber composition is obtained by copolymerizing three types of monomers. It contains 100 parts by weight of the peroxide-crosslinked fluororubber, 55 to 90 parts by weight of carbon black , and liquid fluororubber for adjusting the rubber hardness, and has a Duro-A hardness of 70 to 70. 80 der is, the average particle diameter of the carbon black is 240～320Nm, the liquid fluorine rubber, a fluorine rubber is liquid at room temperature, are configured so that a provided with physical properties as a rubber component that does not crosslink The

As a preferred embodiment of the fluororubber composition of the present invention, the peroxide-crosslinking type fluororubber is a copolymer of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), and hexafluoropropylene (HFP). It is comprised from the fluororubber of the ternary copolymer obtained by this.

In a preferable embodiment of the fluororubber composition of the present invention, the carbon black is composed of sub chromatography circle black.

  The present invention is a composite sealing member obtained by bonding the above-described fluororubber composition to a base of a metal member via an adhesive layer, and the adhesive layer is formed on a joint surface with the base It is comprised so that it may have the vinylsilane type adhesive bond layer formed in the joining surface of the made phenol type adhesive bond layer and a fluororubber composition.

  The present invention is a composite sealing member obtained by joining the above-described fluororubber composition on a substrate of a resin member via an adhesive layer, and the adhesive layer has a vinylsilane-based adhesive layer. Configured as follows. Moreover, as a preferable aspect of the composite seal member, the adhesive layer includes a phenol-based adhesive formed on the bonding surface between the vinyl silane-based adhesive layer formed on the bonding surface with the fluororubber composition and the substrate. Configured to have layers.

  Moreover, as a preferable aspect of the composite sealing member of the present invention, the adhesive layer is constituted by a two-layer laminate of a phenol-based adhesive layer / vinylsilane-based adhesive layer from the substrate side.

  Moreover, as a preferable aspect of the composite sealing member of the present invention, the vinylsilane-based adhesive layer is configured to include vinylethoxysilane as a main component.

  Moreover, as a preferable aspect of the composite sealing member of the present invention, the joining surface of the base of the metal member or the resin member is configured such that an uneven surface is formed by surface treatment.

  As a preferred embodiment of the composite seal member of the present invention, the maximum height roughness Ry of the joint surface of the base of the metal member or resin member is configured to be 5 μm or more.

  Moreover, as a preferable aspect of the composite seal member of the present invention, the resin member is configured to be polyphenylene sulfide resin (PPS).

  The rubber composition of the present invention is a fluororubber composition used by joining a metal member or a resin member via an adhesive layer, and the fluororubber composition is a copolymer of two or more monomers. It contains 100 parts by weight of peroxide-crosslinked fluororubber and 55 to 90 parts by weight of carbon black, and has a DuroA hardness of 70 to 80. The effect of having sufficient durability in hot water (excelling in so-called hot water resistance) is exhibited as well as providing.

  In particular, since the fluororubber composition of the present invention contains 55 to 90 parts by weight of carbon black, the rubber body itself acts as a hot water barrier. Therefore, when considering the hot water resistance based on the composition of the composite seal member in which the fluororubber composition is bonded to the base of the metal member or the resin member via the adhesive layer, the major cause of the loss of the hot water resistance at the bonding interface It has been speculated that hot water that has passed through the inside of the rubber main body will attack the bonding interface. Therefore, the attack from the side surface at the bonding interface can be almost ignored. It can be considered that the vicinity of the side surface is substantially covered and blocked by the fluororubber composition due to the extremely thin film thickness of the adhesive layer and the unevenness of the bonding surface. Because.

FIG. 1 is a schematic perspective view illustrating a simplified structure of a composite seal member of the present invention, in which a fluororubber composition is bonded onto a base of a metal member or a resin member via an adhesive layer. It is a schematic perspective view of a composite sealing member.

  Hereinafter, modes for carrying out the present invention will be described.

  The fluororubber composition of the present invention is a main part of the configuration of the composite seal member of the present invention. Therefore, first, a preferred embodiment of the composite seal member containing the fluororubber composition of the present invention will be described with reference to FIG.

[Description of Structure of Composite Seal Member of the Present Invention]
FIG. 1 shows a schematic perspective view depicting the configuration of the composite seal member 10 of the present invention in a particularly simplified manner. As shown in FIG. 1, the composite seal member 10 of the present invention has a fluororubber composition 40 (rubber layer 40) on a base 20 composed of a metal member or a resin member via an adhesive layer 30. It has a joined structure. The member indicated by a two-dot chain line in FIG. 1 is a disk used when producing a test piece to be described later, and should be ignored in the description of the configuration of the following examples.

