JPWO2015118912A1 - Metal / rubber composite structure - Google Patents

Abstract

In the metal / rubber composite structure formed by bonding a metal member and a rubber member, the metal surface of the metal member to which the rubber member is bonded is subjected to surface roughening treatment, and the rubber member is liquid at 25 ° C. Disclosed is a metal / rubber composite structure excellent in bonding strength between a metal member and a rubber member, which is formed by a crosslinking treatment of a composition containing the above crosslinkable elastomer.

Description

  The present invention relates to a metal / rubber composite structure in which a metal member having fine irregularities on the surface of a metal material typified by an aluminum alloy and a rubber member are joined.

  Conventionally, rubber, especially elastomers represented by silicone rubber, fluoro rubber, and acrylic rubber, are used for interior and exterior of automobiles such as instrument panels, door panels, belt line moldings, roof moldings, glass run channels, gaskets, cap seals, and tubes. It is used for industrial applications such as grips for noise reduction gears, silencers, and tools. When using the rubber for these applications, there are many cases in which a resin member formed of the rubber and a metal member are bonded to each other. However, a technique capable of joining and integrating the resin member and the metal member with an industrially advantageous method with high adhesive strength has not been put into practical use.

  In recent years, as a composite structure of a resin member and a metal member formed of the rubber, for example, there are a gasket and a sealant in which the rubber is made of silicone rubber or acrylic rubber (for example, see Patent Documents 1 to 4). However, silicone rubber has drawbacks in terms of moisture permeation resistance and chemical resistance. Reference 5 describes a rubber / metal bonded composite. In this document, the surface of a metal part that has been electrogalvanized with a metal part is further treated with either zinc yellow chromate treatment or zinc olive chromate treatment as a metal surface treatment agent, and vulcanization. There is a disclosure that rubber that has been subjected to chlorination treatment by applying an organic halogen compound can be bonded to each other using a synthetic resin adhesive. However, in this aspect, the surfaces of both the metal part and the rubber must be treated, and further, a synthetic resin adhesive must be used for bonding the both, so that the manufacturing process becomes complicated and the mass productivity is poor. There was a problem. Furthermore, since the synthetic resin adhesive used is an epoxy resin type or a urethane resin type, there is a possibility that the resin will be hydrolyzed and the adhesive strength may be reduced during long-term use.

JP-A-6-246848 JP 2004-14150 A Special table 2008-529833 gazette Special table 2009-524196 gazette JP-A-9-221552

  The present invention provides a metal / rubber composite structure in which a metal member having fine irregularities on a metal surface and a rubber member are directly and strongly bonded without using an adhesive and have excellent long-term use stability. That is.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention cross-linked a composition containing a crosslinkable elastomer that is liquid at 25 ° C. on the metal surface of the metal member having a concavo-convex shape formed by the surface roughening method. By forming a rubber member by performing the treatment, it was found that a metal / rubber composite structure excellent in bonding strength between the metal member and the rubber member was obtained, and the present invention was completed.

That is, the present invention relates to the following [1] to [8].
[1] In a metal / rubber composite structure formed by joining a metal member and a rubber member,
The metal surface of the metal member to which the rubber member is bonded has been subjected to surface roughening treatment,
A metal / rubber composite structure, wherein the rubber member is formed by a crosslinking treatment of a composition containing a liquid crosslinkable elastomer at 25 ° C.
[2] The rubber member according to [1], wherein the rubber member is formed by directly injection-molding a composition containing a liquid crosslinkable elastomer at 25 ° C. on a metal surface and then performing a crosslinking treatment. Metal / rubber composite structure.
[3] The metal member has a concavo-convex shape having an average length (RSm) of a contour curve element of 10 nm to 100 μm and a ten-point average roughness (Rz) of 10 nm to 300 μm on a metal surface to which a rubber member is bonded. [1] A metal / rubber composite structure according to 1.
[4] The metal / rubber composite structure according to [1], wherein the crosslinkable elastomer is (A) an ethylene / α-olefin / non-conjugated polyene random copolymer.
[5] The composition comprises (A) an ethylene / α-olefin / non-conjugated polyene random copolymer, (B) a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule, and (C) a transition. The metal / rubber composite structure according to [1], comprising a metal catalyst.
[6] The composition according to [1], wherein the composition includes (A) an ethylene / α-olefin / non-conjugated polyene random copolymer, (D) an organic peroxide, and (E) a crosslinking aid. Metal / rubber composite structure.
[7] The (A) ethylene / α-olefin / non-conjugated polyene random copolymer comprises:
The molar ratio of ethylene unit [i] / α-olefin unit [ii] ([i] / [ii]) is 35/65 to 95/5,
The iodine value is in the range of 0.5-50,
The metal / rubber composite structure according to [4], wherein the intrinsic viscosity [η] measured in a decalin solution at 135 ° C. is 0.01 to 5.0 dl / g.
[8] The metal / rubber composite structure according to [1], wherein the composition contains 0.1 to 10000 parts by mass of a filler with respect to 100 parts by mass of the crosslinkable elastomer.
[9] The metal / rubber composite structure according to [2], wherein a liquid injection molding machine (LIM molding machine) is used for the injection molding.

  ADVANTAGE OF THE INVENTION According to this invention, the metal / rubber composite structure excellent in the joining strength of a metal member and a rubber member which was difficult to manufacture with the prior art can be obtained.

  In particular, in the present invention, the metal member and the rubber member can be directly and strongly bonded without using an adhesive, and a metal / rubber composite structure excellent in long-term use stability can be obtained.

  Hereinafter, each component constituting the metal / rubber composite structure according to the present invention, a preparation method thereof, and characteristics of the metal / rubber composite structure will be described. In addition, "-" between the numbers in a sentence represents the following from the above, unless there is particular notice.

<Metal member>
[Metal type of metal member]
In the present invention, the metal constituting the metal member is preferably at least one kind of iron, stainless steel, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, titanium, or titanium alloy. Of these, iron, stainless steel, aluminum alloy, magnesium alloy, copper alloy, and titanium alloy are more preferable, and stainless steel, aluminum alloy, magnesium alloy, and copper alloy are more preferable.

  The metal member is processed by the above method after being processed into the above-described predetermined shape by metal removal such as cutting, pressing, etc., metal processing, punching, cutting, polishing, electric discharge processing, etc. preferable. In short, it is preferable to use a material processed into a necessary shape by various processing methods.

[Metal surface roughening]
The metal member according to the present invention is characterized in that the surface of the joint with the rubber member has a fine uneven shape by a specific roughening treatment.

