The present invention relates to a laminate having a layer made of different kinds of polymers having excellent adhesive strength and its use.
Background technology
[0002]
　Industrial hoses formed from polymers such as synthetic rubber are required to have various physical properties such as strength, flexibility, heat resistance, bending resistance, and solvent resistance, but one type of rubber can meet all the required characteristics. It is difficult to satisfy. For this reason, it is common practice to stack and use polymers (synthetic rubber) having different properties.
[0003]
　Fluorine-based polymers are excellent in heat resistance, oil resistance, chemical resistance, weather resistance, etc., and are useful in industrial materials and other fields. However, fluorinated polymers are expensive, and when used for general purposes in these fields, economic efficiency cannot be ignored, so the amount used can be dramatically increased while having excellent performance. The current situation is that we cannot expect it.
[0004]
　On the other hand, halogen-containing rubbers such as acrylic rubber (ACM) and epichlorohydrin rubber (ECO), which are copolymers of acrylic acid ester and 2-chloroethyl vinyl ether, are excellent in oil resistance, heat resistance, weather resistance and the like. Therefore, it is widely used for various sealing materials, gaskets, packings, oil hoses, air hoses, and other functional parts such as heat-resistant and oil-resistant hoses, mainly for automobiles.
[0005]
　When laminating dissimilar synthetic rubbers, polar synthetic rubbers may be directly bonded to other synthetic rubbers, but non-polar rubbers are generally bonded via an adhesive layer. ..
[0006]
　Rubber hoses around automobile engines are required to have high levels of heat resistance, aging resistance, fatigue resistance, oil resistance, and the like. Therefore, a hose in which expensive fluorine-based rubber and acrylic rubber are laminated has been used. In the bonding between the fluorine-based rubber and the non-polar rubber, it was common to bond them via an adhesive layer (see, for example, Patent Document 1). As a method of adhering without using an adhesive layer, it has been proposed to bond a layer containing fluororubber and a vulcanizing agent and a layer containing non-fluororubber and a vulcanizing agent by vulcanization bonding. (See, for example, Patent Document 2).
[0007]
　In recent years, engines have been downsized and turbo-sized to save fuel in automobiles. The turbocharged engine has a structure in which the air compressed by the compressor wheel is cooled by the charge air cooler and sent to the engine, and the compressor wheel and the charge air cooler are connected by a rubber hose. This turbocharger hose is required to have high heat resistance and aging resistance because high pressure and high temperature (about 180 ° C.) air passes through it. Fatigue resistance is also required to withstand the constant pressure vibration generated by the passage of air. Currently, acrylic rubber, silicone elastomer, etc., which have high heat resistance and aging resistance, are used in such applications.
[0008]
　Industrial hoses such as heat-resistant and oil-resistant hoses are required to have various physical properties such as strength, flexibility, heat resistance, bending resistance, and solvent resistance. Therefore, one type of rubber satisfies all required characteristics. It is difficult. Therefore, it has been attempted to use rubbers having different properties, for example, the above-mentioned fluorine-based polymer and halogen-containing rubber in a laminated manner.
[0009]
　However, since the fluorine-based polymer and the halogen-containing rubber are inferior in adhesiveness, for example, a method of blending a peroxide, a quaternary ammonium bromide, an epoxidized fatty acid ester, or the like with an acrylic elastomer (Patent Document 2). A method of blending a silica-based filler and an organic peroxide in a fluorine-based polymer, a silica-based filler, an organic peroxide and a silane coupling agent in an acrylic rubber (Patent Document 3), a fluorine-based polymer or a halogen-containing rubber. Various methods have been proposed, such as a method of blending a metal oxide with any of the above (Patent Document 4).
[0010]
　Patent Document 4 describes a composition containing an ethylene / alkyl acrylate copolymer and a cured product thereof, and the cured product, which is a vulcanized product, has improved impact fatigue resistance and impact fatigue resistance as compared with the conventional vulcanized product. It is stated that it exhibits heat resistance.
[0011]
　Patent Document 5 describes that the innermost rubber layer made of fluorine-based rubber, silicone rubber, acrylic rubber, and ethylene / acrylic rubber have excellent heat resistance and fatigue resistance and prevent the occurrence of cracks in the inner layer. A pipe fastening structure having an outer skin layer made of such material has been proposed.
[0012]
　Further, it is generally difficult to bond a non-polar rubber such as ethylene propylene diene rubber (EPDM) to another material. Since EPDM is a non-polar rubber, a method of using an adhesive layer when laminating is common (see, for example, Patent Document 6).
[0013]
　Further, Patent Document 7 proposes to add a metal oxide such as magnesium oxide to EPDM to improve the adhesiveness with a fluororubber.
Prior art literature
Patent documents
[0014]
Patent Document 1: Japanese
Patent Application
Laid-Open No. 2005-523181 Patent Document 1: Japanese Patent Application Laid-Open No. 61-189934 Patent Document 2: Japanese Patent Application Laid-Open No. 1-152060
Patent Document 3: International Publication No. 2003/039858
Patent Document 4: Special Publication No. Table 2009-500173
Patent Document 5: Japanese Patent Application Laid-Open No. 2013-221580
Patent Document 6: Japanese Patent Application Laid-Open No. 2014-162823
Patent Document 7: International Publication No. 2017/150612
Outline of the invention
Problems to be solved by the invention
[0015]
　An object of the present invention is a laminate having good adhesive strength between a non-polar polymer such as EPDM, acrylic rubber (ACM), epichlorohydrin rubber (ECO), and a polymer having excellent oil resistance such as fluorine-based rubber. To get.
Means to solve problems
[0016]
　The present invention relates to the following [1] to [19].
[0017]
　[1] The present invention relates to a laminated body including a layer (A) and a layer (B).
[0018]
　Layer (A): A layer containing one or more polymers selected from the following polymers:
　ethylene / α-olefin / non-conjugated polyene copolymer, ethylene / carboxylic acid copolymer, acrylic rubber, and epichlorohydrin rubber. Rubber
　layer (B): A layer
　acrylic rubber containing one or more polymers selected from the following polymers , and a halogen-containing polymer
　[2] The above layer (A) is the following layer (1) and layer (2). ), And the layer (B) is a laminate containing at least one layer selected from the following layers (3) and (4), and the
　layer (1). And at least one layer (A) of at least one layer selected from layer (2) and at least one layer (B) of at least one layer selected from layer (3) and layer (4). Item 6. The laminate according to item [1], wherein the polymers are in direct contact with each other or are in contact with each other via an adhesive layer.
[0019]
　Layer (A)
　Layer (1): Ethylene / α-olefin / non-conjugated polyene copolymer, the ethylene / α-olefin / non-conjugated polyene copolymer: From Group 2 element and Group 13 element with respect to 100 parts by mass A layer comprising a copolymer composition containing 0.1 to 30 parts by mass of an inorganic compound (E) containing at least one selected element and a hydroxyl group.
[0020]
　Layer (2): A layer made of an ethylene / carboxylic acid copolymer.
[0021]
　Layer (B)
　Layer (3): A layer made of acrylic rubber.
[0022]
　Layer (4): A layer made of a halogen-containing polymer.
[0023]
　[3] The layer (1) is characterized by further containing 0.2 parts by mass or more and 10 parts by mass or less of an onium salt with respect to 100 parts by mass of an ethylene / α-olefin / non-conjugated polyene copolymer. Item 2. The laminate according to item [2].
[0024]
　[4] The layer (2) contains an onium salt of 0.2 parts by mass or more per 100 parts by mass of an ethylene-carboxylic acid copolymer, and at least one element selected from Group 2 and Group 13 elements and a hydroxyl group. Item 2. The laminate according to Item [2], which comprises 7 parts by mass or more of an inorganic compound containing the above and 7 parts by mass or more per 100 parts by mass of the ethylene / carboxylic acid copolymer.
[0025]
　[5] The layer (2) is at least one selected from 0.2 parts by mass or more and 10 parts by mass or less and a group 2 element and a group 13 element per 100 parts by mass of the ethylene / carboxylic acid copolymer. Item 2. The laminate according to Item [2], wherein the inorganic compound containing the element and the hydroxyl group is contained in an amount of 7 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the ethylene / carboxylic acid copolymer.
[0026]
　[6] The laminate according to any one of items [2] to [5], wherein the layer (1) and the layer (4) are directly adhered to each other.
[0027]
　[7] A term characterized in that at least one layer (A) selected from the layer (1) and the layer (2) and the layer (3) are adhered to each other via an adhesive layer. The laminate according to any one of [2] to [5].
[0028]
　[8] The laminate according to any one of items [2] to [7], wherein the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the following requirements (I) to (III).
[0029]
　Requirement (I): The molar ratio (ethylene / α-olefin) of the structural unit derived from ethylene to the structural unit derived from α-olefin is 40/60 to 99.9 / 0.1.
[0030]
　Requirement (II): The constituent unit derived from the non-conjugated polyene is 0.07 to 10% by mass in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer.
[0031]
　Requirement (III): The ultimate viscosity [η] measured in decalin at 135 ° C. is 1.0 to 4.0 dl / g.
[0032]
　[9] The item according to any one of Items [2] to [8], wherein the ethylene / α-olefin / non-conjugated polyene copolymer has a structural unit derived from 5-vinyl-2-norbornene (VNB). Laminated body.
[0033]
　[10] The laminate according to any one of Items [2] to [9], wherein the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the following requirement (IV).
[0034]
　Requirement (IV): The B value represented by the following formula (i) is 1.20 or more.
[0035]
　　B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] ... (i)
[Here, [E], [X] and [Y] are , Respectively, show the mole fractions of ethylene, α-olefin, and non-conjugated polyene, and [EX] shows the ethylene-α-olefin diad chain fraction. ]
　[11] a layer according to the claim [1] (A) is the following layer (2-1), a layer (B) is the following layer (2-2), the layer (2-1) Item 2. The laminate according to Item [1], wherein the layer (2-2) below is directly bonded to the layer.
[0036]
　Layer (2-1): Acrylic rubber (A), and (A): Inorganic compound containing at least one element selected from Group 2 element and Group 13 element and a hydroxyl group with respect to 100 parts by mass. A layer composed of a composition containing 1 to 30 parts by mass of (B).