  Hereinafter, each component requirement will be described.

<Description of Fluoro Rubber Composition 40 (Rubber Layer 40)>
The fluororubber composition 40 (rubber layer 40) in the present invention is a peroxide cross-linking type (cross-linking agent) obtained by copolymerizing two or more monomers (especially preferably two or three types of monomers). As a main component).

  Specific examples of fluororubber include vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / propylene / vinylidene fluoride copolymer, tetrafluoroethylene / propylene / vinyl fluoride copolymer, tetra Fluoroethylene / propylene / trifluoroethylene copolymer, tetrafluoroethylene / propylene / pentafluoropropylene copolymer, tetrafluoroethylene / propylene / chlorotrifluoroethylene copolymer, tetrafluoroethylene / propylene / ethylidene norbornene copolymer Terpolymers such as vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer, tetrafluoroethylene / propylene copolymer Body, hexafluoropropylene / ethylene copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer binary copolymer, and the like.

  Among these, in particular, a terpolymer obtained by copolymerizing vinylidene fluoride (VDF), tetrafluoroethylene (TFE), and hexafluoropropylene (HFP), or tetrafluoroethylene (TFE) and It is preferable to use a binary copolymer fluororubber obtained by copolymerizing propylene (P).

  The copolymer composition of vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer is preferably 50/5/45 to 65/30/5 (molar ratio). The copolymer composition of the tetrafluoroethylene / propylene copolymer is preferably 40/60 to 60/40 (molar ratio).

  As the fluororubber crosslinking agent, as described above, peroxide (organic peroxide) is used. This is because rubber of a type that is crosslinked by a peroxide (organic peroxide) crosslinking agent is particularly excellent in hot water resistance. The peroxide cross-linking type fluororubber referred to in the present invention is based on the premise that peroxide is used as a cross-linking agent.

  Specific crosslinking agents include 1,1-di (t-hexylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl. Peroxide, t-butylcumyl peroxide, dicumyl peroxide, α-α'-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxide Oxy) -hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, dibenzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5- Examples include di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-hexylperoxyisopropyl monocarbonate, and the like. The content of such a crosslinking agent is about 0.1 to 5 parts by weight with respect to 100 parts by weight of the fluororubber.

  The fluororubber composition in the present invention preferably contains a crosslinking aid. Specific examples of the crosslinking aid include triallyl cyanate, triallyl isocyanate, triacryl formal, triallyl trimellitate, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate and the like. The content of such a crosslinking aid is about 0.1 to 15 parts by weight with respect to 100 parts by weight of the fluororubber.

  The fluororubber composition of the present invention contains carbon black, and the content thereof is 55 to 90 parts by weight, more preferably 55 to 65 parts by weight with respect to 100 parts by weight of the fluororubber.

  When this content exceeds 90 parts by weight, the hardness of the rubber itself begins to increase extremely, and a large amount of liquid fluororubber must be used to adjust the hardness described later, and the required strength as rubber In addition, the elasticity tends to deteriorate and it becomes extremely difficult to put to practical use. On the other hand, when the content is less than 55 parts by weight, there arises a disadvantage that the characteristics of both good sealing properties and hot water resistance, which are the objects of the present application, cannot be obtained simultaneously.

Examples of the carbon black used include furnace black, acetylene black, thermal black, channel black, and graphite. As such carbon black, those having an average particle diameter of 15 to 350 nm and a specific surface area of 7 to 150 m ² / g can be suitably used. In particular, thermal black having an average particle diameter of 240 to 320 nm and a specific surface area of 7 to 11 m ² / g is used in order to easily adjust the rubber hardness so that it can be easily adjusted to the appropriate amount of liquid fluororubber to be described later. Is preferable, but is not necessarily limited to the physical properties in this range.

  Further, the fluororubber composition of the present invention contains liquid fluororubber. The liquid fluororubber is a fluororubber that is liquid at room temperature, and is used for applications such as improving the workability and reducing the hardness of solid fluororubber. Liquid fluororubber is a rubber component that is not crosslinked. In particular, in the present invention, it is used for maintaining and adjusting the rubber hardness within a suitable range as a sealing member. That is, it is contained in order to exert the effect of lowering the hardness of the rubber hardened by carbon black that is excessively added apart from the general usage amount to an appropriate range.

  Accordingly, the fluororubber composition of the present invention satisfies the range of 70 to 80 in Duro-A hardness despite being contained in a large amount of carbon black that is not normally used, and is suitable as a sealing member. High elasticity and hardness.

