JP7312588B2 - Composite compact and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composite compact and a method for producing the same.

Conventionally, molded articles having corner members such as weatherstrip materials (see, for example, Patent Documents 1 to 4) are generally produced by cutting a crosslinked molded article made of a rubber composition containing an ethylene/propylene/non-conjugated polyene copolymer, setting it in a mold, injecting a rubber molding material of the same type or different type as the rubber composition into the formed cavity, and performing crosslinking molding.

Molded articles obtained by hydrosilyl crosslinking of ethylene/α-olefin/non-conjugated polyene copolymers (see, for example, Patent Document 5) are known to be excellent in rubber elasticity, mechanical strength, heat aging resistance, and the like. Hydrosilyl cross-linking using a platinum-based catalyst is capable of high-speed, low-temperature reaction, and molded articles obtained using this cross-linking reaction are used in various rubber products.

Japanese Unexamined Patent Application Publication No. 2010-012738 Japanese Patent Application Laid-Open No. 2003-011204 Japanese Patent Application Laid-Open No. 2001-310685 JP-A-09-123211 JP 2006-290917 A

The hydrosilyl cross-linking reaction is susceptible to catalyst poisons such as elemental sulfur, which can inhibit the cross-linking reaction. Therefore, it has been difficult to join a crosslinked rubber member containing catalyst poisons such as elemental sulfur and a member requiring hydrosilyl crosslinking with good adhesive strength to form a composite.

The present inventors have studied to solve the above problems, and as a result, have found that the above problems can be solved by the configuration described below, and have completed the present invention. The present invention relates to, for example, the following [1] to [9].

[1] A composite molded article comprising a crosslinked rubber member (I) and a hydrosilyl crosslinked rubber member (II), wherein the member (I) and the member (II) are joined by an adhesive member having a first adhesive layer, a layer containing an ethylene-vinyl alcohol copolymer resin, and a second adhesive layer in this order.
[2] The molded composite article according to [1] above, wherein the crosslinked rubber contained in the member (I) is an ethylene/α-olefin/non-conjugated polyene copolymer crosslinked with a sulfur-based crosslinking agent.
[3] The composite molded article according to [1] or [2] above, wherein the crosslinked rubber contained in the member (II) is an ethylene/α-olefin/non-conjugated polyene copolymer crosslinked with a hydrosilyl crosslinking agent.
[4] The molded composite article according to any one of [1] to [3], wherein the first adhesive layer and the second adhesive layer are each independently composed of at least a modified polyolefin resin.
[5] The molded composite according to any one of [1] to [4], which is an automobile interior/exterior material.
[6] The composite molded article according to [5], wherein the automobile interior and exterior material is a weatherstrip material.
[7] The composite molded article according to [6], wherein the weatherstrip material is a molded body in which a linear member and a corner member are joined, the linear member is made of the crosslinked rubber member (I), the corner member is made of the hydrosilyl crosslinked rubber member (II), and the crosslinked rubber member (I) and the hydrosilyl crosslinked rubber member (II) are joined by the adhesive member.
[8] The step (1) of obtaining a composite (I)/(IIa) by bonding a crosslinked rubber member (I) to a member (IIa) comprising a rubber composition (II) containing a hydrosilyl-crosslinkable rubber component, a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule, and a platinum-based catalyst for hydrosilyl crosslinking with an adhesive member having, in this order, a first adhesive layer, a layer containing an ethylene-vinyl alcohol copolymer resin, and a second adhesive layer; The method for producing a composite molded article according to the above [1], further comprising the step (2) of cross-linking the composites (I)/(IIa).
[9] A step of forming a member (IIa) comprising a rubber composition (II) containing a hydrosilyl-crosslinkable rubber component, a hydrosilyl group-containing compound having at least two hydrosilyl groups per molecule, and a platinum-based catalyst for hydrosilyl crosslinking, on the crosslinked rubber member (I) in which an adhesive member having a first adhesive layer, a layer containing an ethylene-vinyl alcohol copolymer resin, and a second adhesive layer in this order is arranged, to obtain a composite (I)/(IIa) ( 1′) and the step (2) of cross-linking the composites (I)/(IIa).

According to the present invention, it is possible to provide a composite molded product obtained by combining a crosslinked rubber member that normally contains a catalyst poison such as elemental sulfur and a member that requires hydrosilyl crosslinking. Further, the molded composite of the present invention is excellent in adhesive strength between the crosslinked rubber member (I) and the hydrosilyl crosslinked rubber member (II) by the adhesive member.

A mode for carrying out the present invention will be described.
The composite molded body of the present invention is
a crosslinked rubber member (I);
and a hydrosilyl crosslinked rubber member (II).

The member (I) and the member (II) are joined by an adhesive member having a first adhesive layer, a layer containing an ethylene-vinyl alcohol copolymer resin (hereinafter also referred to as an "EVOH resin layer"), and a second adhesive layer in this order.
In addition to the first adhesive layer, the EVOH resin layer and the second adhesive layer, the adhesive member can have other layers such as a resin layer, if necessary.

[EVOH resin layer]
The EVOH resin layer is considered to function as a layer for preventing poisoning of the member (IIa) for forming the hydrosilyl crosslinked rubber member (II) from the crosslinked rubber member (I) during hydrosilyl crosslinking, that is, as a catalyst poison barrier layer.

In the ethylene-vinyl alcohol copolymer resin (EVOH) in the EVOH resin layer, the content of ethylene-derived structural units in the total repeating structural units is preferably 5 to 60 mol%, more preferably 20 to 50 mol%, from the viewpoint of enhancing barrier properties against catalyst poisons. The degree of saponification of EVOH is preferably 70 mol % or more, more preferably 80 mol % or more, and still more preferably 90 mol % or more, from the viewpoint of enhancing the barrier property against catalyst poisons.

The content and degree of saponification of EVOH are measured by ¹ H-NMR.
The melt flow rate (MFR) of EVOH at 190° C. and 2160 g load is preferably 0.5 to 20 g/10 minutes, more preferably 1.5 to 10 g/10 minutes.

The EVOH resin layer can contain one or more EVOH.
The thickness of the EVOH resin layer is usually 5 μm or more, preferably 10 μm or more, more preferably 12 μm or more, and usually 100 μm or less, preferably 50 μm or less.