[0037]
　Layer (2-2): Halogen-containing polymer (C) [However, the acrylic rubber of layer (2-1) is excluded. ] A layer consisting of.
[0038]
　[12] The laminate according to item [11], wherein the halogen-containing polymer (C) is a fluorine-based polymer.
[0039]
　[13] The laminate according to item [12], wherein the halogen-containing polymer (C) of the layer (2-2) is crosslinked with a polyol-based crosslinker.
[0040]
　[14] The layer (A) according to the above item [1] is the following layer (3-1), the layer (B) is the following layer (3-2), and the layer (3-1) and the following. Item 3. The laminate according to item [1], wherein the layer (3-2) is directly bonded to the layer (3-2).
[0041]
　Layer (3-1): Epichlorohydrin rubber (A), and the (A): 100 parts by mass and an inorganic compound containing at least one element selected from Group 2 and Group 13 elements and a hydroxyl group (A). A layer composed of a composition containing 1 to 30 parts by mass of B) and 0.2 parts by mass or more and 10 parts by mass or less of an onium salt.
[0042]
　Layer (3-2): Halogen-containing polymer (C) [However, the epichlorohydrin rubber of layer (1) is excluded. ] A layer consisting of.
[0043]
　[15] The laminate according to item [14], wherein the halogen-containing polymer (C) is a fluorine-based polymer.
[0044]
　[16] The laminate according to item [15], wherein the halogen-containing polymer (C) of the layer (3-2) is crosslinked with a polyol-based crosslinker.
[0045]
　[17] A hose having at least a part of the laminate according to any one of the above items [1] to [16].
[0046]
　[18] The hose according to item [17], which is used for any of automobiles, motorbikes, industrial machines, construction machines and agricultural machines.
[0047]
　[19] The hose according to item [18], which is used for an automobile turbocharger hose.
The invention's effect
[0048]
　Since the laminate of the present invention has good adhesive strength between layers, it can be used for various purposes.
Mode for carrying out the invention
[0049]
　<< Ethylene / α-olefin / non-conjugated polyene copolymer >>
　The polymer forming the layer (A) and the layer (1) of the laminate of the present invention contains the following characteristics of ethylene / α-olefin / non-conjugated polyene. It is a polymer.
[0050]
　As the α-olefin constituting the ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention, an α-olefin having 3 to 20 carbon atoms is preferable. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and the like. Examples thereof include 1-hexadecene and 1-eikosen. Of these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferable, and propylene is particularly preferable. Such an α-olefin has a relatively low raw material cost, the obtained ethylene / α-olefin / non-conjugated polyene copolymer exhibits excellent mechanical properties, and a laminate having rubber elasticity is obtained. It is preferable because it can be used. These α-olefins may be used alone or in combination of two or more.
[0051]
　The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention contains a structural unit derived from at least one α-olefin, and contains a structural unit derived from two or more types of α-olefin. You may.
[0052]
　Examples of the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention include 5-vinyl-2-norbornene (VNB), norbornene, 1,4-hexadiene, dicyclopentadiene and 5-. Echiliden-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) Examples thereof include -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. These non-conjugated polyenes may be used alone or in combination of two or more.
[0053]
　The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention contains a structural unit derived from at least one non-conjugated polyene, and contains a structural unit derived from two or more types of non-conjugated polyene. You may.
[0054]
　As these non-conjugated polyenes, VNB is preferable from the viewpoints of high availability, good reactivity with organic peroxides during the cross-linking reaction after polymerization, and excellent heat resistance and fatigue resistance of the laminate. That is, it is preferable that the ethylene / α-olefin / non-conjugated polyene copolymer has a structural unit derived from VNB. The constituent unit derived from VNB in ​​the ethylene / α-olefin / non-conjugated polyene copolymer is 0.07 to 10% by mass in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It is preferably 0.1 to 8.0% by mass, more preferably 0.5 to 5.0% by mass, and most preferably 0.5 to 5.0% by mass.
[0055]
　Further, as a non-conjugated polyene, it is highly available, has high reactivity with sulfur and a vulcanization accelerator during a crosslinking reaction after polymerization, it is easy to control the crosslinking rate, and it is easy to obtain good mechanical properties. Is preferably ENB. That is, it is preferable that the ethylene / α-olefin / non-conjugated polyene copolymer has a constituent unit derived from ENB.
[0056]
　The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention preferably satisfies at least one of the following requirements (I) to (III), and at least two of the following requirements (I) to (III). It is more preferable to satisfy one of the requirements, and it is particularly preferable to satisfy the following requirements (I) to (III).
[0057]
　Requirement (I): The molar ratio (ethylene / α-olefin) of the structural unit derived from ethylene to the structural unit derived from α-olefin is 40/60 to 99.9 / 0.1.
[0058]
　Requirement (II): The constituent unit derived from the non-conjugated polyene is 0.07 to 10% by mass in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer.
[0059]
　Requirement (III): The ultimate viscosity [η] measured in decalin at 135 ° C. is 1.0 to 4.0 dl / g.
[0060]
　[Requirement (I)] In the
　requirement (I), the molar ratio (ethylene / α-olefin) of the structural unit derived from ethylene to the structural unit derived from α-olefin is 40/60 to 99.9 / 0. It specifies that it is 1.
[0061]
　The molar ratio (ethylene / α-olefin) of the structural unit derived from ethylene to the structural unit derived from α-olefin is more preferably 55/45 to 85/15, and 55/45 to 78/22. Is particularly preferable.
[0062]
　When the ethylene / α-olefin is within the above range, the layer made of the crosslinked product obtained by cross-linking the ethylene / α-olefin / non-conjugated polyene copolymer exhibits excellent rubber elasticity and mechanical strength. It is preferable because it has excellent flexibility. Further, within the above range, ethylene / α-olefin / non-conjugated polyene copolymers are preferable because they exhibit excellent rubber elasticity and are excellent in mechanical strength and flexibility.
[0063]
　The molar ratio of the structural unit derived from ethylene in the ethylene / α-olefin / non-conjugated polyene copolymer to the structural unit derived from α-olefin can be determined by 13 C-NMR.
[0064]
　[Requirement (II)] The
　requirement (II) is that the constituent unit derived from the non-conjugated polyene is 0.07 to 10% by mass in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It identifies that.
[0065]
　The amount of the structural unit derived from the non-conjugated polyene is more preferably 0.1 to 8.0% by mass, and particularly preferably 0.5 to 5.0% by mass. An ethylene / α-olefin / non-conjugated polyene copolymer having a structural unit derived from a non-conjugated polyene within the above range is preferable because it has sufficient hardness and excellent mechanical properties, and has a high crosslink density. Since a crosslinked product can be obtained, the hardness of the layer made of the crosslinked product can be increased, which is preferable.
[0066]
　The amount of the structural unit derived from the non-conjugated polyene can be determined by 13 C-NMR.
[0067]
　[Requirement (III)] The
　requirement (III) is that the ultimate viscosity [η] of the ethylene / α-olefin / non-conjugated polyene copolymer measured in decalin at 135 ° C. is 1.0 to 4.0 dl / g. It identifies that there is.
[0068]
　The ultimate viscosity [η] is more preferably 1.5 to 4.0 dl / g. It is preferable that the ultimate viscosity is within the above range because the balance between physical properties and processability is good. The ultimate viscosity [η] of the ethylene / α-olefin / non-conjugated polyene copolymer can be measured by the method described in Examples.
[0069]
　Further, the ethylene / α-olefin / non-conjugated polyene copolymer preferably satisfies the following requirement (IV).
[0070]
　[Requirement (IV)]
　Requirement (IV) specifies that the B value of the ethylene / α-olefin / non-conjugated polyene copolymer represented by the following formula (i) is 1.20 or more. Is.
[0071]
　B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] ... (i)
　[Here, [E], [X] and [Y] are , Respectively, show the mole fractions of ethylene, α-olefin, and non-conjugated polyene, and [EX] shows the ethylene-α-olefin diad chain fraction. ]
　The B value is more preferably 1.20 to 1.40, and particularly preferably 1.20 to 1.25.
[0072]
　When the B value is within the above range, the ethylene / α-olefin / non-conjugated polyene copolymer is preferable because the compression set at low temperature is small and the rubber elasticity at low temperature and the tensile strength at room temperature are excellent. ..
[0073]
　When the B value of the ethylene / α-olefin / non-conjugated polyene copolymer is 1.20 or more and the non-conjugated polyene is VNB, the laminate of the present invention tends to be particularly excellent in fatigue resistance, which is preferable. ..
[0074]
　The B value is an index showing the randomness of the copolymer chain distribution in the copolymer, and [E], [X], [Y], and [EX] in the above formula (i) are 13 The C-NMR spectrum was measured, and J. C. Randall [Macropolymers, 15, 353 (1982)], J. Mol. It can be obtained based on the report of Ray [Macropolymers, 10, 773 (1977)] et al.
[0075]
　The amount of α-olefin (content of the constituent unit derived from α-olefin) and the amount of non-conjugated polyene (content of the constituent unit derived from the non-conjugated polyene) in the ethylene / α-olefin / non-conjugated polyene copolymer are , 13 Can be determined by C-NMR.
[0076]
　The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention has a structural unit derived from ethylene, α-olefin, and non-conjugated polyene as described above, but does not impair the effects of the present invention. To the extent, it may have building blocks derived from other monomers (monomers other than ethylene, α-olefins, and non-conjugated polyenes). The structural unit derived from the other monomer is preferably 30% by mass or less, more preferably 25% by mass or less, and 20% by mass in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It is particularly preferable that it is% or less. Examples of other monomers include styrene and vinyl acetate.
[0077]
　The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 600,000, more preferably 30,000 to 500,000, and even more preferably. Is 50,000-400,000.
[0078]
　The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention has a molecular weight distribution (Mw / Mn) of preferably 1.8 to 30, more preferably 1.8 to 25.0, and even more preferably 2. It is 0.0 to 20.0. In addition, Mw and Mw / Mn can be obtained as polystyrene-equivalent numerical values ​​measured by gel permeation chromatography (GPC).