  The uneven shape preferably has an average length (RSm) of contour curve elements of 10 nm to 500 μm, more preferably 30 nm to 200 μm, particularly preferably 50 nm to 150 μm, and a ten-point average roughness (Rz) of preferably 10 nm. ˜300 μm, more preferably 10 nm to 100 μm, particularly preferably 30 nm to 50 μm, and most preferably 50 nm to 30 μm.

  Hereinafter, the metal surface roughening process will be described.

  There are the following three types of methods for imparting a fine uneven shape to the surface of the metal material, roughly classified from the shape of the obtained fine uneven surface.

  The first is obtained by immersing a metal in an erodible aqueous solution or erodible suspension, and the surface is covered with countless convex and concave portions as measured by electron microscope observation. The average length (RSm) of the contour curve elements is 10 nm to 300 μm, and the ten-point average roughness (Rz) is 10 nm to 30 μm.

  The second one is obtained by anodizing, and the surface is mainly a metal oxide layer, and the surface layer is covered with, for example, countless number average inner diameter 10 to 200 nm openings. It is.

  The third is a method of forming irregularities on the metal surface by pressing a die punch with irregularities created by mechanical cutting, such as diamond abrasive grinding or blasting, and a metal surface by sandblasting, knurling, or laser processing. The width of the concave portion is, for example, 1 to 100 μm.

  Among these, what was obtained by immersing a metal in the first erodible aqueous solution or erodible suspension is preferable because the metal material can be treated collectively over a wide range.

  The average length (RSm) of the contour curve elements of the convex and concave portions is 10 nm to 500 μm, and the ten-point average roughness (Rz) is 10 nm to 300 μm. Or a method of immersing a metal member in an aqueous solution of an inorganic acid such as hydrochloric acid or nitric acid, a method of treating a metal member by an anodic oxidation method, hydrazine hydrate, ammonia as disclosed in WO2009 / 31632, And a method of immersing the metal member in one or more aqueous solutions selected from water-soluble amine compounds. These methods can be properly used depending on the metal type of the metal member to be used and the uneven shape formed within the interval period.

The metal member according to the present embodiment is JIS B0601 (corresponding to a total of six straight portions including arbitrary three straight portions in parallel relation on the metal member surface and arbitrary three straight portions orthogonal to the three straight portions. It is preferable that the surface roughness measured in accordance with International Standard: ISO 4287) satisfies the following requirements (1) and (2) simultaneously.
(1) One or more straight portions including a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm are 30% or less.
(2) The 10-point average roughness (Rz) of all straight portions at an evaluation length of 4 mm exceeds 2 μm.

For such a metal member that satisfies the requirements (1) and (2), for example, the following steps (a), (b), and (c) are sequentially performed using an etching agent to roughen the metal. Can be formed.
(A) A pretreatment process for removing an oxide film, a hydroxide film or a mechanical oil film attached to the surface of the metal member.
(B) A surface roughening treatment step using an acid-based etchant containing at least one of ferric ions and cupric ions and an acid, and optionally containing manganese ions and various additives.
(C) A post-treatment step such as washing with water and drying to remove smut and the like attached by the treatment with the acid-based etching agent.

  A primer layer may be formed on the surface of the metal member that has been treated by the above method. In the present invention, if a specific uneven shape is formed on the surface of the metal member by the above method, a bond with a rubber member described later is formed with a high strength, but when a stronger bond strength is required. It is also possible to form a primer layer. In particular, when the rubber member contains a polyolefin-based crosslinkable elastomer, a metal / rubber composite structure with even higher bonding strength can be obtained by forming a primer layer on the surface of the metal member.

  Although the material which comprises a primer layer is not specifically limited, Usually, it consists of primer resin material containing a resin component. The primer resin material is not particularly limited, and known materials can be used. Specific examples include known polyolefin-based primers, epoxy-based primers, urethane-based primers, and the like. The method for forming the primer layer is not particularly limited. For example, the primer layer can be formed by applying a solution of the primer resin material or an emulsion of the primer resin material to the surface-treated metal member. Examples of the solvent used for preparing the solution include toluene, methyl ethyl ketone (MEK), dimethylformamide (DMF), methylcyclohexane and the like. Examples of the medium for the emulsion include an aliphatic hydrocarbon medium and water.

<Rubber member>
The rubber member according to the present invention is characterized in that a composition containing a crosslinkable elastomer that is liquid at 25 ° C. is preferably formed by direct injection molding on a metal surface and then subjected to a crosslinking treatment.

[Composition containing a crosslinkable elastomer]
The composition containing a crosslinkable elastomer in the present invention is obtained by mixing a crosslinkable elastomer that is liquid at 25 ° C. and a substance for crosslinking the crosslinkable elastomer, for example. Hereinafter, each component will be described. In the present specification, “liquid state at 25 ° C.” is defined as a liquid having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5000 Pa · s at a shear rate of 10 s ⁻¹ .

○ Crosslinkable elastomer The crosslinkable elastomer used in the present invention can be selected without particular limitation, except that it is liquid at 25 ° C. Examples of such liquid crosslinkable elastomers include fluorine elastomers, silicone elastomers, acrylic elastomers, urethane elastomers, epoxy elastomers, and ethylene / α-olefin / non-conjugated polyene random copolymers. Among these, an ethylene / α-olefin / non-conjugated polyene random copolymer is preferably used because of its excellent long-term use stability as a molded product.

○ Crosslinkable elastomer composition In the present invention, when ethylene / α-olefin / non-conjugated polyene random copolymer is selected as the crosslinkable elastomer, the composition containing the crosslinkable elastomer includes the following two embodiments [1 ] And [2] can be considered.

  [1] An embodiment comprising (A) an ethylene / α-olefin / non-conjugated polyene random copolymer, (B) a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule, and (C) a transition metal catalyst .

  [2] An embodiment comprising (A) an ethylene / α-olefin / non-conjugated polyene random copolymer, (D) an organic peroxide, and (E) a crosslinking aid.

  Hereinafter, the components (A) to (E) will be described.

(A) Ethylene / α-olefin / non-conjugated polyene random copolymer (A) The ethylene / α-olefin / non-conjugated polyene random copolymer used in the present invention is, for example, ethylene and 3 to 20 carbon atoms. A random copolymer of an α-olefin and a non-conjugated polyene.

  Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene. 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11 -Methyl-1-dodecene, 12-ethyl-1-tetradecene and the like. Among these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used.

  These α-olefins are used alone or in combination of two or more.

  The non-conjugated polyene used in the present invention is, for example, a terminal vinyl group-containing norbornene compound represented by the following general formula [I] or [II].

In the general formula [I], n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms of R ¹ is Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, t-pentyl group, neopentyl group Hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Specific examples of the alkyl group having 1 to 5 carbon atoms of R ² include alkyl groups having 1 to 5 carbon atoms among the specific examples of R ¹ described above.