[First and second adhesive layers]
The first adhesive layer is usually a layer that adheres to the crosslinked rubber member (I). The second adhesive layer is usually a layer that adheres to the hydrosilyl crosslinked rubber member (II). These adhesive layers are layers that bond the EVOH resin layer and the member (I) or the member (II) to form a composite.

The first adhesive layer and the second adhesive layer may be the same or different.
The first and second adhesive layers are layers each independently composed of, for example, at least an adhesive resin. Adhesive resins include, for example, Admer manufactured by Mitsui Chemicals, CAX-3036 manufactured by DuPont, Adtex manufactured by Nippon Polyolefin Co., Ltd., and Plexar manufactured by USI.

As the adhesive resin, a modified polyolefin resin is preferable, an acid-modified polyolefin resin is more preferable, and an acid-modified polyolefin resin obtained by graft-polymerizing an unsaturated carboxylic acid, its anhydride, ester or amide to a polyolefin resin is more preferable. Polyolefin resins include polyethylene resins and polypropylene resins. Unsaturated carboxylic acids include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.

In one embodiment, the MFR of the polyethylene-based adhesive resin at 190° C. and a load of 2160 g is preferably 1 to 50 g/10 minutes, more preferably 2 to 10 g/10 minutes.
In one embodiment, the MFR of the polypropylene-based adhesive resin at 230° C. and a load of 2160 g is preferably 1 to 50 g/10 minutes, more preferably 2 to 10 g/10 minutes.

The first adhesive layer can contain one or more adhesive resins.
The second adhesive layer can contain one or more adhesive resins.
The thicknesses of the first and second adhesive layers are each independently usually 0.1 μm or more, preferably 1 μm or more, more preferably 5 μm or more, and usually 100 μm or less, preferably 80 μm or less, more preferably 50 μm or less.

[Crosslinked rubber member (I)]
The molded composite of the present invention has a crosslinked rubber member (I). The crosslinked rubber member (I) usually contains a component that can act as a catalyst poison in the hydrosilyl crosslinking reaction (eg, elemental sulfur, specifically derived from a sulfur-based crosslinking agent, derived from an additive containing elemental sulfur). The crosslinked rubber member (I) includes not only a rubber member crosslinked using a sulfur-based crosslinking agent, but also a rubber member crosslinked using another crosslinking agent, as long as the rubber member contains a component that can be the catalyst poison, but a rubber member crosslinked using a sulfur-based crosslinking agent is preferable.
The crosslinked rubber member (I) is usually formed from a rubber composition (I) containing at least a rubber component and a crosslinking agent such as a sulfur-based crosslinking agent.

<Rubber component>
Examples of rubber components include ethylene/α-olefin/non-conjugated polyene copolymers. The crosslinked rubber member (I) preferably contains a rubber obtained by cross-linking an ethylene/α-olefin/non-conjugated polyene copolymer with a sulfur-based cross-linking agent.

The ethylene/α-olefin/non-conjugated polyene copolymer is preferably a copolymer having ethylene-derived structural units, one or two or more α-olefin-derived structural units having 3 to 20 carbon atoms, and one or two or more non-conjugated polyene-derived structural units.

Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferred, and propylene is more preferred.

Examples of non-conjugated polyenes include linear non-conjugated diene such as 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene. Ene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene , norbornadiene; and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene.

Among these, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene, and 4-ethylidene-8-methyl-1,7-nanodiene are preferred.
In the ethylene/α-olefin/non-conjugated polyene copolymer, the molar ratio (ethylene-derived structural unit/C3-C20 α-olefin-derived structural unit) is preferably 50/50 to 90/10, more preferably 65/35 to 90/10, and still more preferably 65/35 to 85/15. The above range is preferable in that a rubber composition capable of providing a crosslinked rubber member excellent in heat aging resistance, strength properties, rubber elasticity, cold resistance and workability can be obtained.

The content of structural units derived from ethylene and α-olefin in the ethylene/α-olefin/non-conjugated polyene copolymer can be determined by ¹³ C-NMR.
The iodine value of the ethylene/α-olefin/non-conjugated polyene copolymer is preferably 1 to 40 g/100 g, more preferably 1 to 30 g/100 g in terms of obtaining a rubber composition with high cross-linking efficiency and being advantageous in terms of cost.

The ethylene/α-olefin/non-conjugated polyene copolymer may be a so-called oil-extended rubber in which a softening agent such as a mineral oil-based softening agent is blended during its production. Mineral oil-based softeners include conventionally known mineral oil-based softeners such as paraffin-based process oils.

Mooney viscosity ML ₍₁₊₄₎ at 125° C. of the ethylene/α-olefin/non-conjugated polyene copolymer is preferably 5-100, more preferably 20-95, still more preferably 30-90. A copolymer having a Mooney viscosity within the above range tends to exhibit good processability and fluidity, excellent rubber properties, and good post-treatment quality (ribbon handleability). The Mooney viscosity is measured according to ASTM D 1646 using a Mooney viscometer (Model SMV202 manufactured by Shimadzu Corporation).

The ethylene/α-olefin/non-conjugated polyene copolymer is usually obtained by copolymerizing monomers containing ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. The copolymer may be prepared by any production method, and examples include copolymers produced using a metallocene catalyst or a vanadium catalyst.

The rubber composition (I) may contain one or more ethylene/α-olefin/non-conjugated polyene copolymers.
Examples of rubber components include ethylene/α-olefin copolymers such as ethylene/propylene copolymer (EPR), silicone rubber, natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, and chloroprene rubber. These rubber components can also be used together with an ethylene/α-olefin/non-conjugated polyene copolymer.

<Crosslinking agent>
Examples of the cross-linking agent include cross-linking agents generally used for cross-linking rubber components, such as sulfur-based cross-linking agents, organic peroxides, phenol resins, amino resins, quinones or derivatives thereof, amine compounds, azo compounds, epoxy compounds, and isocyanate compounds. Among these, sulfur-based cross-linking agents are preferred.

Examples of sulfur-based cross-linking agents include elemental sulfur and sulfur compounds.
The form of elemental sulfur is not particularly limited, and examples thereof include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur. Examples of sulfur compounds include inorganic sulfur compounds such as sulfur chloride and sulfur dichloride, and organic sulfur compounds such as morpholine disulfide and alkylphenol disulfide.