[0079]
　For example, the laminate having the layer (A) or the layer (1) of the present invention can be used as a heat-resistant hose such as a turbocharger hose for automobiles with a relatively high molecular weight ethylene / α-olefin / non-conjugated polyene. A polymer can be preferably used, and specifically, an ethylene / α-olefin / non-conjugated polyene copolymer having a weight average molecular weight (Mw) of 100,000 to 600,000 can be preferably used.
[0080]
　<< Method for Producing Ethylene / α-olefin / Non-conjugated Polyene Copolymer >> The ethylene / α-olefin / non-conjugated polyene copolymer according to the
　present invention is a monomer composed of ethylene, α-olefin, and non-conjugated polyene. It is a copolymer obtained by copolymerizing.
[0081]
　The ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention may be prepared by any production method, but is obtained by copolymerizing a monomer in the presence of a metallocene compound. Is preferable, and it is more preferable that the monomer is obtained by copolymerizing a monomer in the presence of a catalyst system containing a metallocene compound.
[0082]
　A preferred method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention is specifically described in International Publication No. 2017/150612.
[0083]
　<< Ethylene-carboxylic acid copolymer >>
　The polymer forming the layer (A) and the layer (2) of the laminate of the present invention is an ethylene-carboxylic acid copolymer having the following characteristics.
[0084]
　The ethylene / carboxylic acid copolymer according to the present invention may have a structural unit derived from ethylene and a structural unit derived from carboxylic acid, and is not particularly limited. As the ethylene / carboxylic acid copolymer, an ethylene / unsaturated carboxylic acid copolymer is preferable. In the present invention, the ethylene / carboxylic acid copolymer includes an ethylene / carboxylic acid anhydride copolymer. In this case, it is sufficient to have a structural unit derived from ethylene and a structural unit derived from carboxylic acid anhydride, and there is no particular limitation.
[0085]
　The melt flow rate (MFR) (190 ° C., 2160 g load, JIS K7210 (1999)) of the ethylene / carboxylic acid copolymer according to the present invention is not particularly limited, but is 0.01 g / 10 minutes to 150 g / 10 minutes. It is preferably 0.1 g / 10 minutes to 100 g / 10 minutes, and particularly preferably 0.5 to 50 g / 10 minutes.
[0086]
　
　The ethylene / unsaturated carboxylic acid copolymer according to the present invention refers to at least a copolymer obtained by copolymerizing ethylene and an unsaturated carboxylic acid. That is, the ethylene / unsaturated carboxylic acid copolymer is a copolymer having a structural unit derived from ethylene and a structural unit derived from unsaturated carboxylic acid. As the ethylene / unsaturated carboxylic acid copolymer, a monomer other than ethylene and the unsaturated carboxylic acid may be used. That is, the ethylene / unsaturated carboxylic acid copolymer may have a structural unit derived from a monomer other than ethylene and the unsaturated carboxylic acid.
[0087]
　The ethylene / unsaturated carboxylic acid copolymer according to the present invention is selected from the group consisting of an ethylene / unsaturated carboxylic acid binary copolymer and an ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester ternary copolymer. It is preferable that it is at least one kind.
[0088]
　The content of the structural unit derived from ethylene in the ethylene / unsaturated carboxylic acid copolymer according to the present invention is preferably 60% by mass to 98% by mass with respect to the total amount of the ethylene / unsaturated carboxylic acid copolymer. 70% by mass to 98% by mass is more preferable, and 75% by mass to 97% by mass is particularly preferable.
[0089]
　Examples of the unsaturated carboxylic acid copolymerized with ethylene include α-β unsaturated carboxylic acid, and more specifically, acrylic acid, methacrylic acid, etacrilic acid, itaconic acid, fumaric acid, crotonic acid, and maleic acid. , Maleic acid monoester (monomethyl maleate, monoethyl maleate, etc.) and other unsaturated carboxylic acids or half esters having 4 to 8 carbon atoms. As the unsaturated carboxylic acid, acrylic acid and methacrylic acid are preferable. Further, the unsaturated carboxylic acid may be an acid anhydride of the unsaturated carboxylic acid. Examples of the acid anhydride of the unsaturated carboxylic acid include maleic anhydride, phthalic anhydride, acetic anhydride and the like, and maleic anhydride is preferable.
[0090]
　The content of the structural unit derived from the unsaturated carboxylic acid in the ethylene / unsaturated carboxylic acid copolymer is preferably 2% by mass to 25% by mass with respect to the total amount of the ethylene / unsaturated carboxylic acid copolymer. More preferably, it is from% by mass to 20% by mass.
[0091]
　Examples of the unsaturated carboxylic acid ester copolymerized with ethylene include α-β unsaturated carboxylic acid ester, and α-β unsaturated carboxylic acid alkyl ester having 1 to 8 carbon atoms in the alkyl moiety is preferable, and acrylic is preferable. Methyl acrylate, ethyl acrylate, isobutyl acrylate, normal butyl acrylate, ethyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate are more preferred.
[0092]
　When the ethylene / unsaturated carboxylic acid copolymer according to the present invention has a structural unit derived from the unsaturated carboxylic acid ester, the content of the unsaturated carboxylic acid ester is the same as that of the ethylene / unsaturated carboxylic acid copolymer. With respect to the total amount, it is preferably more than 0% by mass and 25% by mass or less, more preferably 2% by mass to 25% by mass, and particularly preferably 2% by mass to 20% by mass.
[0093]
　In the ethylene / unsaturated carboxylic acid copolymer, as other monomers (monomers other than ethylene, unsaturated carboxylic acid, and unsaturated carboxylic acid ester) that can be copolymerized, carbon monoxide, glycidyl acrylate, glycidyl methacrylate and the like are used. Can be mentioned.
[0094]
　When the ethylene / unsaturated carboxylic acid copolymer according to the present invention contains a structural unit derived from the other monomer, the content of the structural unit derived from the other monomer is the ethylene / unsaturated carboxylic acid copolymer. 20% by mass or less is preferable, 10% by mass or less is more preferable, and 5% by mass or less is further preferable.
[0095]
　Specific examples of the ethylene / carboxylic acid copolymer according to the present invention include an ethylene / methacrylic acid copolymer, an ethylene / acrylic acid copolymer, and an ethylene / maleic anhydride copolymer.
[0096]
　The ethylene / unsaturated carboxylic acid copolymer according to the present invention can be used without particular limitation, including commercially available products. Further, there is no particular limitation on the manufacturing method including the known method.
[0097]
　<< Acrylic rubber >>
　The polymer forming the layers (A) and (2-1) or the layers (B) and (3) of the laminate of the present invention is an acrylic rubber having the following characteristics.
[0098]
　The acrylic rubber according to the present invention is a rubber or composite rubber formed from a polymer having a structural unit derived from a (meth) acrylic monomer. The acrylic rubber is a polymer containing 50 to 100% by mass of a structural unit derived from a (meth) acrylic monomer, and has a structural unit derived from another monomer in the range of 0 to 50% by mass.
[0099]
　In the present invention, the term (meth) acrylic monomer is used to include a methacrylic monomer and an acrylic monomer. The methacrylic monomer is a monomer having one CH 2 = CH (CH 3 ) -COO- structure in the molecule, and the acrylic monomer is a monomer having CH 2 = CH 2- COO- structure in the molecule. It is a monomer that has one.
[0100]
　The composite rubber is a step in which the polymer having a structural unit derived from the (meth) acrylic monomer is not simply polymerized but is polymerized using two or more kinds of monomers. It is a rubber obtained by polymerizing.
[0101]
　The (meth) acrylic monomer is not particularly limited, but (meth) acrylate is usually used. Specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tridecyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, and 4-hydroxybutyl acrylate. , Lauryl acrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate and the like. These may be used alone, or two or more kinds may be used.
[0102]
　Among these monomers, n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, tridecyl acrylate, lauryl methacrylate, tridecyl methacrylate and the like are selected from the viewpoints of rubber elasticity, modulus, mechanical strength and oil resistance. preferable.
[0103]
　The acrylic rubber according to the present invention may have a structural unit derived from a monomer other than the (meth) acrylic monomer. Other monomers include α-olefins such as ethylene, propylene and 1-butene; diene monomers such as 1,3-butadiene, isoprene and chloroprene; aromatic vinyls such as styrene and α-methylstyrene; acrylonitrile, Unsaturated nitriles such as methacrylonitrile; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride and vinylidene bromide; glycidyl acrylate, glycidyl methacrylate and allyl glycidyl Vinyl-based monomers having a glycidyl group such as ether and ethylene glycol glycidyl ether; polyfunctional monomers such as divinylbenzene, ethylene glycol dimethacrylate and 1,3-butylene glycol dimethacrylate can be used. Further, the other monomers may be used alone or in combination of two or more.
[0104]
　When producing the acrylic rubber, a cross-linking agent may be used. As the cross-linking agent, a monomer having two or more unsaturated bonds in the molecule is usually used. When a monomer having two or more unsaturated bonds in the molecule is used, the mass of the monomer used is 100% by mass, and it is preferably used in the range of 0.01 to 2% by mass, 0.05. It is more preferable to use it in the range of about 1.5% by mass.
[0105]
　Examples of the cross-linking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, and polyfunctional methacrylic group-modified silicone. The cross-linking agent may be used alone or in combination of two or more.
[0106]
　The acrylic rubber according to the present invention can be used without particular limitation, including commercially available products. The method for producing the acrylic rubber is not particularly limited, and for example, various surfactants such as an anionic surfactant, a nonionic surfactant, and a cationic surfactant are used as an emulsifier or a dispersion stabilizer. It can be produced by a polymerization method such as emulsion polymerization and suspension polymerization.
[0107]
　<< Epichlorohydrin rubber (A) >>
　The epichlorohydrin rubber (A) forming the layer (A) and the layer (2-1) of the laminate of the present invention is a homopolymer of epichlorohydrin (ECH). Epichlorohydrin such as a copolymer of epichlorohydrin (ECH) and ethylene oxide (EO) and a ternary copolymer of epichlorohydrin (ECH), ethylene oxide (EO) and acrylic glycidyl ether (AEG). It is a polymer containing phosphorus (ECH) as a main component, and is usually a polymer collectively called epichlorohydrin rubber (ECO).