In the general formula [II], R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Specific examples of the alkyl group for R ³ include the same alkyl groups as the specific examples of the alkyl group for R ¹ .

  Specific examples of the norbornene compound represented by the general formula [I] or [II] include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, and 5- (2-propenyl) -2-norbornene. 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3- Butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2 -Norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-nor Lunene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. Among these, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene are preferred. These norbornene compounds can be used alone or in combination of two or more.

In addition to the norbornene compound (for example, 5-vinyl-2-norbornene), the following non-conjugated polyenes can be used in combination as long as the target physical properties of the present invention are not impaired. Specific examples of such a non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, Chain non-conjugated dienes such as 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene , Cyclic non-conjugated dienes such as dicyclopentadiene;
And trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene; and the like.

  The (A) ethylene / α-olefin / non-conjugated polyene random copolymer comprising the above components has, for example, the following constitution and characteristics.

(I) Molar ratio of ethylene and α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin)
(A) The ethylene / α-olefin / non-conjugated polyene random copolymer is composed of (a) a unit derived from ethylene and (b) an α-olefin having 3 to 20 carbon atoms (hereinafter simply referred to as “α-olefin”). ) In the molar ratio [(a) / (b)] to the unit derived from 35/65 to 95/5, preferably 40/60 to 95/5, more preferably 45/55 to 90/10, Preferably it is contained at 50/50 to 85/15, most preferably 55/45 to 80/20.

  When this molar ratio is within the above range, a composition capable of providing a crosslinked elastomer molded article having excellent heat aging resistance, strength characteristics and rubber elasticity, and excellent cold resistance and processability can be obtained.

(Ii) Iodine value (A) The iodine value of the ethylene / α-olefin / non-conjugated polyene random copolymer is 0.5 to 50 (g / 100 g), preferably 0.8 to 40 (g / 100 g), More preferably, it is 1-35 (g / 100g), Most preferably, it is 1.5-30 (g / 100g).

  When the iodine value is within the above range, a composition having a fast crosslinking rate at room temperature can be obtained, and a crosslinked elastomer molded product having excellent resistance to compression set and excellent environmental resistance (= heat aging resistance). A composition capable of providing An iodine value exceeding 50 is not preferable because it is disadvantageous in terms of cost.

(Iii) Intrinsic viscosity (A) The intrinsic viscosity [η] of an ethylene / α-olefin / nonconjugated polyene random copolymer measured in decalin at 135 ° C. is 0.01 to 5.0 dl / g, preferably 0.8. 01 to 2 dl / g, more preferably 0.02 to 1.8 dl / g, particularly preferably 0.05 to 1.5 dl / g, and most preferably 0.07 to 1.0 dl / g. When the intrinsic viscosity [η] is within the above range, a composition excellent in fluidity and capable of providing a crosslinked elastomer molded article excellent in strength characteristics and compression set resistance can be obtained.

  Further, from the viewpoint of emphasizing moldability, adhesiveness, and strength after adhesion, the intrinsic viscosity [η] is 0.01 to 2.0 dl / g, preferably 0.05 to 1.0 dl / g, particularly Preferably, it is 0.07 to 0.8 dl / g, and most preferably 0.07 to 0.7 dl / g.

  Furthermore, from the viewpoint of emphasizing moldability, adhesiveness, and spreading to the interface at the time of adhesion, this intrinsic viscosity [η] is 0.01 to 0.5 dl / g, preferably 0.01 dl / g or more. And less than 0.4 dl / g, particularly preferably in the range of 0.05 to 0.3 dl / g.

(Iv) Molecular weight distribution (Mw / Mn)
(A) The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin / non-conjugated polyene random copolymer measured by GPC is 1 to 100, preferably 1.5 to 50, more preferably 2.0 to 10. It is.

  When this molecular weight distribution (Mw / Mn) is within the above range, a composition capable of providing a crosslinked elastomer molded article having excellent processability and excellent strength characteristics can be obtained.

(B) Hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule Hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule (in the present invention, compound (B) or SiH group) (Sometimes referred to as a containing compound) acts as a crosslinking agent that reacts with the copolymer (A). This compound (B) is not particularly limited as long as it contains at least 2, preferably 3 or more, hydrogen atoms directly bonded to silicon atoms, that is, SiH groups, in the molecule, and thus has been conventionally produced. For example, any resinous material such as a linear, annular, branched structure or three-dimensional network structure can be used.

As the compound (B), the following general composition formula [III]
^{_{R 4 b H c SiO (4}} -b-c) / 2 ··· [III]
The compound represented by these can be used.

In the general formula [III], R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, excluding an aliphatic unsaturated bond. In addition to the alkyl group exemplified for R ¹ in the general formula [I], a phenyl group and a halogen-substituted alkyl group such as a trifluoropropyl group can be exemplified. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

  Further, b is 0 ≦ b <3, preferably 0.6 <b <2.2, particularly preferably 1.5 ≦ b ≦ 2, and c is 0 <c ≦ 3, preferably 0.002. ≦ c <2, particularly preferably 0.01 ≦ c ≦ 1, and b + c is 0 <b + c ≦ 3, preferably 1.5 <b + c ≦ 2.7.

The compound (B) is an organohydrogenpolysiloxane having preferably 2 to 1000, particularly preferably 2 to 300, most preferably 2 to 200 silicon atoms in one molecule. Siloxane oligomers such as 1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7,8-pentamethylpentacyclosiloxane; Siloxy group-blocked methyl hydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methyl hydrogen siloxane copolymer, molecular chain both ends silanol group-blocked methyl hydrogen polysiloxane, molecular chain both ends silanol group-blocked dimethyl siloxane・ Methylhydrogensiloxane co-polymer Dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane and methylhydrogensiloxane Polymer, consisting of R ⁴ ₂ (H) SiO _1/2 units and SiO _4/2 units, optionally R ⁴ ₃ SiO _1/2 units, R ⁴ ₂ SiO _2/2 units, R ⁴ (H) SiO Mention may be made of silicone resins which may contain _2/2 units, (H) SiO _3/2 or R ⁴ SiO _3/2 units.

Examples of the trimethylsiloxy group-blocked methyl hydrogen polysiloxane having both molecular chain ends include, for example, a compound represented by the following general formula [IV], and further, a part or all of the methyl group in the following general formula [IV] is an ethyl group, Examples include compounds substituted with a propyl group, a phenyl group, a trifluoropropyl group, and the like.
_{(CH 3) 3 SiO - (} - SiH (CH 3) -O-) d -Si (CH 3) 3 ··· [IV]
In the formula (VI), d is an integer of 2 or more.