Rubber composition (I) may contain one or more cross-linking agents.
The cross-linking agent is usually 0.1 to 10 parts by mass, preferably 0.5 to 7 parts by mass, more preferably 0.7 to 5 parts by mass with respect to 100 parts by mass of the rubber component such as the ethylene/α-olefin/non-conjugated polyene copolymer.

<Vulcanization accelerator>
When using a sulfur-based cross-linking agent as a cross-linking agent, it is preferable to use a vulcanization accelerator together.
Examples of vulcanization accelerators include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N'-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole (e.g., Suncellar M (trade name; manufactured by Sanshin Kagaku Kogyo Co., Ltd.)), 2-(4-morpholinodithio)benzothiazole (e.g., Noxceler MDB-P (trade name; Ouchi Shinko Kagaku) Kogyo Co., Ltd.)), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide (e.g. Suncellar DM (trade name; Sanshin Chemical Industry Co., Ltd.)); guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine and diorthotrilguanidine; and butyraldehyde/aniline condensates; imidazoline vulcanization accelerators such as 2-mercaptoimidazoline; Thiuram-based vulcanization accelerators such as tetrabutyl thiuram disulfide (e.g. Sansera TBT (trade name; Sanshin Kagaku Kogyo Co., Ltd.)) and dipentamethylenethiuram tetrasulfide (e.g. Sansera TRA (trade name; Sanshin Kagaku Kogyo Co., Ltd.)); Dithioate-based vulcanization accelerators such as EZ, Suncellar BZ (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.) and tellurium diethyldithiocarbamate (e.g., Suncellar TE-G (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)); , N'-dibutylthiourea; and xanthate-based vulcanization accelerators such as zinc dibutylxathate.

Rubber composition (I) may contain one or more vulcanization accelerators.
In one embodiment, the vulcanization accelerator is usually 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the rubber component such as the ethylene/α-olefin/non-conjugated polyene copolymer.

<Vulcanization aid>
When using a sulfur-based compound as a cross-linking agent, a vulcanization aid can be used in combination.
Examples of the vulcanizing aid include zinc oxide (e.g., ZnO #1, zinc oxide type 2, manufactured by Hakusui Tech Co., Ltd.), zinc oxide (e.g., "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)), and magnesium oxide.

Rubber composition (I) may contain one or more vulcanizing aids.
In one embodiment, the vulcanization aid is usually used in a range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component such as the ethylene/α-olefin/non-conjugated polyene copolymer.

<Additive>
The rubber composition (I) can contain conventionally known additives such as ordinary additives used in rubber, such as reinforcing agents, softening agents, processing aids, activators, anti-aging agents, moisture absorbers, foaming agents, foaming aids, defoaming agents, heat stabilizers, weather stabilizers, antistatic agents, and colorants, as long as they do not impair the purpose of the present invention. Each of these can be used alone or in combination of two or more.

≪Reinforcing agent≫
The reinforcing agent is a known rubber reinforcing agent compounded in the rubber composition, and examples thereof include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate such as light calcium carbonate, heavy calcium carbonate, activated calcium carbonate, fine powder talc, and differential silicic acid.

In one embodiment, the reinforcing agent is usually used in a range of 70 to 200 parts by mass with respect to 100 parts by mass of the rubber component such as the ethylene/α-olefin/non-conjugated polyene copolymer.

≪Softener≫
The softening agent is a known softening agent blended in the rubber composition, for example, petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petroleum jelly; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil; Synthetic polymer substances such as indene resin; Ester-based softeners such as dioctyl phthalate and dioctyl adipate; Others include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub (factice). Among these, petroleum-based softeners are preferred, and process oils are more preferred.

In one embodiment, the softener is usually used in an amount of 40 to 100 parts by mass, preferably 40 to 90 parts by mass, per 100 parts by mass of the rubber component such as the ethylene/α-olefin/non-conjugated polyene copolymer.

≪Processing aid≫
As the processing aid, a wide variety of processing aids that are generally blended with rubber can be used. Examples of processing aids include fatty acids such as ricinoleic acid, stearic acid, palmitic acid, and lauric acid, and fatty acid derivatives. Examples of fatty acid derivatives include fatty acid salts such as barium stearate, zinc stearate, and calcium stearate, fatty acid esters such as ricinoleic acid esters, stearic acid esters, palmitic acid esters, and lauric acid esters, and N-substituted fatty acid amides. Among these, stearic acid is preferred.

In one embodiment, the processing aid is usually used in an amount of 10 parts by mass or less, preferably 8 parts by mass or less per 100 parts by mass of the rubber component such as the ethylene/α-olefin/non-conjugated polyene copolymer.

≪Activator≫
Active agents include, for example, amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; active agents such as diethylene glycol, polyethylene glycol, lecithin, triarylutemellilate, zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids; zinc peroxide preparations; ktadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

In one embodiment, the activator is usually used in an amount of 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the rubber component such as the ethylene/α-olefin/non-conjugated polyene copolymer.

<Production of rubber composition (I) and crosslinked rubber member (I)>
The rubber composition (I) can be prepared, for example, by kneading each component described above at a desired temperature using a kneader such as a mixer, kneader, or roll. Specifically, using a conventionally known kneader such as a mixer or a kneader, the rubber component and, if necessary, other components are kneaded at a predetermined temperature and time, for example, 80 to 200° C. for 1 to 30 minutes, then a crosslinking agent and, if necessary, other components are added to the resulting kneaded product, kneaded at a predetermined temperature and time, for example, a roll temperature of 30 to 80° C. for 1 to 30 minutes using a roll, and then separated to obtain the rubber composition (I). can be obtained.

The crosslinked rubber member (I) is obtained, for example, by molding the rubber composition (I) into a desired shape and subjecting it to crosslinking treatment. For the molding, for example, a molding machine such as an extrusion molding machine, a press molding machine, an injection molding machine, a transfer molding machine, or a calendar roll can be used. The crosslinked rubber member (I) is preferably an extruded member. For the cross-linking treatment, for example, a cross-linking apparatus such as a hot air cross-linking tank or a microwave cross-linking tank can be used. The heating temperature during crosslinking is usually 100 to 300°C, preferably 150 to 250°C. The heating time is usually 5 to 20 minutes, preferably 5 to 15 minutes.