[0108]
　The epichlorohydrin rubber (A) according to the present invention can be used without particular limitation, including commercially available products.
[0109]
　<< Halogen-containing polymer >> The halogen-containing polymer
　forming the layer (B) and layer (4), or the layer (2-2) or layer (3-2) of the laminate of the present invention is a halogen having the following characteristics. It is a containing polymer.
[0110]
　The halogen-containing polymer according to the present invention is a polymer excluding the above-mentioned acrylic rubber and the above-mentioned epichlorohydrin rubber.
[0111]
　The halogen-containing polymer according to the present invention is a polymer containing a halogen atom in the molecule, and is preferably a polymer having a structural unit derived from a halogen-containing monomer.
[0112]
　Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the halogen-containing polymer, a polymer containing a fluorine atom, that is, a fluorine atom-containing polymer is preferable.
[0113]
　The halogen-containing polymer is preferably rubber, and the rubber of the fluorine atom-containing polymer, that is, the fluorine-based rubber is more preferable.
[0114]
　
　Examples of the fluorine-based rubber according to the present invention include vinylidene fluoride (VdF) / hexafluoropropylene (HFP) copolymer, VdF / tetrafluoroethylene (TFE) / HFP copolymer, and VdF / TFE. VdF / perhaloolefin-based elastomers such as / perfluoro (alkyl vinyl ether) (PAVE) copolymer, VdF / chlorotrifluoroethylene (CTFE) copolymer; TFE / propylene / VdF copolymer, HFP / ethylene / VdF VdF / non-perhaloolefin-based elastomers such as copolymers; perfluoroepolymers such as TFE / PAVE copolymers; non-perfluoroepolymers such as TFE / propylene copolymers and HFP / ethylene copolymers; fluorosilicone rubbers, etc. can give.
[0115]
　The fluoro (alkyl vinyl ether) may contain a plurality of ether bonds. Further, the molecular weight of the fluororubber is preferably 20,000 to 300,000, preferably 50,000 to 200,000 in terms of number average molecular weight.
[0116]
　Of these, from the viewpoint of heat resistance, oil resistance, and chemical resistance, VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / TFE / PAVE copolymer, TFE / propylene / VdF copolymer. , HFP / ethylene / VdF copolymer, TFE / propylene copolymer, HFP / ethylene copolymer elastomer is preferable, and VdF / HFP copolymer, VdF / TFE / HFP copolymer elastomer is particularly preferable.
[0117]
　The fluororubber may copolymerize a polyfunctional monomer having a plurality of vinyl groups or allyl groups or an iodine or bromine-containing monomer as a crosslinkable group-containing unit. Further, a double bond serving as a cross-linking point may be generated in the molecule by promoting dehydrofluoric acid by performing heat treatment or the like. In particular, a fluororubber having an olefin iodide or an olefin bromide as the crosslinkable unit and having a structural unit derived from the olefin iodide or a structural unit derived from the olefin bromide is preferable.
[0118]
　Further, the content of cross-linking points in the fluororubber (for example, when olefin bromide is used as the cross-linking unit, the content of the structural unit derived from olefin bromide) is preferably 0.05 to 5 mol%. , More preferably 0.15 to 3 mol%, and particularly preferably 0.25 to 2 mol%. If the number of cross-linking points is less than this, the sealing property and adhesive strength become insufficient, and if the number of cross-linking points is more than this, the elasticity and flexibility are lowered, and the rubber elasticity is lost.
[0119]
　<< Layer (1) >>
　The layer (A) and layer (1) of the laminate of the present invention are layers composed of a copolymer composition containing the above ethylene / α-olefin / non-conjugated polyene copolymer as a main component. be.
[0120]
　The copolymer composition according to the present invention is at least one selected from Group 2 element and Group 13 element with respect to the ethylene / α-olefin / non-conjugated polyene copolymer and the polymer: 100 parts by mass. A composition containing an inorganic compound containing the element and a hydroxyl group (hereinafter, may be abbreviated as "inorganic compound") in the range of 0.1 to 30 parts by mass, preferably 0.5 to 25 parts by mass. Is.
[0121]
　When the copolymer composition layer according to the present invention contains the inorganic compound in the above amount, the adhesive strength between the layer (1) and the layer (B) below (3) or the layer (4) below is good. Can be obtained.
[0122]
　
　The inorganic compound according to the present invention is an inorganic compound containing at least one element selected from Group 2 and Group 13 elements and a hydroxyl group, and specifically, calcium hydroxide and hydroxide. It is a hydroxide such as magnesium and aluminum hydroxide.
[0123]
　 In
　addition to the inorganic compounds, the copolymer composition layer according to the present invention includes, for example, organic peroxides, carbon blacks, antiaging agents, softeners, metal oxides, cross-linking aids, and onium salts. , (I) Inorganic compounds containing at least one element selected from Group 2 elements and Group 13 elements and oxygen may be added (blended).
[0124]
　[Organic Peroxide] As the
　organic peroxide, any organic peroxide that can act as a cross-linking agent for ethylene, α-olefin, and non-conjugated polyene copolymer can be preferably used.
[0125]
　Specific examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-di- (tert). -Butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexin-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-butyl Examples thereof include peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butyl cumyl peroxide.
[0126]
　The organic peroxide may be used alone or in combination of two or more.
[0127]
　When the copolymer composition layer according to the present invention contains an organic peroxide, 0.1 to 5 parts by mass, preferably 0.% by mass, based on 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It is desirable to use it in the range of 5 to 5 parts by mass, more preferably 0.5 to 4 parts by mass. When the blending amount of the organic peroxide is within the above range, there is little bloom on the surface of the crosslinked molded product, and the layer (1) exhibits excellent crosslinking characteristics, which is preferable.
[0128]
　[Carbon black] As
　carbon black, various carbon blacks such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT, etc .; surface-treated carbon black obtained by surface-treating these carbon blacks with a silane coupling agent or the like. And so on.
[0129]
　When the copolymer composition layer according to the present invention contains carbon black, the blending amount thereof is 10 to 300 parts by mass, preferably 10 to 300 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It can be about 10 to 200 parts by mass, more preferably about 10 to 100 parts by mass.
[0130]
　If the layer (1) according to the present invention contains carbon black within the above range, a laminated body having improved mechanical properties such as tensile strength and wear resistance can be obtained, and other than the laminated body. It is preferable because its hardness can be increased without impairing the physical properties of.
[0131]
　[Anti-aging agent] When the
　layer (1) according to the present invention contains an anti-aging agent, the product life of the obtained laminate can be extended. As the anti-aging agent, conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents and the like can be used.
[0132]
　Specific examples of the anti-aging agent include phenylbutylamine, N, N-di-2-naphthyl-p-phenylenediamine, and 4,4'-bis (α, α-dimethylbenzyl) diphenylamine (also known as 4,4). Aromatic secondary amine-based antioxidants such as'-benzyl-diphenyllamine), amine-based antioxidants such as 2,2,4-trimethyl-1,2-dihydroquinolin polymer, dibutylhydroxytoluene, tetrakis [methylene] (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] Phenolic anti-aging agents such as methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t- Butylphenyl] Thioether-based anti-aging agents such as sulfide; Dithiocarbamate-based anti-aging agents such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, distearyl Examples include sulfur-based anti-aging agents such as thiodipropionate.
[0133]
　The anti-aging agent may be used alone or in combination of two or more.
[0134]
　When the layer (1) according to the present invention contains an antioxidant, the blending amount thereof is 0.5 to 5.0 mass by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. Parts, preferably 0.5 to 4.5 parts by mass, more preferably 0.5 to 4.0 parts by mass. When it is within the above range, the obtained laminate is preferable because it has excellent heat aging resistance.
[0135]
　[Softener] As the
　softener, components known as softeners, processing aids and the like conventionally blended in rubber can be widely used.
[0136]
　Specifically, petroleum-based softeners such as paraffin-based process oils, naphthen-based process oils, and aroma-based process oils; synthetic oil-based softeners; co-oligomers of ethylene and α-olefins; paraffin waxes; liquid paraffins; white Oil (white oil); petrolatum; hydrocarbon softeners such as hydrocarbons, hydrocarbon pitches; hydrocarbon oils, brocade oils, flaxseed oils, rapeseed oils, palm oils, palm oils, soybean oils, peanut oils, wood wax, Vegetable oil-based softeners such as rosin, pine oil, dipentene, pinetal, and tall oil; subs such as black sub, white sub, and candy sub (factis); waxes such as beeswax, carnauba wax, and lanolin; , Stearic acid, linoleic acid, laurate, myristic acid, barium stearate, calcium stearate, magnesium stearate, zinc stearate, zinc laurate and other fatty acids, fatty acid salts and esters; dioctyl phthalate, dioctyl adipate, dioctyl sebacate Ester-based plasticizers such as; kumaron-inden resin; phenol-formaldehyde resin; terpen-phenol resin; polyterpene resin; synthetic polyterpene resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin Petroleum-based such as aliphatic / alicyclic petroleum resin, aliphatic / aromatic petroleum resin, hydrogenated modified alicyclic hydrocarbon resin, hydrogenated hydrocarbon resin, liquid polybutene, liquid polybutadiene, atactic polypropylene, etc. Hydrocarbon resins and the like can be mentioned.
[0137]
　Among these softeners, fatty acids, petroleum-based softeners, phenol / formaldehyde resins, and petroleum-based hydrocarbon resins are preferable, fatty acids, petroleum-based softeners, and petroleum-based hydrocarbon resins are more preferable, and fatty acids and petroleum-based softeners are used. Especially preferable.
[0138]
　Among the petroleum-based softeners, petroleum-based process oils are preferable, and among them, paraffin-based process oils, naphthenic process oils, aroma-based process oils and the like are more preferable, and paraffin-based process oils are particularly preferable. Among the petroleum-based hydrocarbon resins, an aliphatic cyclic hydrocarbon resin is preferable. Among these softeners, paraffin-based process oil is particularly preferable.
[0139]
　These softeners may be used alone or in combination of two or more.