As the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with a trimethylsiloxy group at both ends of the molecular chain, a compound represented by the following general formula [V], and a part or all of the methyl groups in the following general formula [V] are ethylated. And a compound substituted with a group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.
_{(CH 3) 3 SiO - (} - Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 3 ··· [V]
Note that e in the formula [V] is an integer of 1 or more, and f is an integer of 2 or more.

Examples of the methyl hydrogen polysiloxane blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following general formula [VI], and further a part or all of the methyl group in the following general formula [VI]: an ethyl group, a propyl group, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.
_{HOSi (CH 3) 2 O -} (- SiH (CH 3) -O-) 2 -Si (CH 3) 2 OH ··· [VI]

Examples of the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following general formula [VII], and further a part or all of the methyl group in the following general formula [VII]. And compounds substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.
_{HOSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 2 OH ··· [VII]
Note that e in the formula [VII] is an integer of 1 or more, and f is an integer of 2 or more.

Examples of the dimethylpolysiloxane blocked with a dimethylhydrogensiloxy group at both ends of the molecular chain include, for example, a compound represented by the following general formula [VIII], and further a part or all of the methyl group in the following general formula [VIII] is an ethyl group, propyl And a compound substituted with a group, a phenyl group, a trifluoropropyl group, and the like.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e -Si (CH 3) 2 H ··· [VIII]
Note that e in the formula [VIII] is an integer of 1 or more.

Examples of the molecular chain both-end dimethylhydrogensiloxy group-capped methylhydrogenpolysiloxane include, for example, a compound represented by the following general formula [IX], and further a part or all of the methyl group in the following general formula [IX] as an ethyl group, Examples include compounds substituted with a propyl group, a phenyl group, a trifluoropropyl group, and the like.
_{HSi (CH 3) 2 O -} (- SiH (CH 3) -O-) e -Si (CH 3) 2 H ··· [IX]
Note that e in the formula [XI] is an integer of 1 or more.

Examples of the dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of the molecular chain include, for example, a compound represented by the following general formula [X], and further a part of the methyl group in the following general formula [X] Examples thereof include compounds in which all are substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) h -Si (CH 3) 2 H ··· [X]
Note that e and h in the formula [X] are each an integer of 1 or more.

  Such a compound can be produced by a known method. For example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane and hexamethyldisiloxane or 1,3-dihydro-1, which can be a terminal group. A compound containing a triorganosilyl group or a diorganohydrogensiloxy group, such as 1,3,3-tetramethyldisiloxane, in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, and the like. It can be easily obtained by equilibrating at a temperature of about 0 ° C to + 40 ° C.

  These compounds (B) can be used alone or in combination of two or more.

(C) Transition Metal Catalyst The (C) transition metal catalyst used in the present invention is an addition reaction catalyst, and an addition reaction between the alkenyl group in the copolymer (A) and the SiH group of the compound (B) ( The catalyst is not particularly limited as long as it promotes the hydrosilylation reaction of an alkene. For example, an addition reaction catalyst composed of a platinum group element such as a platinum-based catalyst, a palladium-based catalyst, a rhodium-based catalyst (group 8 metal, group 8) Group 8 metal catalysts such as metal complexes and Group 8 metal compounds). Moreover, in this invention, it is desirable to use the complex of a periodic table group 8 element metal and the compound containing a vinyl group and / or a carbonyl group. As the group 8 element metal of the periodic table, platinum is particularly preferable.

  The platinum-based catalyst may be a known one that is usually used for addition-curing type curing, such as a finely powdered platinum metal catalyst described in US Pat. No. 2,970,150, US Pat. No. 2,823, No. 218, chloroplatinic acid catalyst, U.S. Pat. No. 3,159,601 and U.S. Pat. No. 159,662, complex compounds of platinum and hydrocarbons, U.S. Pat. Complex of chloroplatinic acid and olefin described in US Pat. No. 5,516,946, platinum and vinylsiloxane described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780 And complex compounds. More specifically, examples include platinum alone (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, or a carrier such as alumina or silica on which a platinum carrier is supported.

  As the compound containing a vinyl group, a vinyl group-containing organosiloxane is preferable. Specific examples of complexes of these with platinum include platinum-divinyltetramethyldisiloxane complex, platinum-divinyltetraethyldisiloxane complex, platinum-divinyltetrapropyldisiloxane complex, platinum-divinyltetrabutyldisiloxane complex, platinum -Divinyltetraphenyldisiloxane complex.

  As the compound containing a carbonyl group, carbonyl, octanal and the like are preferable. Specific examples of the complex of these with platinum include a platinum-carbonyl complex, a platinum-octanal complex, a platinum-carbonylbutyl cyclic siloxane complex, and a platinum-carbonylphenyl cyclic siloxane complex.

  Among the vinyl group-containing organosiloxanes, vinyl group-containing cyclic organosiloxanes are preferable. Examples of the complex of platinum with platinum include a platinum-vinylmethyl cyclic siloxane complex, a platinum-vinylethyl cyclic siloxane complex, and a platinum-vinylpropyl cyclic siloxane complex. The vinyl group-containing organosiloxane itself may be a ligand for a metal, but may be used as a solvent for coordinating other ligands. A complex in which a vinyl group-containing organosiloxane is used as a solvent and the above-mentioned compound containing a carbonyl group is a ligand is particularly preferred as a catalyst used in the hydrosilylation reaction of the present invention.

  Specific examples of such complexes include a platinum-carbonyl complex vinylmethyl cyclic siloxane solution, a platinum-carbonyl complex vinylethyl cyclic siloxane solution, a platinum-carbonyl complex vinylpropyl cyclic siloxane solution, and a platinum-carbonyl complex divinyl. Tetramethyldisiloxane solution, platinum-carbonyl complex divinyltetraethyldisiloxane solution, platinum-carbonyl complex divinyltetrapropyldisiloxane solution, platinum-carbonyl complex divinyltetrabutyldisiloxane solution, platinum-carbonyl complex divinyltetraphenyldi A siloxane solution is mentioned.

  The catalyst comprising these complexes may further contain components other than the compound containing a vinyl group and / or a carbonyl group. For example, a solvent other than a compound containing a vinyl group and / or a carbonyl group may be contained. Examples of these solvents include various alcohols and xylene, but are not limited thereto.

  Specific examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol. , Aliphatic saturated alcohols such as capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and eicosyl alcohol; fats such as allyl alcohol and crotyl alcohol Unsaturated alcohols; cycloaliphatic alcohols such as cyclopentanol and cyclohexanol; benzyl alcohol, Aromatic alcohols such as runner mill alcohol; and heterocyclic alcohols such as furfuryl alcohol.