[Hydrosilyl crosslinked rubber member (II)]
The molded composite of the present invention has a hydrosilyl crosslinked rubber member (II).
The hydrosilyl-crosslinked rubber member (II) is usually formed from a rubber composition (II) containing a hydrosilyl-crosslinkable rubber component, a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule, and a platinum catalyst for hydrosilyl crosslinking.

The hydrosilyl crosslinked rubber member (II) is excellent in rubber elasticity, mechanical strength, heat aging resistance and the like. For example, the hydrosilyl crosslinked rubber member (II) has a small compression set and is superior to members made of a thermoplastic elastomer.

<Rubber component>
Examples of hydrosilyl-crosslinkable rubber components include ethylene/α-olefin/non-conjugated polyene copolymer (S) (hereinafter also referred to as “copolymer (S)”). The hydrosilyl cross-linked rubber member (II) preferably contains a rubber obtained by cross-linking the copolymer (S) with a hydrosilyl-based cross-linking agent.

The copolymer (S) is preferably a copolymer having a structural unit derived from ethylene (A), a structural unit derived from one or more α-olefins having 3 to 20 carbon atoms (B), and a structural unit derived from one or more non-conjugated polyenes (C). The non-conjugated polyene (C) contains a total of two or more at least one partial structure selected from formulas (I) and (II) in the molecule.

Examples of α-olefins (B) having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferred, and propylene is more preferred.

Non-conjugated polyenes (C) include, for example, 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene and dicyclopentadiene. Among these, the non-conjugated polyene (C) preferably contains VNB, and the non-conjugated polyene (C) is more preferably VNB, because it is easily available, has good hydrosilyl cross-linking, and tends to improve the heat resistance of the composition.

The copolymer (S) can further have structural units derived from the non-conjugated polyene (D) containing only one partial structure selected from formulas (I) and (II) in the molecule.
Non-conjugated polyenes (D) include, for example, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 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-norbornene, 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-hexenyl)-2-norbornene, 5- (5-ethyl-5-hexenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene. Among these, ENB is preferable because it is easily available, the speed of crosslinking during hydrosilyl crosslinking is easily controlled, and good mechanical properties are easily obtained.

The copolymer (S) may contain structural units derived from at least one non-conjugated polyene (D), and may contain structural units derived from two or more non-conjugated polyenes (D).
In the copolymer (S), the molar ratio (constituent unit derived from ethylene (A)/constituent unit derived from α-olefin having 3 to 20 carbon atoms (B)) is preferably 40/60 to 99.9/0.1, more preferably 50/50 to 90/10, still more preferably 55/45 to 85/15. Such a copolymer is preferable because the resulting crosslinked rubber member exhibits excellent rubber elasticity and is excellent in mechanical strength and flexibility.

In 100% by mass of the copolymer (S) (that is, in the total 100% by mass of the content of all structural units), the content of the structural unit derived from the non-conjugated polyene (C) is usually 0.07 to 10% by mass, preferably 0.1 to 8% by mass, more preferably 0.5 to 5% by mass. Such a copolymer is preferable because the resulting crosslinked rubber member has sufficient hardness and excellent mechanical properties, and is preferable because it exhibits a high crosslinking rate when hydrosilyl crosslinked.

The content of structural units derived from the non-conjugated polyene (D) in 100% by mass of the copolymer (S) is usually 0 to 20% by mass, preferably 0 to 8% by mass.
The content of structural units derived from ethylene (A), α-olefin (B), non-conjugated polyene (C), and non-conjugated polyene (D) in copolymer (S) can be determined by ¹³ C-NMR.

The intrinsic viscosity [η] of the copolymer (S) measured in decalin at 135° C. is preferably 0.1 to 5.0 dL/g, more preferably 0.5 to 5.0 dL/g, still more preferably 0.9 to 4.0 dL/g.

The copolymer (S) is usually obtained by copolymerizing monomers containing ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. The copolymer may be prepared by any production method, and examples include copolymers produced using a metallocene catalyst or a vanadium catalyst.

The rubber composition (II) can contain one or more copolymers (S).
The rubber composition (II) can also contain rubber components such as silicone rubber, ethylene/propylene random copolymer rubber (EPR), natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, and chloroprene rubber.

<Hydrosilyl group-containing compound>
The hydrosilyl group-containing compound acts as a hydrosilyl cross-linking agent that reacts with the copolymer (S). The hydrosilyl group-containing compound can be used in any structure, such as linear, cyclic, branched structures or three-dimensional network structure resinous substances, which are conventionally produced and commercially available.

The hydrosilyl group-containing compound contains at least two hydrosilyl groups in one molecule. Examples of the hydrosilyl group-containing compound include compounds represented by the following formulas.
_RbHcSiO (4 _{- bc)/2}

In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, excluding aliphatic unsaturated bonds. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, nonyl group and decyl group; phenyl group; and halogenated alkyl groups such as trifluoropropyl group. Among these, a methyl group, an ethyl group, a propyl group, a phenyl group and a trifluoropropyl group are preferred, and a methyl group and a phenyl group are more preferred.

In the above formula, b is 1≤b<3, preferably 1≤b<2.2, particularly preferably 1.5≤b≤2, c is 0.6≤c≤3, preferably 0.6≤c<2, and b+c is b+c≤3, preferably b+c≤2.7.

Hydrosillyl group -containing compounds, for example, are preferably 2 to 1000 pieces, 2 to 300 pieces, more preferably 4 to 200, more preferably 4 to 200 pieces, for example, 1,1,3,3 -3 -3 -3 -Tetramethyloxyloxan, 1,3,5, 5, 3 -3 -3 -3 -3 -3 -Tetramethylxyloxan, 1,3,5, 5, specifically. 7 -Tetramethyltetetetetra cycliciloxane, 1,3, 5, 7,8 -pentonamethylpa sycloxloxan, etc., molecular chain both ends trimethyl syroxy, trimethyl syroxy, methyl hydrojen polyquisloxane, molecular chain bilateral tip, trimethyl syroxy base chain. Saint -methyl hydrojenchiloxan coalition, molecular chain both ends of bilateral bilateral siranol, methyl hydrogen polyciroxane, molecular chain chain chain chain chain bilateral siranol base chain chain dimethyl syroxan methyl hydrojenchiloxan co -integration, molecular chain dip -end dimethyl hydrojensiloxyloxyroxy Shiki Finding Chain Dimethyl Polyshieloxan, Molecular Chain Both Dynasty Dimethyl Hydro Gensiloxiloxy Balded Methyl Hydrojen Polishiroxan, Molecular Chain Dimethyl Hydrojenciroxiloxyroxy Base Interfeion Zimethyl Siloxan Methyl Hydrojen Roxan Integration, R₂(H)SiO_1/2units and SiO_4/2and optionally R₃SiO_1/2unit, R₂SiO_2/2unit, R(H)SiO_2/2unit, (H)SiO_3/2or RSiO_3/2Examples include silicone resins that may contain units.