  Such a liquid fluororubber is generally insoluble in water and has solubility in lower ketones and esters. An example of a specific product name is “DAIEL (registered trademark) G-101”.

  The content of such a liquid fluororubber can be appropriately set in consideration of the content of carbon black, the rubber hardness associated therewith, and the like. If the content of the liquid fluororubber is too large, the rubber elasticity is lost and the original rubber function as a sealing material is lost.

  As other additives, fillers (excluding carbon black), processing aids such as lubricants, lubricants, flame retardants, antistatic agents, colorants, and the like may be included.

  Examples of the filler include fluororesin, glass fiber, and carbon fiber. Examples of the processing aid include alkali metal salts of higher fatty acids, and stearates and laurates are particularly preferable.

  Examples of the method for producing the fluororubber composition used in the present invention include blending and adding a fluororubber, a liquid fluororubber, carbon black, a crosslinking agent, a crosslinking aid, and other additives, and then a kneader such as a kneader. What is necessary is just to knead | mix using.

<Description of Base 20 of Metal Member or Resin Member>
The selection of the metal member or resin member used as the substrate 20 is not particularly limited. That is, various metals or alloys can be used as the metal member, and various thermoplastic resins, heat or photo-curable resins can be used as the resin member. However, considering the heating temperature for rubber vulcanization, so-called heat resistant resin is preferable among the resin members.

  The bonding surface of the metal member or resin member base is preferably formed with an uneven surface by surface treatment. As described above, it can be considered that the vicinity of the side surface is substantially covered and blocked by the fluororubber composition due to the formation of irregularities on the joint surface, and the hot water resistance from the side surface is reduced. It is because it improves. In particular, the maximum height roughness Ry of the surface-treated surface is preferably set to 5 μm or more (particularly about 9 to 15 μm). The maximum height roughness Ry is the sum of the maximum value of the peak height Rp and the maximum value of the valley height Rv of the roughness curve. In the present invention, the surface roughness meter (Surfcom 2800E manufactured by Tokyo Seimitsu Co., Ltd.) Use to measure.

<Description of Adhesive Layer 30>
An adhesive layer 30 is formed on a base member 20 made of a metal member or a resin member, and the above-described fluororubber composition 40 is bonded thereon.

  In this embodiment, the adhesive layer 30 is composed of a two-layer laminate of a phenol-based adhesive layer 31 (undercoat layer) / vinylsilane-based adhesive layer 35 (overcoat layer), and a phenol-based adhesive is bonded to the joint surface with the substrate 20. It is preferable that the agent layer 31 is provided and the vinylsilane-based adhesive layer 35 is provided on the joint surface with the fluororubber composition 40.

  In addition, when using the base | substrate of a resin member, it can be set as 1 layer structure only of the vinylsilane type adhesive bond layer 35, without providing the phenol type adhesive bond layer 31. FIG.

  The phenol-based adhesive layer 31 has a function as a so-called undercoat (primer) and is formed on the base member 20 side of the metal member or the resin member as described above. Examples of the phenol-based adhesive layer 31 include Metallok PH-50 as a suitable specific product.

  The vinyl silane-based adhesive layer 35 preferably contains vinyl alkoxysilane as a main component at the application stage, and particularly preferably contains vinyl triethoxysilane as a main component. For example, a coating solution containing 10 to 20% vinyltriethoxysilane in an ethanol solution can be exemplified. Examples of the vinyl silane-based adhesive layer 35 include CILBOND R-6829 (synonymous with the new trade name CINBOND 36) as a suitable specific product.

Hereinafter, the present invention will be described in more detail with reference to specific examples.
<Preparation of Sample of Example 1>

(Fluoro rubber)
The following two types of fluororubber were prepared.
Type 1: Vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene terpolymer (trade name “Technoflon P-757”; manufactured by Solvay Solexis)
Type 2: Tetrafluoroethylene / propylene binary copolymer (trade name “Aphras 150P”; manufactured by Asahi Glass Co., Ltd.)
In Example 1, a terpolymer of type 1 was used among the above two types.

(Liquid fluoro rubber)
・ Daiel G-101 (Daikin Industries)

(Carbon black)
・ Thermax N990 (manufactured by cancarb); average particle size 280 nm

(Crosslinking agent)
・ Percadex ((made by Kayaku Akzo); 1,3-bis (t-butylperoxyisopropyl) benzene)

(Crosslinking aid)
・ TAIC: Nippon Kasei Co., Ltd., triallyl isocyanate

  Using the above raw materials for blending, rubber compounds were obtained with the blending contents shown in Table 1 below.