  An example of using alcohol as a solvent is a platinum-octanal / octanol complex. By including these solvents, there are advantages such as easy handling of the catalyst and easy mixing with the composition. Among the various catalysts mentioned above, a platinum-carbonyl complex vinylmethyl cyclic siloxane solution (a complex represented by the following chemical formula 1 is preferred), a platinum-vinylmethyl cyclic siloxane complex (a complex represented by the chemical formula 2 is particularly preferred). ), A platinum-divinyltetramethyldisiloxane complex (in particular, a complex represented by Chemical Formula 3), a platinum-octanal / octanol complex and the like are practically preferred, and among them, a platinum-carbonylvinylmethyl cyclic siloxane complex is particularly preferred.

Chemical formula 1: Pt ⁰ · CO · (CH ₂ ═CH (Me) SiO) ₄
Chemical formula 2: Pt ⁰ · (CH ₂ ═CH (Me) SiO) ₄
Chemical formula 3: Pt ⁰ -1.5 [(CH ₂ ═CH (Me) ₂ Si) ₂ O]
The palladium-based catalyst is composed of palladium, a palladium compound, chloropalladic acid, and the rhodium-based catalyst is composed of rhodium, a rhodium compound, rhodium chloride, and the like.

  Examples of the catalyst other than the above include Lewis acid and cobalt carbonyl.

  These catalysts can be used alone or in combination of two or more.

  The proportion of Group 8 element metal (preferably platinum) contained in these catalysts is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, and more preferably 2 to 4% by mass.

(D) Organic peroxide As the organic peroxide, organic peroxides usually used as a crosslinking agent in EPR and EPDM can be used without particular limitation. For example, the following general formula (a) and the following general formula The organic peroxide represented by (b) is mentioned.

X ¹ —O—O—X ² —O—O—X ³ (a)
(In Formula (a), X ¹ , X ² and X ³ each independently represents an organic group having 4 or more carbon atoms)
Y ¹ —O—O—Y ² (b)
(In formula (b), Y ¹ and Y ² each independently represents an organic group having 4 or more carbon atoms)

  Specific examples of such organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5 -Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5 -Trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-Butylperoxyisopropyl Carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-2,5 amyl peroxide, t- Butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl Dialkyl peroxides such as -2,5-mono (t-butylperoxy) hexane and α, α'-bis (t-butylperoxy-m-isopropyl) benzene; t-butylperoxyacetate, t-butyl Peroxyisobutyrate, t-butyl peroxybivalate, t-butyl peroxy Maleic acid, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate, 1,1-bis-t-butylperoxy-3,3,5-tri-methyl Examples thereof include peroxyesters such as cyclohexane, ketone peroxides such as dicyclohexanone peroxide, and mixtures thereof. Among these, organic peroxides having a temperature giving a half-life of 1 minute in the range of 130 ° C. to 200 ° C. are preferable.

  Among these, dicumyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2 are preferred in terms of reactivity, odor, and scorch stability. Bifunctional organic peroxides such as 1,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (-(tertbutylperoxyisopropyl) benzene are particularly preferable. -Dimethyl-2,5-di- (tert-butylperoxy) hexane and dicumyl peroxide are more preferable.

  These organic peroxides may be used alone or in combination of two or more.

(E) Crosslinking aid Examples of the crosslinking aid include allylic compounds such as diallyl phthalate, triallyl isocyanurate, and trimethallyl isocyanurate.

  Among these, a crosslinking aid (triallyl isocyanurate) represented by the following formula (c) and / or a crosslinking aid (trimethallyl isocyanurate) represented by the following formula (d) is preferably used.

  These crosslinking aids may be used alone or in combination of two or more.

  Moreover, as a crosslinking adjuvant, crosslinking assistants other than the crosslinking assistant consisting of the said allyl type compound may be contained. Examples of such crosslinking aids include sulfur; quinone dioxime compounds such as P-quinone dioxime; acrylic compounds such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; other maleimide compounds, divinylbenzene ( DVB) and the like.

  In the present invention, the composition containing a crosslinkable elastomer comprises (A) an ethylene / α-olefin / nonconjugated polyene random copolymer, and (B) a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule, (C) When it is an aspect containing a transition metal catalyst, a compound (B) is 0.1-100 mass parts normally with respect to 100 mass parts of said copolymers (A), Preferably it is 0.1-75 mass. Parts, more preferably 0.1 to 50 parts by weight, particularly preferably 0.2 to 30 parts by weight, and most preferably 0.2 to 20 parts by weight. Within the above range, a composition capable of forming a crosslinked rubber molded article having excellent compression set resistance, moderate crosslinking density and excellent strength properties and elongation properties can be obtained. Use of the compound (B) in a proportion exceeding 100 parts by mass is not preferable because it is disadvantageous in terms of cost. Moreover, (C) transition metal catalyst is 0.01-10 mass parts normally with respect to 100 mass parts of said copolymers (A), Preferably it is 0.1-5 mass parts, More preferably, 0.1-0.1 mass parts. It is used at a ratio of 3 parts by mass. When used within this range, a crosslinked rubber molded article having a moderate crosslinking density and excellent strength and elongation properties can be formed. If it is used in a proportion exceeding 10 parts by mass, it is not preferable because it is disadvantageous in terms of cost.

  In the present invention, the composition containing a crosslinkable elastomer is an embodiment containing (A) an ethylene / α-olefin / non-conjugated polyene random copolymer, (D) an organic peroxide, and (E) a crosslinking aid. In this case, the organic peroxide (D) is usually 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, more preferably 0.5 to 100 parts by weight of the copolymer (A). To 15 parts by mass, particularly preferably 1.0 to 10 parts by mass, and most preferably 2.0 to 7.0 parts by mass. It is excellent in the point of the balance of crosslinking efficiency and cost as it is in the said range. Moreover, (E) crosslinking adjuvant is 0.1-10 mass parts normally with respect to 100 mass parts of said copolymers (A), Preferably it is 0.2-7 mass parts, More preferably, it is 0.5-. It is used at a ratio of 5 parts by mass. Use within this range is excellent in terms of crosslinking efficiency, cost, and compatibility.

  Furthermore, in the present invention, the composition containing a crosslinkable elastomer may further contain a filler.

  As the filler, one or more kinds from the group consisting of glass fiber, carbon fiber, carbon particle, clay, talc, silica, mineral, cellulose fiber, carbonate such as calcium carbonate and sodium carbonate, metal oxide, metal hydroxide You can choose. Of these, glass fiber, carbon fiber, talc, silica, mineral, carbonate, metal oxide, metal hydroxide, and carbon are preferable.

  The shape of the filler may be any shape such as a fiber shape, a particle shape, or a plate shape.

  The filler may be one type or two or more types.

  In addition, when the said composition contains a filler, the content becomes with respect to 100 mass parts of said crosslinkable elastomers, Preferably it is 0.1-10000 mass parts, More preferably, it is 1-500 mass parts. Especially preferably, it is 5-400 mass parts, Most preferably, it is 10-300 mass parts.