Examples of the trimethylsiloxy-group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain include compounds represented by the following formula, and compounds in which some or all of the methyl groups in the following formula are substituted with ethyl, propyl, phenyl, trifluoropropyl, or the like.
(CH ₃ ) ₃ SiO--(--SiH(CH ₃ )--O--) _d --Si(CH ₃ ) ₃
d in the formula is an integer of 2 or more.

Examples of the dimethylsiloxane/methylhydrogensiloxane copolymer having trimethylsiloxy groups blocked at both ends of the molecular chain include compounds represented by the following formula, and compounds in which some or all of the methyl groups in the following formula are substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.
(CH ₃ ) ₃ SiO—(—Si(CH ₃ ) ₂ —O—) _e —(—SiH(CH ₃ )—O—) _f —Si(CH ₃ ) ₃
e in the formula is an integer of 1 or more, and f is an integer of 2 or more.

Examples of the dimethylpolysiloxane blocked with dimethylhydrogensiloxy groups at both ends of the molecular chain include compounds represented by the following formula, and compounds in which some or all of the methyl groups in the following formula are substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.
HSi( _CH3 ) _2O -(-Si( _CH3 ) _2- O-) _e -Si( _CH3 ) _2H
e in the formula is an integer of 1 or more.

Examples of the methylhydrogenpolysiloxane blocked with dimethylhydrogensiloxy groups at both ends of the molecular chain include compounds represented by the following formulas, and compounds in which some or all of the methyl groups in the following formulas are substituted with ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups, and the like.
HSi( _CH3 ) _2O -(-SiH( _CH3 )-O-) _e -Si( _CH3 ) _2H
e in the formula is an integer of 1 or more.

Examples of the dimethylsiloxane/methylhydrogensiloxane copolymer having dimethylhydrogensiloxy groups blocked at both ends of the molecular chain include compounds represented by the following formulas, and compounds in which some or all of the methyl groups in the following formulas are substituted with ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups, or the like.
HSi( _CH3 ) _2O -(-Si( _CH3 ) _2- O-) _e -(-SiH( _CH3 )-O-) _h -Si( _CH3 ) _2H
e and h in the formula are each an integer of 1 or more.

The above compounds can be produced by a known method, for example, by equilibrating octamethylcyclotetrasiloxane and/or tetramethylcyclotetrasiloxane with a compound containing a triorganosilyl group or diorganohydrogensiloxy group, such as hexamethyldisiloxane or 1,3-dihydro-1,1,3,3-tetramethyldisiloxane, which can serve as a terminal group, in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, or methanesulfonic acid at a temperature of about -10°C to +40°C. can be obtained easily.

The rubber composition (II) may contain one or more of the above hydrosilyl group-containing compounds.
The content of the hydrosilyl group-containing compound in the rubber composition (II) is usually 0.1 to 100 parts by mass, preferably 0.1 to 75 parts by mass, more preferably 0.1 to 50 parts by mass, per 100 parts by mass of the hydrosilyl crosslinkable rubber component such as the copolymer (S).

<Platinum catalyst>
The platinum-based catalyst for hydrosilyl cross-linking is an addition reaction catalyst, and can be used without particular limitation as long as it promotes the addition reaction (alkene hydrosilylation reaction) between the alkenyl group of the rubber component and the hydrosilyl group of the hydrosilyl group-containing compound.

Illustrative platinum-based catalysts can be those known in common use in addition-cure cures, such as finely divided metallic platinum catalysts as described in U.S. Pat. No. 2,970,150, chloroplatinic acid catalysts as described in U.S. Pat. 46, complex compounds of chloroplatinic acid and olefins, and complex compounds of platinum and vinyl siloxane described in US Pat. Nos. 3,775,452 and 3,814,780.

More specific examples include simple platinum (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, and platinum carriers carried on carriers such as alumina and silica.

The rubber composition (II) may contain one or more of the above platinum-based catalysts.
The content of the platinum-based catalyst in the rubber composition (II) is usually 0.1 to 100000 ppm by weight, preferably 0.1 to 10000 ppm by weight, more preferably 1 to 5000 ppm by weight. When the platinum-based catalyst is used at a ratio within the above range, a composition can be obtained which has an appropriate crosslink density and can form a molded article having excellent strength properties and elongation properties.

<Reaction inhibitor>
The rubber composition (II) preferably further contains a reaction inhibitor.
The reaction inhibitor is a compound having a function of inhibiting the cross-linking reaction between the alkenyl group of the rubber component and the hydrosilyl group of the hydrosilyl group-containing compound (hydrosilylation addition reaction to alkene or the like). In the case of a composition using the rubber component and the hydrosilyl group-containing compound, the hydrosilyl cross-linking reaction already starts from the initial stage of kneading where temperature is applied, so processability may gradually decrease during kneading. It is preferable to add a reaction inhibitor to the composition because the processability of the composition during kneading and molding is stabilized.

Examples of reaction inhibitors include benzotriazole; acetylene alcohols such as 1-hexyne-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 1-ethynylcyclohexanol, and 3,5-dimethyl-1-hexyne-3-ol; acrylonitrile; Amide compounds such as amide, N,N-diallylbenzamide, N,N,N',N'-tetraallyl-o-phthalic diamide, N,N,N',N'-tetraallyl-m-phthalic diamide, N,N,N',N'-tetraallyl-p-phthalic diamide; Others, sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinylcyclotetrasiloxane, hydroperoxide, etc. of organic peroxides. Among these, 3,5-dimethyl-1-hexyn-3-ol is preferred.