[0140]
　When the layer (1) according to the present invention contains a softening agent, the blending amount thereof is usually less than 200 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer, which is preferable. Is 0 to 100 parts by mass, more preferably 0 to 80 parts by mass, still more preferably 0 to 70 parts by mass, and particularly preferably 0 to 60 parts by mass.
[0141]
　[Metal oxide] The
　metal oxide can be appropriately selected depending on the intended use of the laminate, and can be used alone or in combination of two or more. Specific examples of the metal oxide include zinc oxide (for example, META-Z102) (trade name: zinc oxide manufactured by Inoue Lime Industry Co., Ltd.), magnesium oxide and the like.
[0142]
　When the layer (1) according to the present invention contains a metal oxide, the blending amount thereof is usually 0.5 to 20 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It is preferably 0.5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass.
[0143]
　[Cross-linking aid]
　Examples of the cross-linking aid include sulfur; quinone-dioxime-based compounds such as p-quinone-dioxime; and (meth) acrylate-based compounds such as polyfunctional monomers such as trimethylolpropane triacrylate and polyethylene glycol dimethacrylate. Allyl compounds such as diallyl phthalate and trimethylol cyanurate; maleimide compounds such as m-phenylene bismaleimide; divinylbenzene and the like can be mentioned. The cross-linking aid may be used alone or in combination of two or more.
[0144]
　When the layer (1) according to the present invention contains a cross-linking aid, the blending amount thereof is usually 0 to 4.0 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It is preferably 0 to 3.5 parts by mass, more preferably 0 to 3.0 parts by mass, and further preferably 0.1 to 3.0 parts by mass.
[0145]
　It is also desirable that the amount of the cross-linking aid compounded is preferably 0.5 to 2 mol, more preferably approximately equimolar amount, with respect to 1 mol of the organic peroxide.
[0146]
　[Onium salt]
　Examples of the onium salt include a quaternary ammonium salt, a quaternary phosphonium salt, an oxonium salt, a sulfonium salt, a cyclic amine and a monofunctional amine compound, and among these, a quaternary ammonium salt. , A quaternary phosphonium salt is preferred.
[0147]
　The onium salt may be used alone or in combination of two or more.
[0148]
　The quaternary ammonium salt is not particularly limited, for example, dialkyl (C14-18) dimethylammonium chloride, 1,8-diazabicyclo [5,4,0] -7-undecenium salt, 8-methyl-1,8. -Diazabicyclo [5,4,0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium iodide, 8-methyl-1,8- Diazabicyclo [5,4,0] -7-undecenium hydroxyside, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium methylsulfate, 8-ethyl-1, 8-Diazabicyclo [5,4,0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5,4,0] -7-undecenium bromide, 8-dodecyl-1,8- Diazabicyclo [5,4,0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxyside, 8-eicosyl-1,8- Diazabicyclo [5,4,0] -7-undecenium chloride, 8-tetracocil-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [ 5,4,0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8 -Penetyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8- (3-phenylpropyl) -1,8-diazabicyclo [5,4,0] -7-undecenium Examples include chloride. Among these, dialkyl chloride (C14-18) dimethylammonium is preferable.
[0149]
　The quaternary phosphonium salt is not particularly limited, and for example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl. -2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride and the like can be mentioned, and among these, benzyltriphenylphosphonium chloride (BTPPC) is preferable from the viewpoint of solubilization property and physical properties of the sulfide product. ..
[0150]
　Further, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, and a compound disclosed in JP-A-11-147891 can also be used.
[0151]
　Examples of the amine compound include hexamethylenediamine carbamate, N, N'-dicinnamylidene-1,6-hexamethylenediamine, and 4,4'-bis (aminocyclohexyl) methanecarbamate. Of these, N, N'-dicinenamylden-1,6-hexamethylenediamine is preferable.
[0152]
　As the onium salt, a commercially available product may be used, for example, "Lipocard 2HT flakes" (manufactured by Lion Specialty Chemicals Co., Ltd., dialkyl (C14-18) dimethylammonium chloride, and "Lipocard 2HTF" in the present invention. (Note) can be used.
[0153]
　When the layer (1) according to the present invention contains an onium salt, the blending amount thereof is preferably 0.2 parts by mass or more with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer, and is 0. .2 parts by mass or more and 10 parts by mass or less are more preferable, and 0.5 parts by mass or more and 8 parts by mass or less are further preferable.
[0154]
　[Inorganic compound containing at least one element selected from Group 2 and Group 13 elements and oxygen] Inorganic compound containing
　at least one element selected from Group 2 and Group 13 elements and oxygen Examples thereof include, but are not limited to, oxides, carbonates, and hydrotalcite compounds containing at least one element selected from Group 2 elements and Group 13 elements.
[0155]
　Examples of at least one element selected from Group 2 elements and Group 13 elements include at least one element selected from Mg, Ca, Ba, and Al.
[0156]
　As the inorganic compound containing at least one element selected from Group 2 elements and Group 13 elements and oxygen, a commercially available product may be used, for example, "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd.). , Hydrotalcite compounds: Mg 4.3 Al 2 (OH) 12.6 CO 3 · mH 2 O) can be used.
[0157]
　When the layer (1) according to the present invention contains an inorganic compound containing at least one element selected from Group 2 elements and Group 13 elements and oxygen, the blending amount thereof is ethylene, α-olefin, or non-ethylene. 7 parts by mass or more is preferable, and 7 parts by mass or more and 100 parts by mass or less are more preferable with respect to 100 parts by mass of the conjugated polyene copolymer.
[0158]
　The lower limit of the inorganic compound containing oxygen and at least one element selected from Group 2 elements and Group 13 elements is particularly preferably 10 parts by mass or more. As the upper limit, 80 parts by mass or less is even more preferable, 50 parts by mass or less is particularly preferable, 40 parts by mass or less is particularly preferable, and 35 parts by mass or less is most preferable.
[0159]
　In addition to the above additives, the layer (1) according to the present invention includes various additives conventionally added to rubber compositions, such as fillers, foaming agents, antioxidants, processing aids, surfactants, and weather resistant agents. It may contain an agent component. Further, a resin component other than the above ethylene / α-olefin / non-conjugated polyene copolymer may be contained, if necessary.
[0160]
　[Filler]
　Examples of the filler include inorganic fillers such as silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, fine powder talc, talc, fine powder silicic acid, and clay. These fillers can be about 0 to 300 parts by mass, preferably about 0 to 200 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. By using a filler, a laminated body having improved mechanical properties such as tensile strength, tear strength and wear resistance can be obtained, and the hardness of the laminated body can be increased without impairing other physical properties of the obtained laminated body. Can be done.
[0161]
　[Antioxidant]
　The layer (1) according to the present invention preferably contains an antioxidant from the viewpoint that the material life thereof can be extended.
[0162]
　Antioxidants include aromatic secondary amine stabilizers such as phenylnaphthylamine, 4,4'-(α, α-dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine; 2,6-di-t-butyl-4-methylphenol, tetrakis- [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Phenol stabilizers such as methane Bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] thioether-based stabilizers such as sulfide; benzimidazole-based stabilizers such as 2-mercaptobenzimidazole; dibutyldithiocarbamic acid Dithiocarbamate-based stabilizers such as nickel; quinoline-based stabilizers such as polymers of 2,2,4-trimethyl-1,2-dihydroquinolin can be mentioned. These can be used alone or in combination of two or more.
[0163]
　When the layer (1) according to the present invention contains an antioxidant, the blending amount thereof is, for example, 5 parts by mass or less, preferably 3 parts by mass, based on 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It can be used in an amount of parts by mass or less.
[0164]
　Further, the layer (1) according to the present invention may appropriately contain, if necessary, various additives that can be blended in a known rubber composition, in addition to the ethylene / α-olefin / non-conjugated polyene copolymer. can.
[0165]
　A surfactant may be blended in the layer (1) according to the present invention. Surfactants include di-n-butylamine, dicyclohexylamine, monoelanolamine, triethanolamine, amines such as "Acting B (manufactured by Yoshitomi Pharmaceutical Co., Ltd.)," Acting SL (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), and polyethylene. Zinc compounds of glycols, diethylene glycols, polyethylene glycols, lecithins, trialilutomeritates, aliphatic and aromatic carboxylic acids (eg, "Structol activator 73", "Structor IB 531", "Structor FA541" Schill & Seiracher, Inc.) "ZP" (manufactured by Nippon Zeon Co., Ltd.), octadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compound (eg, "Lipocard 2 HTF" (manufactured by Lion Specialty Chemicals Co., Ltd.), dialkyl chloride (C14-18) ) Dimethylammonium) and the like. As the surfactant, Lipocard 2 HTF is most preferable.
[0166]
　When the layer (1) according to the present invention contains a surfactant, the blending amount thereof is, for example, 0.2 to 10 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It is preferably 0.3 to 8 parts by mass, more preferably 0.3 to 7 parts by mass, particularly preferably 0.5 to 7 parts by mass, and most preferably 1 to 6 parts by mass. The surfactant can be appropriately selected depending on the intended use, and can be used alone or in combination of two or more.
[0167]
　Further, a pseudo-gel inhibitor may be blended in the layer (1) according to the present invention. Examples of the pseudo-gel inhibitor include "NHM-007" (manufactured by Mitsui Chemicals, Inc.).
[0168]
　When the layer (1) according to the present invention contains a pseudo-gel inhibitor, the blending amount thereof is usually 0.1 to 15 mass by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. Parts, preferably 0.5 to 12 parts by mass, more preferably 1.0 to 10 parts by mass.
[0169]
　If necessary, other additives may be further added to the layer (1) according to the present invention. Examples of other additives include heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, colorants, lubricants, thickeners and the like.
[0170]
　The layer (1) according to the present invention may contain other resin components other than ethylene, α-olefin, and non-conjugated polyene copolymer, if necessary. Examples of other resin components include, but are not limited to, polyolefin resins.
[0171]
　By blending a polyolefin resin with an ethylene / α-olefin / non-conjugated polyene copolymer, the product hardness can be adjusted and the compound viscosity at the processing temperature can be lowered, so that the processability can be further improved. Further, it can be handled as a thermoplastic elastomer, which is preferable because it has a wide range of handleability and kneading method.