  These fillers have the effect of reducing and controlling the linear expansion coefficient of the rubber member in addition to the effect of increasing the rigidity of the resin member. In particular, in the case of the composite of the metal member and the rubber member according to the present embodiment, the temperature dependence of the shape stability of the metal member and the rubber member is often greatly different. It tends to be distorted. By containing the filler, this distortion can be reduced. Moreover, reduction of toughness can be suppressed because content of a filler exists in the said range.

[Other ingredients]
In the present invention, the composition containing a crosslinkable elastomer may contain a compounding agent for the purpose of imparting individual functions.

  Examples of the compounding agent include a heat stabilizer, an antioxidant, a pigment, a weathering agent, a flame retardant, a plasticizer, a dispersant, a lubricant, a release agent, and an antistatic agent.

[Other resins]
In the present invention, the composition containing a crosslinkable elastomer may contain a resin for the purpose of imparting individual functions.

  Examples of the resin include polyethylene, polypropylene, vinyl chloride resin, natural rubber, acrylic resin, epoxy resin, silicone resin, fluorine resin, urethane, polyamide, polyester resin, and polyimide.

(Preparation of composition)
The composition comprises the components (A) to (E) described above and, if necessary, a filler, other compounding agents, and other resins, a planetary mixer, a rotation and revolution type stirrer, a Banbury mixer, a uniaxial It can be obtained by mixing or heating and mixing with a mixing apparatus such as an extruder, a twin-screw extruder, a high-speed twin-screw extruder, a two-roll, a three-roll, or a bead mill.

  The injection molding conditions and the crosslinking treatment conditions for the composition containing the crosslinkable elastomer will be described later in the description of the method for producing a metal / rubber composite structure.

<Metal / Rubber composite structure>
The metal / rubber composite structure according to the present invention includes the metal member and the rubber member.

  More specifically, in the metal / rubber composite structure according to the present invention, a composition containing a crosslinkable elastomer that is liquid at 25 ° C., which is a raw material for forming the rubber member, is formed on the surface of the metal member. It is obtained by intruding into and joining a specific uneven shape portion (surface roughened portion) and then performing a crosslinking treatment so that the rubber member enters and joins the uneven shape portion on the metal surface.

  In a general prior art, when a composite structure composed of a metal member and a rubber member is manufactured, the rubber member is formed by preliminarily cross-linking a crosslinkable elastomer and shaping and a metal member. Are bonded using an adhesive. However, since this method is based on the chemical bonding force through the bonding adhesive between both members, the bonding strength tends to be relatively low, and external factors such as moisture and light If the adhesive component deteriorates due to the influence of the above, it is mentioned as a material of concern that the bonding strength is significantly reduced.

  On the other hand, in the present invention, by using a crosslinkable elastomer that is liquid at 25 ° C., it is possible to easily enter the concavo-convex shape portion formed on the surface of the metal member, and in this state, the crosslinking treatment is performed. Therefore, a part of the rubber member is held in a state where the rubber member firmly enters the concavo-convex shape portion of the metal member. That is, since both members are joined by a physical coupling force, it can be expected that the joining strength can be increased. Further, since the bonding is physically generated, there is no possibility that the bonded portion deteriorates in the use environment like the above-described adhesive, and therefore the metal / rubber composite structure in the present invention is used for a long time. It can be expected to have excellent stability.

[Method for producing metal / rubber composite structure]
The method for producing the metal / rubber composite structure of the present invention is not particularly limited, and the above composition is preferably bonded to the metal member having the above characteristics while being molded into a desired rubber member shape. Is obtained.

  Rubber member molding methods include injection molding, extrusion molding, heat press molding, compression molding, transfer molding, casting molding, laser welding molding, reaction injection molding (RIM molding), rim molding (LIM molding), and thermal spray molding. A resin molding method such as a dispenser can be employed.

Among these, liquid injection molding, that is, rim molding (LIM molding) is preferable because the composition is liquid at 25 ° C. Specifically, the metal member is inserted into the cavity portion of the rim molding die. And it is preferable to manufacture by the method of inject | pouring the said composition into a metal mold | die. Specifically, the following steps (i) to (iv) are included.
(I) Step of preparing the composition (ii) Step of installing a metal member in a mold for rim molding (iii) The mold so that the composition is in contact with at least a part of the metal member Step (iv) of injecting into the mold, and heating the mold to cross-link the composition to form a rubber member

  Hereinafter, each step will be described.

  (I) About the process of preparing the said composition, as above-mentioned, each component of (A)-(E), and a filler, another compounding agent, and other resin as needed, a planetary mixer, It can be obtained by mixing or heating and mixing with a mixing device such as a rotation and revolution type stirrer, Banbury mixer, single-screw extruder, twin-screw extruder, high-speed twin-screw extruder, two-roll, three-roll, or bead mill. .

  Next, an injection molding method according to steps (ii) to (iv) will be described.

  First, a mold for rim molding is prepared, the mold is opened, and a metal member is installed on a part thereof. Thereafter, the mold is closed, and the composition obtained in step (i) is injected into the mold so that at least a part of the composition is in contact with the surface of the metal member formed with the concave shape. . Then, a metal / rubber composite structure can be obtained by heating a metal mold | die to the conditions which a crosslinkable elastomer bridge | crosslinks, forming a rubber member, and finally opening and releasing a metal mold | die.

[Use of metal / rubber composite structure]
Since the metal / rubber composite structure of the present invention has high productivity and high degree of freedom in shape control, it can be developed for various applications.

  For example, sealing members such as waterproof packing, vacuum packing, packing for pressure devices, stress relaxation members, members for portable devices, members for solar cells, members for lithium ion batteries, members for residential construction, members for automobiles, members for aerospace Etc.

  More specifically, waterproof seals for mobile devices such as mobile phones, smartphones, tablets, hard disk drives, digital cameras, watches, waterproof seals for household appliances such as washing machines and pots, fuel cell gaskets, and packings for lithium-ion batteries. Can be mentioned.

  The use of the metal / rubber composite structure of the present invention has been described above, but these are examples of the use of the present invention, and various configurations other than those described above can also be adopted.

  Embodiments of the present invention will be described below by way of examples, but the present embodiments are not limited to these.