Rubber composition (II) may contain one or more reaction inhibitors.
The content of the reaction inhibitor in the rubber composition (II) is usually 0.05 to 5 parts by mass, preferably 0.07 to 5 parts by mass, more preferably 0.07 to 4.5 parts by mass, per 100 parts by mass of the hydrosilyl crosslinkable rubber component such as the copolymer (S). Such an aspect is preferable in terms of obtaining an appropriate cross-linking speed.

<Additive>
The rubber composition (II) can contain conventionally known additives such as usual additives used in rubber, such as reinforcing agents, softening agents, processing aids, activators, antioxidants, moisture absorbers, foaming agents, foaming aids, defoaming agents, heat stabilizers, weather stabilizers, antistatic agents, and colorants, as long as they do not impair the purpose of the present invention. Each of these can be used alone or in combination of two or more.

≪Reinforcing agent≫
The reinforcing agent is a known rubber reinforcing agent blended in the rubber composition, and examples thereof include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate such as light calcium carbonate, heavy calcium carbonate, activated calcium carbonate, fine powder talc, and differential silicic acid.
In one embodiment, the reinforcing agent is generally used in the range of 70 to 200 parts by mass with respect to 100 parts by mass of the hydrosilyl-crosslinkable rubber component such as copolymer (S).

≪Softener≫
The softening agent is a known softening agent blended in the rubber composition, for example, petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petroleum jelly; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil; Synthetic polymer substances such as indene resin; Ester-based softeners such as dioctyl phthalate and dioctyl adipate; Others include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub (factice). Among these, petroleum-based softeners are preferred, and process oils are more preferred.

In one embodiment, the softener is usually used in an amount of 40 to 100 parts by weight, preferably 40 to 90 parts by weight, per 100 parts by weight of the hydrosilyl-crosslinkable rubber component such as copolymer (S).

<Production of rubber composition (II)>
The rubber composition (II) can be prepared, for example, by kneading the above components at a desired temperature using a kneader such as a mixer, kneader, or roll. Specifically, using a conventionally known kneader such as a mixer or a kneader, the hydrosilyl-crosslinkable rubber component and, if necessary, other components are kneaded at a predetermined temperature and time, for example, 80 to 170°C for 1 to 30 minutes, and then a hydrosilyl group-containing compound, a platinum-based catalyst, and optionally other components are added to the resulting kneaded product, and rolls are used at a predetermined temperature and time, for example, a roll temperature of 40 to 130°C, preferably 40 to 80°C. After kneading for 5 to 30 minutes, the rubber composition (II) can be obtained by dispensing.

The resulting rubber composition (II) can be preformed into a desired shape using a molding machine such as an extruder, a press molding machine, an injection molding machine, a transfer molding machine, or a calendar roll to form the member (IIa).

[Manufacturing method of composite compact]
The composite molded article of the present invention can be produced, for example, by the following production method.
That is, the method for producing a composite molded article of the present invention is
Step (1) of obtaining a composite (I)/(IIa) by bonding the crosslinked rubber member (I) and the member (IIa) made of the rubber composition (II) described above with the adhesive member having, in this order, a first adhesive layer, a layer containing an ethylene-vinyl alcohol copolymer resin, and a second adhesive layer;
and a step (2) of cross-linking the composite (I)/(IIa).
The step (1) may be a step (1′) of forming a member (IIa) made of the rubber composition (II) described above on the adhesive member of the crosslinked rubber member (I) on which the adhesive member is arranged to obtain the composite (I)/(IIa).

<Steps (1), (1′)>
In the step (1), the crosslinked rubber member (I) prepared in advance and the member (IIa) composed of the rubber composition (II) are adhered via the adhesive member to obtain the composite (I)/(IIa). For example, a portion of the crosslinked rubber member (I) and a portion of the member (IIa) are adhered via the adhesive member.

In the step (1'), for example, a member (IIa) made of the rubber composition (II) is formed on the adhesive member of the crosslinked rubber member (I) in which the adhesive member is arranged at a predetermined portion. In one embodiment, the adhesive member portion of the crosslinked rubber member (I) in which the adhesive member is arranged at a predetermined portion is set in a mold, and then the melt of the rubber composition (II) is injected into the mold onto the adhesive member and solidified, thereby bonding the crosslinked rubber member (I) and the member (IIa) via the adhesive member. Such insert molding can be used in the present invention.

<Step (2)>
In step (2), the complexes (I)/(IIa) obtained in steps (1) and (1′) are subjected to cross-linking treatment (specifically, hydrosilyl cross-linking treatment). In the present invention, hydrosilyl cross-linking can proceed well. The steps (1') and (2) may be performed simultaneously, that is, the molding of the member (IIa) and its cross-linking may be performed simultaneously.

For the cross-linking treatment, for example, the heating temperature is usually 80 to 250° C., preferably 100 to 200° C., and the heating time is usually 0.1 to 20 minutes, preferably 0.1 to 5 minutes. Hydrosilyl cross-linking can often proceed in a short time compared to, for example, sulfur cross-linking, so that the time required to produce a composite molded article can be shortened.
As described above, a molded composite having excellent adhesive strength between the crosslinked rubber member (I) and the hydrosilyl crosslinked rubber member (II) can be obtained.

[Uses of composite moldings]
INDUSTRIAL APPLICABILITY The composite molded article of the present invention is preferably used as an automobile interior and exterior material, and more preferably used as a weatherstrip material. In one embodiment, the weatherstrip material is a molded body in which a linear member and a corner member are joined, the linear member is made of the crosslinked rubber member (I), the corner member is made of the hydrosilyl crosslinked rubber member (II), and the crosslinked rubber member (I) and the hydrosilyl crosslinked rubber member (II) are joined by the adhesive member.

The weatherstrip material, in one embodiment, is composed of two linear members and corner members formed when the linear members are connected from different directions. The linear member has a linear shape in the longitudinal direction.