[0172]
　As the polyolefin resin, usually, a polyolefin resin having a number average molecular weight of 10,000 or more in terms of standard polystyrene measured by GPC is preferably used.
[0173]
　Examples of the polyolefin resin include α-olefin homopolymers and α-olefin copolymers. Examples of the α-olefin homopolymer include polyethylene and polypropylene, and examples of the α-olefin copolymer include an ethylene / α-olefin copolymer having 3 to 20 carbon atoms. Examples of the ethylene / olefin copolymer having 3 to 20 carbon atoms include ethylene / propylene rubber (EPR), propylene / ethylene rubber (PER), ethylene / butene rubber (EBR), and ethylene / octene rubber (EOR). Can be mentioned.
[0174]
　Among these, as the polyolefin resin, polyethylene, an ethylene / α-olefin copolymer, and polypropylene are preferable.
[0175]
　The polyolefin resin may be used alone or in combination of two or more.
[0176]
　When the layer (1) according to the present invention contains a polyolefin resin, the blending amount thereof is, for example, 1 to 100 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It is about 5 to 80 parts by mass, more preferably about 10 to 50 parts by mass.
[0177]
　Within the above range, the hardness of the obtained laminate can be adjusted and the compound viscosity at the processing temperature can be lowered, so that the processability can be further improved. Further, it can be handled as a thermoplastic elastomer, which is preferable because it has a wide range of handleability and kneading method.
[0178]
　<< Layer (2) >>
　The layer (A) and the layer (2) of the laminate of the present invention are layers prepared by using the above-mentioned ethylene / carboxylic acid copolymer.
[0179]
　The layer (2) according to the present invention may be prepared using at least an ethylene / carboxylic acid copolymer, but usually, not only the ethylene / carboxylic acid copolymer but also other components are used as raw materials. It is a layer to be produced.
[0180]
　The layer (2) according to the present invention is usually a layer prepared by cross-linking using an ethylene / carboxylic acid copolymer. As the components other than the ethylene / carboxylic acid copolymer, for example, an inorganic compound containing at least one element selected from the Group 2 element and the Group 13 element described in the description of the layer (1) and a hydroxyl group. , Organic peroxides, carbon blacks, antioxidants, softeners, metal oxides, cross-linking aids, onium salts and other components.
[0181]
　As for the blending amount of the additive in the layer (2), the ethylene / α-olefin / non-conjugated polyene copolymer was replaced with an ethylene / carboxylic acid copolymer in the same manner as in the layer (1). It can be used in quantity.
[0182]
　<< Layer (3) >>
　The layer (B) and the layer (3) of the laminated body of the present invention are layers produced by using the above-mentioned acrylic rubber.
[0183]
　The layer (3) according to the present invention may be produced by using at least an acrylic rubber, but is usually a layer produced by using not only the acrylic rubber but also other components as raw materials. ..
[0184]
　The layer (3) according to the present invention is a layer formed by cross-linking, usually using an acrylic rubber. Examples of the components other than the acrylic rubber include an inorganic compound containing at least one element selected from the Group 2 element and the Group 13 element described in the description of the layer (1) and a hydroxyl group, and an organic peroxide. Examples include compounds, carbon blacks, antioxidants, softeners, metal oxides, cross-linking aids, onium salts, and other components.
[0185]
　As the blending amount of the additive in the layer (3), the ethylene / α-olefin / non-conjugated polyene copolymer should be replaced with an acrylic rubber in the same manner as in the layer (1). Can be mentioned.
[0186]
　<< Layer (4) >>
　The layer (B) and layer (4) of the laminate of the present invention are layers prepared by using the above-mentioned halogen-containing polymer.
[0187]
　The layer (4) according to the present invention may be prepared by using at least a halogen-containing polymer, but usually, a layer prepared by using not only the halogen-containing polymer but also other components as raw materials. Is.
[0188]
　The layer (4) of the laminate of the present invention is preferably a fluorine-based polymer.
[0189]
　The layer (4) according to the present invention is a layer prepared by cross-linking, usually using a halogen-containing polymer. Examples of the components other than the halogen-containing polymer include an inorganic compound containing at least one element selected from the Group 2 element and the Group 13 element described in the description of the layer (1) and a hydroxyl group, and an organic compound. Examples include oxides, carbon blacks, antioxidants, softeners, metal oxides, cross-linking aids, onium salts and other components.
[0190]
　As the blending amount of the additive in the layer (4), the ethylene / α-olefin / non-conjugated polyene copolymer is replaced with a halogen-containing polymer in the same manner as in the layer (1). Can be mentioned.
[0191]
　As a method for cross-linking a halogen-containing polymer such as a fluorine-based polymer, polyol cross-linking, peroxide cross-linking, and amine cross-linking are generally known. Among these, amine cross-linking is rarely used at present because it is difficult to store the material.
[0192]
　When performing peroxide cross-linking of a halogen-containing polymer such as a fluorine polymer, the organic peroxide can be used.
[0193]
　When cross-linking a halogen-containing polymer such as a fluorine-based polymer with a polyol, a polyol-based cross-linking agent can be used.
[0194]
　As the polyol-based cross-linking agent, bisphenols are preferable. Specifically, for example, 2,2'-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxyphenyl) hexafluoropropane [bisphenol AF], bis (4-hydroxyphenyl). ) Polysulfone [bisphenol S], bisphenol A bis (diphenyl phosphate), 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) butane [bisphenol B], etc. Hydroaromatic compounds can be mentioned.
[0195]
　As the polyol-based cross-linking agent, bisphenol A and bisphenol AF are preferably used. Further, as the polyol-based cross-linking agent, an alkali metal salt or an alkaline earth metal salt of the polyhydroxy aromatic compound can also be used.
[0196]
　Further, as the polyol-based cross-linking agent, a commercially available master batch containing a halogen-containing polymer and a polyol-based cross-linking agent may be used. Examples of commercially available master batches include Curative VC # 30 (manufactured by DuPont Dow Elastomer: containing 50 wt% of a cross-linking agent [bisphenol AF]).
[0197]
　The cross-linking agent may be used alone or in combination of two or more.
[0198]
　The layer (4) according to the present invention is a metal hydroxide such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide; and a carbonate such as magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate; Sirates such as magnesium silicate, calcium silicate, sodium silicate, aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate, barium sulfate; metallic sulfides such as synthetic hydrotalcite, molybdenum disulfide, iron sulfide, copper sulfide; wet Silicon oxides such as silica, dry silica, quartz fine powder, glass fiber; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, talc, mica powder, In addition to inorganic fillers such as wallastonite, carbon fiber, aramid fiber, and various whiskers, an organic reinforcing agent, an organic filler, and the like may be contained.
[0199]
　Further, the halogen-containing polymer can be optionally blended with an acid receiver, an ultraviolet absorber, a flame retardant, an oil resistance improver, a scorch inhibitor, a tackifier and the like.
[0200]
　The layer (4) according to the present invention may be formed by using a commercially available composition containing a fluorine-based polymer which is a halogen-containing polymer and a cross-linking agent.
[0201]
　Examples of commercially available compositions containing a fluorine-based polymer and a cross-linking agent include Daiel DC-2270F and Daiel DC-4070 (both manufactured by Daikin Industries, Ltd.). Daiel DC-2270F is a composition containing a polyol-based cross-linking agent, a filler, and an antacid in addition to the fluorine-based polymer, and Daiel DC-4070 is an organic peroxide and a filler in addition to the fluorine-based polymer. It is a composition containing.
[0202]
　<< Layer (2-1) >>
　The layer (2-1) of the laminate of the present invention includes the acrylic rubber (A) and the acrylic rubber (A): Group 2 elements and Group 13 with respect to 100 parts by mass. An inorganic compound containing at least one element selected from the elements and a hydroxyl group [hereinafter, may be abbreviated as "inorganic compound". ] Is a layer composed of 1 to 30 parts by mass, preferably 1 to 25 parts by mass.
[0203]
　<< Inorganic compound >> The inorganic compound
　blended in the acrylic rubber (A) forming the layer (2-1) of the laminate of the present invention contains at least one element selected from Group 2 elements and Group 13 elements. An inorganic compound containing a hydroxyl group, specifically, a hydroxide such as calcium hydroxide, magnesium hydroxide, or aluminum hydroxide, which forms the layer (1) of the laminate. It is the same compound as the inorganic compound blended in the olefin / non-conjugated polyene copolymer.
[0204]
　In addition to the inorganic compound, various additives usually blended in rubber can be added to the layer (2-1) according to the present invention.
[0205]
　Examples of other additives include the following additives.
[0206]
　More specifically, organic peroxides, carbon blacks, antioxidants, softeners, metal oxides, cross-linking aids, onium salts, fillers, antioxidants, and surfactants blended in the layer (1). Examples include agents and pseudogelling agents.
[0207]
　When the organic peroxide according to the present invention is blended with the acrylic rubber (A), it is usually 0.1 to 5 parts by mass, preferably 0.5 parts by mass with respect to 100 parts by mass of the acrylic rubber (A). It is desirable to use in the range of ~ 5 parts by mass, more preferably 0.5 to 4 parts by mass. When the blending amount of the organic peroxide is within the above range, there is little bloom on the surface of the laminate, and the layer (2-1) exhibits excellent cross-linking characteristics, which is preferable.
[0208]
　When the carbon black according to the present invention is blended with the acrylic rubber (A), the blending amount of the carbon black is usually 10 to 300 parts by mass, preferably 10 to 300 parts by mass with respect to 100 parts by mass of the acrylic rubber (A). It can be about 10 to 200 parts by mass, more preferably about 10 to 100 parts by mass.
[0209]
　If carbon black is contained within the above range, a laminated body having improved mechanical properties such as tensile strength and wear resistance can be obtained, and the hardness of the laminated body is increased without impairing other physical properties of the laminated body. It is preferable because it can be used.