(Measurement of load length ratio (Rmr), ten-point average roughness (Rz), and average length (RSm) of roughness curve elements on the surface of a metal member)
Unless otherwise specified, the load length of the roughness curve among the surface roughness measured using the surface roughness measuring device “Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)” according to JIS B0601 (corresponding ISO 4287). The roughness ratio (Rmr), ten-point average roughness (Rz), and average length (RSm) of the roughness curve elements were measured. The measurement conditions are as follows.
・ Tip tip radius: 5μm
・ Standard length: 0.8mm
・ Evaluation length: 4mm
・ Measurement speed: 0.06mm / sec
The measurement was performed on a total of six straight line portions including arbitrary three straight line portions in parallel relation on the surface of the metal member and arbitrary three straight line portions orthogonal to the straight line portion.

(Molding speed evaluation)
In the range of a molding temperature of 170 to 230 ° C., the case where the molded product was cured within 10 minutes was evaluated as “◯”, and the case where the molded product was not cured was expressed as “X”.

(Joint strength evaluation)
The shear joint strength of the metal / rubber composite structure samples produced in each example and comparative example was evaluated. For the evaluation, a sample in which a resin portion (width 10 mm × length 45 mm × thickness 3 mm) was joined to an end portion 1 cm ² of an aluminum metal plate (width 18 mm × length 45 mm × thickness 1.6 mm) was used. A tensile tester (manufactured by Toyo Seiki Seisakusho, Strograph E3) was used as the evaluation device. The metal end was fixed to the lower chuck of the testing machine, and the upper end of the rubber was pulled up at a speed of 50 mm / sec by the upper chuck of the testing machine to evaluate the shear bonding strength. A sample having a shear strength of 0.5 MPa or more was evaluated as ◯, and a sample having a lower shear strength was evaluated as ×.

(Heat resistance evaluation)
The heat resistance of the molded rubber member was evaluated. A rubber member is placed in an oven at 250 ° C. for 30 minutes and melted. A sample that was not melted and maintained in a state was marked with a circle.

(Evaluation of moisture permeability)
The moisture permeation resistance of the molded rubber member was evaluated by a cup method (based on JIS Z 0208). The rubber member was cut into a size of 70 mmφ and placed in a moisture permeable cup in which calcium chloride (anhydrous) was enclosed as a hygroscopic agent. The moisture permeable cup was put into a moist heat tester of 40 ° C. × 90% RH, and the weighing operation was repeated every 24 hours, and the increase in mass of the cup was evaluated as the amount of water vapor permeated. A thing with a water vapor permeability of 100 g / m ² · day or less. More than that was marked with x.

[Example 1]
Preparation of composition (A) As crosslinkable elastomer, ethylene / α-olefin / non-molecular weight Mn = 3,500-4,500, viscosity 450-850 Pa · s, ethylene content 52 wt%, VNB content 4.7 wt% Conjugated polyene random copolymer (product name: PX062 manufactured by Mitsui Chemicals), and ethylene having a molecular weight Mn = 900 to 1,000, a viscosity of 8,000 to 12,000 mPa · s, an ethylene content of 50 wt%, and a VNB content of 11.3 wt% Α-olefin / non-conjugated polyene random copolymer (Mitsui Chemicals, brand name PX068), (B) hydrosilyl group-containing compound (manufactured by Shin-Etsu Chemical Co., Ltd.) as a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule Brand name X93-916 (refer to the following formula 1)), reaction inhibitor (manufactured by Shin-Etsu Chemical, brand name X93-103) (See formula 2)), silica (Tosoh Silica manufactured as filler, stock name SS95, dimethylsiloxane treated silica) were weighed in accordance with the composition of Table 1.

  The weighed sample was stirred at 2,000 rpm for 10 minutes using THINKY Awtori Nertaro (registered trademark) (AR-250). After cooling, as a transition metal catalyst (C), a platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., brand name X93-1410, (see the following formula 3)) was stirred at 2,000 rpm for 1 minute to obtain a composition.

○ Metal surface treatment (Method A)
Concavity and convexity treatment was performed on one surface of an aluminum metal plate (18 mm × 45 mm × thickness 1.6 mm) to be joined as a metal member. First, after degreasing the metal surface with acetone or the like, an aqueous solution containing 3.5% monohydric hydrazine at 60 ° C. was prepared in another tank, and the metal plate was immersed in this for 2 minutes and washed with water. Subsequently, it put into the warm air dryer which was 67 degreeC for 15 minutes, and dried. When the treated surface was observed with a laser microscope after drying, it was confirmed that the treated surface was covered with a recess having a diameter of 50 to 100 nm.

○ Manufacture of metal / rubber composite structure A small dumbbell metal insert mold is mounted on a liquid injection molding machine (LIM molding machine: NEX50) manufactured by Nissei Plastic Industry Co., Ltd. A metal piece (18 mm x 45 mm x thickness 2 mm) was placed. Subsequently, the prepared composition was injected into the mold to obtain a metal / rubber composite structure. Molding was performed under the conditions of a mold temperature of 170 ° C., an injection speed of 100 mm / sec, a holding pressure of 10 MPa, and a holding time of 1 minute. The obtained metal / rubber composite structure was subjected to various evaluations by the above methods. The evaluation results are shown in Table 1.

[Example 2]
○ Preparation of composition As crosslinkable elastomer, ethylene, α-olefin, non-conjugated polyene random, molecular weight Mn = 3,500-4,500, viscosity 450-850 Pa · s, ethylene content 52 wt%, VNB content 4.7 wt% Copolymer (made by Mitsui Chemicals, brand name PX062), and ethylene / α- with molecular weight Mn = 900 to 1,000, viscosity 8,000 to 12,000 mPa · s, ethylene content 50 wt%, and VNB content 11.3 wt% Olefin / Nonconjugated Polyene Random Copolymer (Mitsui Chemicals, Brand Name PX068), (D) Organic Peroxide, Brand Name Perbutyl I-75 (see Formula 4 below), (E ) As a crosslinking aid, triallyl isocyanurate (manufactured by Nippon Kasei Chemical, brand name TAIC (see the following formula 5)) is weighed according to the composition shown in Table 1. It was.

  The weighed sample was stirred at 2,000 rpm for 10 minutes using Awatori Nertaro (registered trademark) (AR-250) manufactured by THINKY, to obtain a composition.

Production of metal / rubber composite structure A metal / rubber composite structure was produced and evaluated in the same manner as in Example 1 except that the composition prepared above was used and the molding time was 5 minutes. It was. The evaluation results are shown in Table 1.

[Example 3]
Preparation of composition (A) As crosslinkable elastomer, ethylene / α-olefin / non-molecular weight Mn = 3,500-4,500, viscosity 450-850 Pa · s, ethylene content 52 wt%, VNB content 4.7 wt% Conjugated polyene random copolymer (Mitsui Chemicals, brand name PX062), (B) Hydrosilyl group-containing compound as hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule (Shin-Etsu Chemical Co., brand name X93-916) Then, a reaction inhibitor (manufactured by Shin-Etsu Chemical Co., Ltd., brand name X93-1036) and silica (manufactured by Tosoh Silica Co., Ltd., brand name SS95, dimethylsiloxane-treated silica) were weighed according to the composition shown in Table 1.