A weatherstrip material can be obtained, for example, as follows.
Two members 1 and 2 are prepared in which the above-described adhesive member is attached to the ends of the crosslinked rubber member (I). A mold for injection molding is preheated to a predetermined temperature. The ends of the members 1 and 2 where the bonding member is arranged are inserted into the mold. Next, the melted rubber composition (II) is injected into the cavity of the mold, and the member (IIa) composed of the rubber composition (II) is formed on the adhesive member and joined, followed by hydrosilyl cross-linking treatment. Thus, a weatherstrip material in which the members 1 and 2 are joined by the corner member 3 can be obtained.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In the following description, "parts" means "parts by mass" unless otherwise specified.
[Production Example 1]
As the first step, 84 parts of Mitsui EPT 3062EM (manufactured by Mitsui Chemicals, Inc.; oil extension amount: 20 phr) and 30 parts of Mitsui EPT 3091 (manufactured by Mitsui Chemicals, Inc.) were masticated for 30 seconds using a BB-4 type Banbury mixer (manufactured by Kobe Steel, Ltd.), and then 95 parts of FEF carbon black (Asahi #60UG, manufactured by Asahi Carbon Co., Ltd.), heavy calcium carbonate (Whiten SB, white Calcium stone Co., Ltd.]), zinc oxide (ZnO#1, zinc oxide type 2, Hakusui Tech Co., Ltd.) 3 parts, stearic acid 1 part, polyethylene glycol (PEG4000, Sanyo Chemical Industries Co., Ltd.) 1 part, paraffin-based process oil (Diana Process Oil PA-90, Idemitsu Kosan Co., Ltd.) 70 parts were added and kneaded at 140 ° C. for 2 minutes. After that, the ram was raised and cleaned, kneaded for 1 minute, discharged at about 150° C., and compound A1 was obtained.

Next, as the second step, compound A1 is wound around a 14-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 60 ° C., rear roll surface temperature 60 ° C., front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm). Sanshin Kagaku Kogyo Co., Ltd.) 1.0 parts, zinc dibutyldithiocarbamate (Sansera BZ, Sanshin Kagaku Kogyo Co., Ltd.) 2.0 parts, and tellurium diethyldithiocarbamate (Sansera TE-G, Sanshin Kagaku Kogyo Co., Ltd.) 0.02 parts were added and kneaded for 10 minutes to obtain Compound B1.
Compound B1 was then vulcanized by heating at 170° C. for 10 minutes using a 150-ton press to obtain a sulfur vulcanized sheet of 100 mm×50 mm×1 mmt.

[Production Example 2]
An ethylene/propylene/VNB copolymer (S-1) was produced as follows.
In a polymerization reactor having a volume of 300 liters, 58.3 L/hr of a dehydrated and purified hexane solvent was fed from line 1, 4.5 mmol/hr of triisobutylaluminum (TiBA), 0.150 mmol/hr of (C ₆ H ₅ ) ₃ CB(C ₆ F ₅ ) ₄ from line 2, and di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride. Lid was continuously supplied at 0.030 mmol/hr. At the same time, 6.6 kg/hr of ethylene, 9.3 kg/hr of propylene, 18 liters/hr of hydrogen, and 340 g/hr of VNB were continuously fed into the polymerization reactor from separate lines, respectively, and copolymerization was carried out under the conditions of a polymerization temperature of 87° C., a total pressure of 1.6 MPaG, and a residence time of 1.0 hour.

The ethylene/propylene/VNB copolymer solution produced in the polymerization reactor was continuously discharged at a flow rate of 88.0 L/hr, heated to 170°C (pressure increased to 4.1 MPaG), and supplied to a phase separator. At this time, ethanol as a polymerization inhibitor was continuously introduced into the discharge line in an amount of 0.1 mol times the amount of TiBA in the liquid component extracted from the polymerization reactor.

In the phase separator, the ethylene-propylene-VNB copolymer solution was separated into a rich phase (lower phase) containing most of the ethylene-propylene-VNB copolymer and a dilute phase (upper phase) containing a small amount of polymer.

The separated dense phase was led to a heat exchanger at 85.4 liters/hr and then to a hopper where the solvent was evaporated to obtain an ethylene/propylene/VNB copolymer (S-1) in an amount of 7.8 kg/hr.

The obtained ethylene/propylene/VNB copolymer (S-1) had a molar ratio (ethylene units/propylene units) of 62/38, a VNB unit content of 0.9% by mass, and an intrinsic viscosity [η] measured in decalin at 135°C of 2.4 dL/g.

As the first step, 115 parts of the copolymer (S-1) was masticated for 30 seconds using a BB-4 type Banbury mixer (manufactured by Kobe Steel, Ltd.), then carbon black (Asahi #50G, manufactured by Asahi Carbon Co., Ltd.) 102 parts, heavy calcium carbonate (Whiten SB, manufactured by Shiraishi Calcium Co., Ltd.) 60 parts, paraffin-based process oil (Diana Process Oil PW-430, manufactured by Idemitsu Kosan Co., Ltd.) 77. parts were added and kneaded at 140° C. for 2 minutes. After that, the ram was raised and cleaned, kneaded for 1 minute, discharged at about 150° C., and compound A2 was obtained.

Next, as the second step, compound A2 is wound around an 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and a hydrosilyl group-containing compound (Shin-Etsu Chemical Co., Ltd.: X-93-1346, (CH₃)₃SiO-(SiH(CH₃)-O-)₆-Si(CH₃)₂-O-Si(C₆H._Five)₂-O-Si(CH₃)₃) 4 parts, platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd.: X-93-1410, chloroplatinic acid + [CH₂=CH(Me)SiO]_Fourcomplex) and 0.7 part of a reaction inhibitor (manufactured by Shin-Etsu Chemical Co., Ltd.: X-93-1036, 3,5-dimethyl-1-hexyn-3-ol) were added and kneaded for 10 minutes to obtain compound B2.

[Example 1]
The sulfur-vulcanized sheet obtained in Production Example 1 was placed on one side of a 100 mm×100 mm×2 mmt mold. Next, on the sulfur-vulcanized sheet, a polyethylene-based Admer film (NF518, manufactured by Mitsui Chemicals, Inc.), an EVOH film (EVAL F101B, manufactured by Kuraray Co., Ltd.), and a polyethylene-based Admer film (NF518), each having the same size as the sulfur-vulcanized sheet, were laminated in this order. Both films are 50 μm thick. The compound B2 (HS compound) obtained in Production Example 2 was placed on the polyethylene Admer film of the uppermost layer, and a metal plate was placed thereon, followed by press molding (180° C. for 5 minutes, 50 t electric heating semi-automatic press (manufactured by Kotaki Co., Ltd./model: KMF100-1E)) to crosslink the HS compound.