Next, a stainless steel plate (SUS) having a shape in which a disk having a diameter of 12 mm and a thickness of 6 mm and a disk having a diameter of 15.8 mm and a thickness of 4 mm (a member indicated by a two-dot chain line in FIG. 1) are integrated into a metal member The substrate 20 was prepared, and the circular surface as the connection surface was subjected to a sandblast treatment, and then subjected to a roughening treatment by degreasing treatment by alkali cleaning.
The maximum height roughness Ry of the surface-treated surface was 10.8 μm.

  After applying a primer (“Metallock PH-50” manufactured by Toyo Kagaku Co., Ltd.) as a primer to the entire circular surface, which is the connection surface of the stainless steel plate (SUS) after the above treatment, baking treatment is performed at 160 ° C. for 15 minutes. Was done. A vinylsilane-based adhesive (CILBOND R-6829) was applied and formed on such an undercoat layer and baked at 150 ° C. for 20 minutes.

  The above rubber compound is adhered on the overcoat layer formed in this manner, and then subjected to treatment at primary vulcanization 170 ° C., 10 minutes, secondary vulcanization 200 ° C., 4 hours, and the composite sealing member of the present application. Got.

  In order to perform an adhesive strength test described later, a test piece in which a rubber compound is sandwiched between two stainless steel plates (SUS) via an adhesive layer, that is, a stainless steel plate (SUS) / undercoat layer / overcoat layer / A test piece consisting of rubber compound (fluororubber composition) / overcoat layer / undercoat layer / stainless steel plate (SUS) was produced.

<Production of Samples of Other Examples and Comparative Examples>
In accordance with the sample preparation of Example 1 above, Example Samples and Comparative Example Samples were prepared according to the blending procedure as shown in Table 1 below. As can be seen from the blending contents shown in Table 1 below, the blending of the rubber compound (fluororubber composition) and the overcoat layer / undercoat layer is appropriately changed in each example and comparative example.

  Furthermore, as another experimental sample configuration example, for the fluororubber compositions (Example Samples 1-8, Comparative Samples 1-3, and Reference Example 2) described in Table 1 below, the substrate is made of a stainless steel plate (SUS). Except for the change to polyphenylene sulfide resin (PPS), in accordance with the above method, polyphenylene sulfide resin (PPS) / undercoat layer / overcoat layer / rubber compound (fluororubber composition) / overcoat layer / undercoat layer / polyphenylene sulfide A test piece made of Fido resin (PPS) was produced. At this time, the maximum height roughness Ry of the surface treatment surface of the polyphenylene sulfide resin (PPS) was 9.2 μm.

  For each sample prepared, (1) Rubber remaining rate (%), (2) Duro-A hardness, (3) Tensile strength (MPa), and (4) Elongation (%) ) Rubber properties were determined.

<Measurement of rubber properties>
(1) Rubber remaining rate (%)
As described above, a test piece in the form in which the fluororubber composition is sandwiched between two disc-shaped substrates (stainless steel plate (SUS) or polyphenylene sulfide resin (PPS)) via an adhesive layer is prepared, and the test is performed. The piece was immersed in hot water at 100 ° C. for 168 hours.
Thereafter, the disk-shaped substrate bonded to the upper and lower surfaces of the fluororubber composition was fixed to a tensile tester and gradually pulled up and down. After the rubber was cut, the ratio of the rubber cut surface remaining on the substrate was examined (measurement of rubber remaining rate). The rubber remaining rate of 100% is a state where the adhesive interface between the rubber and the substrate is covered with 100% rubber, and the rubber remaining rate of 0% is a state where the rubber is removed from the surface portion of the substrate.

The contents of evaluation of the rubber remaining rate were divided into the following three levels.
A ... Rubber remaining rate of 80% or more B ... Rubber remaining rate of 70% or more and less than 80% X ... Rubber remaining rate of less than 70% The target value of the rubber remaining rate of the present invention is 70% or more.

(2) Duro-A hardness Determined based on JIS K6253.
The target value of the present invention is in the range of 70-80.

(3) Tensile strength (MPa)
Test values were determined based on JIS K6251.
The target value of the present invention is 15 MPa or more.

(4) Elongation (%)
Test values were determined based on JIS K6251.
The target value of the present invention is 230% or more.

The above (2) Duro-A hardness, (3) Tensile strength (MPa), and (4) Elongation (%) values are immersed in hot water at 100 ° C. for 168 hours. It is a value measured before.
The experimental results are shown in Table 1 below.

<Adhesion comparison test with substrate (Description of Reference Example 2)>
Regarding the fluororubber composition (carbon black amount: 70 parts by weight) according to Example 4 shown in Table 1, the substrate used was a stainless steel plate (SUS) and a polyphenylene sulfide resin (PPS). A test piece was prepared. At this time, the adhesive layer was one layer.