  The weighed sample was stirred at 2,000 rpm for 10 minutes using Awatori Nertaro (registered trademark) (AR-250) manufactured by THINKY, to obtain a composition.

○ Metal surface treatment (Method B)
An aluminum plate (thickness: 2.0 mm) was cut into a length of 45 mm and a width of 18 mm. This aluminum plate was treated with an acid-based etching agent (sulfuric acid: 8.2% by mass, ferric chloride: 7.8% by mass (Fe ³⁺ : 2.7% by mass), cupric chloride: 0.4% by mass (Cu Etching was performed by immersing in ( ²⁺ : 0.2% by mass) ion-exchanged water: remainder (30 ° C.) for 80 seconds and rocking. Subsequently, ultrasonic cleaning (in water, 1 minute) was performed with running water and dried to obtain a surface-treated metal member.

The surface roughness of the obtained metal member was measured using a surface roughness measuring device “Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)”, and cutting levels of 10%, 20%, 30%, and 40 were obtained for the six straight portions. The load length ratio (Rmr), the ten-point average roughness (Rz), and the average length (RSm) of the contour curve element at%, 50%, 60%, 70% and 80% were determined. Among these, the Rmr (20%) value at a cutting level of 20%, the number of straight portions where the Rmr (20%) value is 30% or less, the Rmr (40%) value at a cutting level of 40%, the Rmr (40%) ) The etching rate was calculated from the number of straight portions with a value of 60% or less, the Rz value of 6 straight portions, the average length (RSm) of the contour curve elements, and the mass ratio of the metal members before and after the etching process.
The obtained results are shown below.

Rmr (20%) value at 20% cutting level: 17.5, 10.3, 13.4, 10.6, 3.8, 7.4
Number of straight portions where the Rmr (20%) value is 30% or less: 6
Rmr (40%) values at 40% cleavage level: 43.6, 26.1, 48.0, 46.7, 33.5, 34.2
Number of straight portions where Rmr (40%) value is 60% or less: 6
Rz value [μm] of 6 linear portions: 17.8, 18.1, 19.6, 17.8, 17.2, 18.0
RSm value [μm] of 6 straight portions: 104, 83.0, 85.6, 98.7, 106.6, 103.1
Etching rate [% by mass]: 2.6

Production of metal / rubber composite structure A metal / rubber composite structure was produced and evaluated in the same manner as in Example 1 except that the composition prepared above was used and the molding time was 1 minute. It was. The evaluation results are shown in Table 1.

[Comparative Example 1]
A metal / rubber composite structure was produced and evaluated in the same manner as in Example 1 except that the metal surface treatment was not performed. The evaluation results are shown in Table 1.

[Comparative Example 2]
A small dumbbell metal insert mold is mounted on an injection molding machine (J85AD110H) manufactured by Nippon Steel Works Co., Ltd., and a metal piece (18 mm × 45 mm × thickness 2 mm) subjected to metal surface treatment by the above-described method is placed in the mold. installed. Next, a metal / resin composite structure was injected by injecting a propylene resin (manufactured by Prime Polymer: Prime Polypro (registered trademark) J705UG, MFR (230 ° C., 2.16 kg load) 9.0 g / 10 min) into the mold. Obtained. Molding was performed under the conditions of a cylinder temperature of 250 ° C., a mold temperature of 120 ° C., an injection speed of 25 mm / sec, a holding pressure of 20 MPa, and a holding time of 30 seconds. The obtained metal / resin composite structure was subjected to various evaluations by the above methods. The evaluation results are shown in Table 1.

[Comparative Example 3]
Preparation of composition The composition was prepared by mixing 5.3 parts by mass of an epoxy resin (Mitsui Chemicals, Epomic R139S) and 14.7 parts by mass of Jeffermin RT1000 (manufactured by Huntsman, polyetheramine) with a rotating and rotating stirrer. Prepared by kneading.

○ Production of metal / rubber composite structure A metal / rubber composite was prepared in the same manner as in Example 1 except that the composition prepared above was used, and the mold temperature was 180 ° C. and the molding time was 30 minutes. The structure was manufactured and evaluated. The evaluation results are shown in Table 1.

  The metal / rubber composite structure in the present invention is excellent in the bonding strength between the metal member and the rubber member, which has been difficult to manufacture by the prior art. In particular, the metal member and the rubber member have an adhesive. Since it is directly and strongly bonded without being used, and is excellent in long-term use stability, industrial applicability is high.

Claims (9)

In a metal / rubber composite structure formed by joining a metal member and a rubber member,
The metal surface of the metal member to which the rubber member is bonded has been subjected to surface roughening treatment,
A metal / rubber composite structure, wherein the rubber member is formed by a crosslinking treatment of a composition containing a liquid crosslinkable elastomer at 25 ° C.   2. The metal / rubber according to claim 1, wherein the rubber member is formed by directly injection-molding a composition containing a liquid crosslinkable elastomer at 25 ° C. onto a metal surface and then performing a crosslinking treatment. Composite structure.   2. The metal member according to claim 1, wherein the metal member has a concavo-convex shape having an average length (RSm) of 10 nm to 500 μm and a ten-point average roughness (Rz) of 10 nm to 300 μm on a metal surface to which the rubber member is bonded. Metal / rubber composite structure.   The metal / rubber composite structure according to claim 1, wherein the crosslinkable elastomer is (A) an ethylene / α-olefin / non-conjugated polyene random copolymer.   The composition comprises (A) an ethylene / α-olefin / non-conjugated polyene random copolymer, (B) a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule, and (C) a transition metal catalyst. The metal / rubber composite structure according to claim 1, comprising:   The metal / rubber according to claim 1, wherein the composition comprises (A) an ethylene / α-olefin / non-conjugated polyene random copolymer, (D) an organic peroxide, and (E) a crosslinking aid. Composite structure. The (A) ethylene / α-olefin / non-conjugated polyene random copolymer is
The molar ratio of ethylene unit (a) / α-olefin unit (b) ((a) / (b)) is 35/65 to 95/5,
The iodine value is in the range of 0.5-50 g / 100 g,
The metal / rubber composite structure according to claim 4, wherein the intrinsic viscosity [η] measured in a decalin solution at 135 ° C is 0.01 to 5.0 dl / g.   The metal / rubber composite structure according to claim 1, wherein the composition contains 0.1 to 10000 parts by mass of a filler with respect to 100 parts by mass of the crosslinkable elastomer.   The metal / rubber composite structure according to claim 2, wherein a liquid injection molding machine (LIM molding machine) is used for the injection molding.