In this way, a 2 mm-thick composite molded body consisting of the sulfur vulcanized sheet/adhesive member (NF518/EVOH film/NF518)/hydrosilyl (HS) crosslinked sheet was obtained.
A peel test was performed on the obtained composite molded body. At room temperature, the sulfur-vulcanized sheet was peeled off from the interface with a finger, and it was observed whether interface peeling or substrate failure occurred. Further, the release surface of the HS crosslinked sheet was rubbed with a finger to observe whether it was crosslinked or not crosslinked due to poisoning.

As a result of the above peeling test, the rubber phase of the sulfur-vulcanized sheet or the HS-crosslinked sheet or the resin layer was destroyed (substrate failure), and the sulfur-vulcanized sheet and the HS-crosslinked sheet were well bonded by the adhesive member. In addition, HS cross-linking was progressing satisfactorily.

[Example 2]
The procedure of Example 1 was repeated except that a polypropylene Admer film (QF551, manufactured by Mitsui Chemicals, Inc.) was used instead of the polyethylene Admer film (NF518, manufactured by Mitsui Chemicals, Inc.).

As a result of the above peeling test, the rubber phase of the sulfur-vulcanized sheet or the HS-crosslinked sheet or the resin layer was destroyed (substrate failure), and the sulfur-vulcanized sheet and the HS-crosslinked sheet were well bonded by the adhesive member. In addition, HS cross-linking was progressing satisfactorily.

[Comparative Example 1]
After washing the sulfur-vulcanized sheet obtained in Production Example 1 with ethanol, it was placed on one side of a 100 mm×100 mm×2 mmt mold. Next, the compound B2 (HS compound) obtained in Production Example 2 was placed on the sulfur-vulcanized sheet, and crosslinked in the same manner as in Example 1 at 180° C. for 5 minutes.
The above test results showed that HS cross-linking did not progress due to poisoning in the vicinity of the interface, and interfacial peeling occurred.

[Comparative Example 2]
The sulfur-vulcanized sheet obtained in Production Example 1 was placed on one side of a 100 mm×100 mm×2 mmt mold. Next, a polyethylene film of the same size (DND2450, manufactured by Nihon Unicar Co., Ltd.) was overlaid on the sulfur-vulcanized sheet. Compound B2 (HS compound) obtained in Production Example 2 was placed on the polyethylene film, and crosslinked in the same manner as in Example 1 at 180° C. for 5 minutes.

The above test results showed that HS cross-linking did not progress due to poisoning in the vicinity of the interface, and interfacial peeling occurred. It is considered that the barrier property of the polyethylene film was insufficient, and the HS cross-linking was poisoned by the sulfur contained in the sulfur-vulcanized sheet.

[Comparative Example 3]
The sulfur-vulcanized sheet obtained in Production Example 1 was placed on one side of a 100 mm×100 mm×2 mmt mold. Next, a polyethylene Admer film (NF518) of the same size was overlaid on the sulfur-vulcanized sheet. Compound B2 (HS compound) obtained in Production Example 2 was placed on the polyethylene Admer film, and crosslinked in the same manner as in Example 1 at 180° C. for 5 minutes.
The above test results showed that HS cross-linking did not progress due to poisoning in the vicinity of the interface, and interfacial peeling occurred.

[Comparative Example 4]
The sulfur-vulcanized sheet obtained in Production Example 1 was placed on one side of a 100 mm×100 mm×2 mmt mold. Next, an EVOH film of the same size (EVAL F101B, manufactured by Kuraray Co., Ltd.) was superimposed on the sulfur vulcanized sheet. Compound B2 (HS compound) obtained in Production Example 2 was placed on the EVOH film, and crosslinked in the same manner as in Example 1 at 180° C. for 5 minutes.

The above test results show that cross-linking was achieved without poisoning of the HS cross-linking at the interface, but interfacial delamination occurred in both the EVOH film and the sulfur-vulcanized sheet, and the EVOH film and the HS cross-linked sheet, due to insufficient adhesive strength.

Claims (6)

a crosslinked rubber member (I);
A composite molded body having a hydrosilyl crosslinked rubber member (II),
The member (I) and the member (II) are joined by an adhesive member having a first adhesive layer, a layer containing an ethylene-vinyl alcohol copolymer resin, and a second adhesive layer in this order,
The cross-linked rubber contained in the member (I) is a rubber obtained by cross-linking an ethylene/α-olefin/non-conjugated polyene copolymer with a sulfur-based cross-linking agent,
The crosslinked rubber contained in the member (II) is a rubber obtained by crosslinking an ethylene/α-olefin/non-conjugated polyene copolymer with a hydrosilyl crosslinking agent,
A molded composite article, wherein the first adhesive layer and the second adhesive layer are each independently a layer composed of at least a modified polyolefin resin. The composite molded article according to claim 1, which is an automobile interior/exterior material. 3. The composite molded article according to claim 2 , wherein the automotive interior and exterior material is a weatherstrip material. 4. The composite molded article according to claim 3 , wherein the weatherstrip material is a molded article in which a linear member and a corner member are joined, the linear member is made of the crosslinked rubber member (I), the corner member is made of the hydrosilyl crosslinked rubber member (II), and the crosslinked rubber member (I) and the hydrosilyl crosslinked rubber member (II) are joined by the adhesive member. a step (1) of obtaining a composite (I)/(IIa) by bonding a crosslinked rubber member (I) to a member (IIa) comprising a rubber composition (II) containing a hydrosilyl-crosslinkable rubber component, a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule, and a platinum catalyst for hydrosilyl crosslinking, with an adhesive member having, in this order, a first adhesive layer, a layer containing an ethylene-vinyl alcohol copolymer resin, and a second adhesive layer;
2. The method for producing a molded composite according to claim 1, further comprising a step (2) of cross-linking said composite (I)/(IIa). A step (1') of forming a member (IIa) comprising a rubber composition (II) containing a hydrosilyl-crosslinkable rubber component, a hydrosilyl group-containing compound having at least two hydrosilyl groups per molecule, and a platinum-based catalyst for hydrosilyl crosslinking, on the crosslinked rubber member (I) on which an adhesive member having a first adhesive layer, a layer containing an ethylene-vinyl alcohol copolymer resin, and a second adhesive layer in this order is arranged, to obtain a composite (I)/(IIa). and
2. The method for producing a molded composite according to claim 1, further comprising a step (2) of cross-linking said composite (I)/(IIa).