  Specifically, after applying the vinylsilane-based adhesive (CILBOND R-6829) used above to the connection surface of the substrate, baking treatment was performed at 160 ° C. for 15 minutes, and no further treatment with the adhesive was performed. . That is, it was set as the adhesive layer of one layer of the vinylsilane type adhesive agent. Other than that, a test piece having a laminated structure of base / adhesive layer (1 layer) / rubber compound (fluororubber composition) / adhesive layer (1 layer) / substrate was formed in the same manner as in the above example. A stainless steel plate (SUS) and a polyphenylene sulfide resin (PPS) were prepared.

  The two test pieces prepared above were immersed in hot water at 100 ° C. for 168 hours, and the same adhesion test was performed. The results are shown in Table 1 (Reference Example 2).

  According to the above experiment, when a base 20 made of a heat-resistant resin made of a resin material such as polyphenylene sulfide resin (PPS) is used instead of the base 20 made of a stainless steel plate (SUS) metal member, a better experimental result is obtained. It was confirmed that

  The effect of the present invention is clear from the experimental results shown above. That is, the rubber composition of the present invention is a fluororubber composition used by joining a metal member or resin member via an adhesive layer, and the fluororubber composition contains two or more types of monomers. It contains 100 parts by weight of peroxide-crosslinked fluororubber obtained by copolymerization and 55 to 90 parts by weight of carbon black, and is configured to have a DuroA hardness of 70 to 80. The effect of having sufficient durability in hot water (excellent in so-called hot water resistance) is exhibited as well as having properties.

  It can be used in the industrial field of fluororubber compositions that require hot water resistance and composite seal members using the same.

DESCRIPTION OF SYMBOLS 10 ... Composite sealing member 20 ... Base | substrate 30 ... Adhesive layer 31 ... Phenolic adhesive layer (undercoat layer)
35 ... Vinylsilane adhesive layer (overcoat layer)
40. Fluoro rubber composition

Claims (11)

A fluororubber composition used by joining a metal member or resin member via an adhesive layer,
The fluororubber composition is composed of 100 parts by weight of a peroxide-crosslinking type fluororubber obtained by copolymerizing three kinds of monomers,
Carbon black 55-90 parts by weight;
Containing liquid fluororubber for adjusting the rubber hardness ,
Duro A (Duro-A) hardness of 70 to 80 der is,
The carbon black has an average particle size of 240 to 320 nm,
The liquid fluororubber is a fluororubber is liquid at room temperature, fluororubber composition characterized Rukoto such includes the physical properties of the rubber components not crosslinked. The peroxide crosslinking type fluorine rubber, a vinylidene fluoride (VDF), and tetrafluoroethylene (TFE), fluorine rubber ternary copolymer obtained by copolymerizing hexafluoropropylene (HFP) The fluororubber composition according to claim 1. The carbon black is fluororubber composition according to claim 1 or 2 Ru thermal black der. A composite seal member formed by bonding the fluororubber composition according to any one of claims 1 to 3 on an adhesive layer on a base of a metal member,
It said adhesive layer comprises a phenol-based adhesive layer formed on the bonding surface with the substrate to become configured to have a vinylsilane adhesive layer formed on the junction surface between the fluorine rubber composition A composite seal member. A composite seal member obtained by bonding the fluororubber composition according to any one of claims 1 to 4 on an adhesive layer on a base of a resin member,
The said adhesive bond layer is comprised so that it may have a vinylsilane type adhesive bond layer, The composite sealing member characterized by the above-mentioned. The adhesive layer, said vinylsilane adhesive layer formed on the junction surface between the fluorine rubber composition, comprising is configured to have a phenolic adhesive layer formed on the bonding surface of said substrate The composite seal member according to claim 5 . The adhesive layer is a composite sealing member according to claim 4 or claim 6 wherein the base side a two-layer laminate of the phenol-based adhesive layer / the vinyl adhesive layer. The composite seal member according to claim 4 , wherein the vinylsilane-based adhesive layer contains vinylethoxysilane as a main component. The composite sealing member according to any one of claims 4 to 8 , wherein an uneven surface formed by a surface treatment is formed on a joint surface of the base of the metal member or the resin member. The composite seal member according to claim 9 , wherein the maximum height roughness Ry of the joint surface of the base of the metal member or the resin member is 5 μm or more. Composite sealing member according to any one of the resin member is polyphenylene sulfide resin (PPS) Der Ru請 Motomeko 5 through claim 10.

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