[0210]
　When the anti-aging agent according to the present invention is blended with the acrylic rubber (A), the blending amount of the anti-aging agent is usually 0.5 to 5. With respect to 100 parts by mass of the acrylic rubber (A). It is 0 parts by mass, preferably 0.5 to 4.5 parts by mass, and more preferably 0.5 to 4.0 parts by mass. When it is within the above range, the obtained laminate is preferable because it has excellent heat aging resistance.
[0211]
　When the softening agent according to the present invention is blended with the acrylic rubber (A), the amount is usually less than 200 parts by mass, preferably 0 to 100 parts by mass, based on 100 parts by mass of the acrylic rubber (A). Parts, more preferably 0 to 80 parts by mass, still more preferably 0 to 70 parts by mass, and particularly preferably 0 to 60 parts by mass.
[0212]
　When the metal oxide according to the present invention is blended with the acrylic rubber (A), it is usually 0.5 to 20 parts by mass, preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the acrylic rubber (A). It is 15 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass.
[0213]
　When the cross-linking aid according to the present invention is blended with the acrylic rubber (A), it is usually 0 to 4.0 parts by mass, preferably 0 to 3 parts by mass with respect to 100 parts by mass of the acrylic rubber (A). It is 5 parts by mass, more preferably 0 to 3.0 parts by mass, and further preferably 0.1 to 3.0 parts by mass. It is also desirable that the amount of the cross-linking aid compounded is preferably 0.5 to 2 mol, more preferably approximately equimolar amount, with respect to 1 mol of the organic peroxide.
[0214]
　When the onium salt according to the present invention is blended with the acrylic rubber (A), it is usually preferably 0.2 parts by mass or more, preferably 0.2 parts by mass or more, with respect to 100 parts by mass of the acrylic rubber (A). 10, 10 parts by mass or less is more preferable, and 0.5 parts by mass or more and 8 parts by mass or less are further preferable. When the onium salt according to the present invention is used in the above range and used in combination with the inorganic compound, the adhesive strength with the layer (2-2) is further improved.
[0215]
　When the filler according to the present invention is blended with the acrylic rubber (A), it is usually 0 to 300 parts by mass, preferably about 0 to 200 parts by mass with respect to 100 parts by mass of the acrylic rubber (A). be able to. By using the filler, it is possible to obtain a laminated body having improved mechanical properties such as tensile strength, tear strength and wear resistance, and it is possible to increase the hardness of the laminated body without impairing other physical properties of the laminated body. ..
[0216]
　When the antioxidant according to the present invention is blended with the acrylic rubber (A), the amount is usually 5 parts by mass or less, preferably 3 parts by mass or less, based on 100 parts by mass of the acrylic rubber (A). Can be used in.
[0217]
　When the surfactant according to the present invention is blended with the acrylic rubber (A), it is usually 0.2 to 10 parts by mass, preferably 0.3, with respect to 100 parts by mass of the acrylic rubber (A). It is ~ 8 parts by mass, more preferably 0.3 to 7 parts by mass, particularly preferably 0.5 to 7 parts by mass, and most preferably 1 to 6 parts by mass. The surfactant can be appropriately selected depending on the intended use, and can be used alone or in combination of two or more.
[0218]
　When the pseudo-gelling inhibitor according to the present invention is blended with the acrylic rubber (A), it is usually 0.1 to 15 parts by mass, preferably 0.% by mass with respect to 100 parts by mass of the acrylic rubber (A). It is 5 to 12 parts by mass, more preferably 1.0 to 10 parts by mass.
[0219]
　If necessary, other additives may be further added to the acrylic rubber (A) forming the layer (2-1) according to the present invention. Examples of other additives include heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, colorants, lubricants, thickeners and the like.
[0220]
　<< Layer (2-2) >>
　The layer (2-2) laminated with the layer (2-1) is the same as the layer prepared by using the above-mentioned halogen-containing polymer forming the layer (4). It is a layer.
[0221]
　The layer (2-2) according to the present invention may be prepared by using at least a halogen-containing polymer, but is usually prepared by using not only the halogen-containing polymer but also other components as raw materials. Layer.
[0222]
　The layer (2-2) of the laminate of the present invention is preferably a fluorine-based polymer.
[0223]
　<< Layer (3-1) >>
　The layer (3-1) of the laminate of the present invention contains the above-mentioned epichlorohydrin rubber (A) and epichlorohydrin rubber (A): Group 2 elements and 100 parts by mass. An inorganic compound containing at least one element selected from Group 13 elements and a hydroxyl group [sometimes abbreviated as "inorganic compound". ] Is 1 to 30 parts by mass, preferably 1 to 25 parts by mass, and 0.2 parts by mass or more and 10 parts by mass or less, preferably 0.5 parts by mass or more and 8 parts by mass or less of the onium salt. ..
[0224]
　When the composition layer according to the present invention contains the inorganic compound in the above amount and the layer (3-1) and the following layer (3-2) are directly bonded to each other, the composition layer has a strong adhesive strength. You can get a body.
[0225]
　<< Inorganic compound (B) >>
　The inorganic compound to be blended in the epichlorohydrin rubber (A) forming the layer (3-1) of the laminate of the present invention is at least one selected from Group 2 and Group 13 elements. The above-mentioned inorganic compound containing a seed element and a hydroxyl group, specifically, a hydroxide such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, etc., which forms the layer (1) of the laminate. It is the same compound as the inorganic compound blended in the ethylene / α-olefin / non-conjugated polyene copolymer or the inorganic compound blended in the acrylic rubber (A) forming the layer (2-1).
[0226]
　In addition to the inorganic compound, various additives usually blended in rubber can be added to the layer (3-1) according to the present invention.
[0227]
　 In addition
　to the above-mentioned inorganic compound (B), various additives usually blended in rubber are added to the epichlorohydrin rubber (A) forming the layer (3-1) according to the present invention. be able to.
[0228]
　Examples of other additives include the following additives.
[0229]
　More specifically, examples thereof include organic peroxides, carbon blacks, antiaging agents, softeners, metal oxides, cross-linking aids, and onium salts blended in the layer (1).
[0230]
　When the organic peroxide according to the present invention is blended with the epichlorohydrin rubber (A), it is usually 0.1 to 5 parts by mass, preferably 0 with respect to 100 parts by mass of the epichlorohydrin rubber (A). It is desirable to use in the range of .5 to 5 parts by mass, more preferably 0.5 to 4 parts by mass. When the blending amount of the organic peroxide is within the above range, there is little bloom on the surface of the laminate, and the layer (3-1) exhibits excellent cross-linking characteristics, which is preferable.
[0231]
　When the carbon black according to the present invention is blended with the epichlorohydrin rubber (A), the blending amount of the carbon black is usually 10 to 300 parts by mass with respect to 100 parts by mass of the epichlorohydrin rubber (A). It can be preferably about 10 to 200 parts by mass, more preferably about 10 to 100 parts by mass.
[0232]
　If carbon black is contained within the above range, a laminated body having improved mechanical properties such as tensile strength and wear resistance can be obtained, and the hardness of the laminated body is increased without impairing other physical properties of the laminated body. It is preferable because it can be used.
[0233]
　When the anti-aging agent according to the present invention is blended with the epichlorohydrin rubber (A), the blending amount of the anti-aging agent is usually 0.5 to 0.5 to 100 parts by mass of the epichlorohydrin rubber (A). It is 5.0 parts by mass, preferably 0.5 to 4.5 parts by mass, and more preferably 0.5 to 4.0 parts by mass. When it is within the above range, the obtained laminate is preferable because it has excellent heat aging resistance.
[0234]
　When the softening agent according to the present invention is blended with the epichlorohydrin rubber (A), the amount is usually less than 200 parts by mass, preferably 0 to 0 to 100 parts by mass with respect to 100 parts by mass of the epichlorohydrin rubber (A). It is 100 parts by mass, more preferably 0 to 80 parts by mass, still more preferably 0 to 70 parts by mass, and particularly preferably 0 to 60 parts by mass.
[0235]
　When the metal oxide according to the present invention is blended with the epichlorohydrin rubber (A), it is usually 0.5 to 20 parts by mass, preferably 0.% by mass, based on 100 parts by mass of the epichlorohydrin rubber (A). It is 5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass.
[0236]
　When the cross-linking aid according to the present invention is blended with the epichlorohydrin rubber (A), it is usually 0 to 4.0 parts by mass, preferably 0 to 4.0 parts by mass with respect to 100 parts by mass of the epichlorohydrin rubber (A). It is 3.5 parts by mass, more preferably 0 to 3.0 parts by mass, and further preferably 0.1 to 3.0 parts by mass. It is also desirable that the amount of the cross-linking aid compounded is preferably 0.5 to 2 mol, more preferably approximately equimolar amount, with respect to 1 mol of the organic peroxide.
[0237]
　When the onium salt according to the present invention is blended with the epichlorohydrin rubber (A), it is usually 0.2 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more, with respect to 100 parts by mass of the epichlorohydrin rubber (A). , 0.5 parts by mass or more and 8 parts by mass or less. When the onium salt according to the present invention is used in the above range and used in combination with the inorganic compound, the adhesive strength with the layer (3-2) is further improved.
[0238]
　 In addition to the
　above additives, the following additives can be added to the epichlorohydrin rubber (A) forming the layer (3-1) according to the present invention.
[0239]
　Examples of other components according to the present invention include various additive components usually added to rubber compositions, such as fillers, foaming agents, antioxidants, processing aids, surfactants, and weather resistant agents. Further, a resin or rubber component other than epichlorohydrin rubber (A) may be contained as required.
[0240]
　When the filler according to the present invention is blended with the epichlorohydrin rubber (A), it is usually about 0 to 300 parts by mass, preferably about 0 to 200 parts by mass with respect to 100 parts by mass of the epichlorohydrin rubber (A). Can be. By using the filler, it is possible to obtain a laminated body having improved mechanical properties such as tensile strength, tear strength and wear resistance, and it is possible to increase the hardness of the laminated body without impairing other physical properties of the laminated body. ..
[0241]
　When the antioxidant according to the present invention is blended with the epichlorohydrin rubber (A), it is usually 5 parts by mass or less, preferably 3 parts by mass or less, based on 100 parts by mass of the epichlorohydrin rubber (A). Can be used in the amount of.
[0242]
　When the surfactant according to the present invention is blended with the epichlorohydrin rubber (A), it is usually 0.2 to 10 parts by mass, preferably 0, based on 100 parts by mass of the epichlorohydrin rubber (A). It is 3 to 8 parts by mass, more preferably 0.3 to 7 parts by mass, particularly preferably 0.5 to 7 parts by mass, and most preferably 1 to 6 parts by mass. The surfactant can be appropriately selected depending on the intended use, and can be used alone or in combination of two or more.
[0243]
　When the pseudo-gelling inhibitor according to the present invention is blended with the epichlorohydrin rubber (A), it is usually 0.1 to 15 parts by mass, preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the epichlorohydrin rubber (A). It is 0.5 to 12 parts by mass, more preferably 1.0 to 10 parts by mass.
[0244]
　The epichlorohydrin rubber (A) forming the layer (3-1) according to the present invention may further contain other additives, if necessary. Examples of other additives include heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, colorants, lubricants, thickeners and the like.
[0245]
　<< Layer (3-2) >>
　The layer (3-2) laminated with the layer (3-1) is the above-mentioned halogen-containing polymer forming the above-mentioned layer (4) or the above-mentioned layer (3-2). It is the same layer as the layer produced using it.
[0246]
　The layer (3-2) according to the present invention may be prepared by using at least a halogen-containing polymer, but is usually prepared by using not only the halogen-containing polymer but also other components as raw materials. Layer.
[0247]
　The layer (3-2) of the laminate of the present invention is preferably a fluorine-based polymer.
[0248]
　
　The laminated body of the present invention is a laminated body including the following layer (A) and the following layer (B).
[0249]
　Layer (A): A layer containing one or more polymers selected from the following polymers:
　ethylene / α-olefin / non-conjugated polyene copolymer, ethylene / carboxylic acid copolymer, acrylic rubber, and epichlorohydrin rubber. Rubber
　layer (B): A layer
　acrylic rubber containing one or more polymers selected from the following polymers , and a halogen-containing polymer.
　The laminate of the present invention includes the layer (1) and the layer (2). ), And a laminate containing at least one layer selected from the layer (3) and the layer (4), the layer (1) and the layer (1). Whether at least one layer of at least one layer selected from 2) is in direct contact with at least one layer of at least one layer selected from said layer (3) and said layer (4). Alternatively, it is a laminate that is in contact with each other via an adhesive layer.
[0250]
　More specifically, a laminate composed of the layer (1) and the layer (3), a laminate composed of the layer (1) and the layer (4), the layer (2) and the layer (3). It is a laminated body composed of, and a laminated body composed of the layer (2) and the layer (4).
[0251]
　Examples of the laminated body composed of the layer (1) and the layer (3) include a laminated body of the layer (1) / layer (3) and a laminated body of the layer (1) / layer (3) / layer (1). Body, layer (3) / layer (1) / layer (3) laminate, layer (1) / layer (3) / layer (1) / layer (3) laminate, layer (1) / layer ( 3) / Adhesive layer / Laminate of layer (2) and the like can be mentioned.
[0252]
　Further, as an example of the laminated body composed of the layer (1) and the layer (4), the laminated body of the layer (1) / layer (4) and the layer (1) / layer (4) / layer (1) Laminate, layer (4) / layer (1) / layer (4) laminate, layer (1) / layer (4) / layer (1) / layer (4) laminate, layer (1) / layer (4) / adhesive layer / layer (2) and the like can be exemplified.
[0253]
　The thickness of each layer constituting the laminate of the present invention is not particularly limited, but the layer (1) is usually 0.1 to 30 mm, preferably 1 to 10 mm, and the layer (2) is , Usually 0.1 to 30 mm, preferably 1 to 5 mm, layer (3) is usually 0.1 to 30 mm, preferably 1 to 5 mm, and layer (4) is usually , 0.1 to 30 mm, preferably 1 to 5 mm. The thickness of the entire laminate is not particularly limited, but is usually 5 to 31 mm, preferably 5 to 20 mm. The thickness of the adhesive layer is not particularly limited, but is usually 0.05 to 5 mm, preferably 0.1 to 5 mm.
[0254]
　Further, the laminated body of the present invention is a laminated body in which the layer (2-1) and the layer (2-2) are directly bonded.
[0255]
　The thickness of the layer (2-1) and the layer (2-2) constituting the laminate of the present invention is not particularly limited, but the layer (1) is usually 0.1 to 30 mm, which is preferable. Is 1 to 5 mm, and the layer (2) is usually 0.1 to 30 mm, preferably 1 to 5 mm. The thickness of the entire laminate is not particularly limited, but is usually 2 to 31 mm, preferably 5 to 20 mm.
[0256]
　The laminate of the present invention is not particularly limited to the layer (2-) as long as it has a layer in which the layer (2-1) and the layer (2-2) are directly bonded to each other. Another layer is laminated on the outside of 1) [the surface where the layer (2-2) is not joined] or the outside of the layer (2-2) [the surface where the layer (2-1) is not joined]. You may be.
[0257]
　Further, the laminated body of the present invention is a laminated body in which the layer (3-1) and the layer (3-2) are directly bonded.
[0258]
　The thickness of the layer (3-1) and the layer (3-2) constituting the laminate of the present invention is not particularly limited, but the layer (3-1) is usually 0.1 to 30 mm. The layer (3-2) is usually 0.1 to 30 mm, preferably 1 to 5 mm. The thickness of the entire laminate is not particularly limited, but is usually 1 to 31 mm, preferably 5 to 20 mm.
[0259]
　The laminate of the present invention is not particularly limited to the layer (3-1) as long as it has a layer in which the layer (3-1) and the layer (3-2) are directly bonded to each other. Another layer is laminated on the outside of 1) [the surface where the layer (3-2) is not bonded] or the outside of the layer (3-2) [the surface where the layer (3-1) is not bonded]. You may be.
[0260]
　<
　Method for Producing a Laminated Body > The method for producing a laminated body of the present invention is not particularly limited, and examples thereof include a method for obtaining a laminated body by the following methods (a) to (e). In addition, the crosslinked polymer may be subjected to a cross-linking step after obtaining the laminate by the methods (a) to (e), or a secondary vulcanization step is carried out in an oven or the like after the primary vulcanization. Alternatively, a laminate having a layer containing rubber may be obtained. The layer (1) and at least one layer selected from the layer (2), the layer (2-1) and the layer (3-1) are also referred to as a layer (A), and the layer (3). And at least one layer selected from the layer (4), said layer (2-2) and said layer (3-2) are also referred to as layer (B).
[0261]
　(A) The layer (A) is formed by kneading the material constituting the layer (A) and the material constituting the layer (B) with a mixer such as a kneader, a roll, a Banbury mixer, or an intermixer, and simultaneously extruding the layer (A). A method for obtaining a laminate in which A) and layer (B) are in direct contact with each other.
[0262]
　(B) The material constituting the layer (A) is kneaded with a mixer such as a kneader, a roll, a Banbury mixer, or an intermixer, and extruded by an extruder to form the layer (A), and the layer (B) is formed. The constituent materials are kneaded with a mixer such as a kneader, a roll, a Banbury mixer, or an intermixer, and extruded onto the layer (A) by an extruder so that the layer (A) and the layer (B) are in direct contact with each other. How to get a laminate.
[0263]
　(C) The material constituting the layer (B) is kneaded with a mixer such as a kneader, a roll, a Banbury mixer, or an intermixer, and extruded by an extruder to form the layer (B), and the layer (A) is formed. The constituent materials are kneaded with a mixer such as a kneader, a roll, a Banbury mixer, or an intermixer, and extruded onto the layer (B) by an extruder so that the layer (A) and the layer (B) are in direct contact with each other. How to get a laminate.
[0264]
　(D) The material constituting the layer (A) is kneaded with a mixer such as a kneader, a roll, a Banbury mixer, or an intermixer, and extruded by an extruder to form the layer (A), and the layer (B) is formed. The constituent materials are kneaded with a mixer such as a kneader, a roll, a Banbury mixer, or an intermixer, and extruded by an extruder to form a layer (B), and the layer (A) and the layer (B) are directly connected. A method of obtaining a laminate in which a layer (A) and a layer (B) are in contact with each other via an adhesive layer by adhering.
[0265]
　(E) The material constituting the layer (A) is kneaded with a mixer such as a kneader, a roll, a Banbury mixer, and an intermixer, and extruded by an extruder to form the layer (A), and the layer (B) is formed. The constituent materials are kneaded with a mixer such as a kneader, a roll, a Banbury mixer, or an intermixer, and extruded by an extruder to form a layer (B), and the layer (A) and the layer (B) are adhered to each other. A method of obtaining a laminate in which a layer (A) and a layer (B) are in contact with each other via an adhesive layer by adhering with an agent.
[0266]
　In the production of the laminated body, the layer (A) and the layer (B) are press-molded by press-molding the laminated body in which the layer (A) and the layer (B) are in contact with each other directly or via an adhesive layer. It is preferable from the viewpoint of increasing the peel strength from B).
[0267]
　[Crossing step,
　primary vulcanization ] In the cross-linking step or the primary vulcanization, components necessary for cross-linking such as a cross-linking agent are mixed in advance with the materials constituting the layers (A) and (B). Examples thereof include a step of performing cross-linking by heating (for example, 150 to 240 ° C.) and a step of performing cross-linking by irradiating the laminate with an electron beam (for example, an electron beam having an energy of 0.1 to 10 MeV). The electron beam irradiation is performed so that the absorbed dose of the laminated body is usually 0.5 to 36 Mrad, preferably 0.5 to 20 Mrad, and more preferably 1 to 10 Mrad.
[0268]
　In the cross-linking step or the primary vulcanization, when cross-linking by heating, it is preferable to heat while performing press molding from the viewpoint of increasing the peel strength between the layer (A) and the layer (B). ..
[0269]
　[
　Secondary vulcanization ] The secondary vulcanization is a step performed after the primary vulcanization, and is a step of sufficiently promoting vulcanization (crosslinking) by heating (for example, 150 to 200 ° C.). be.
[0270]
　
　The laminate of the present invention can be used for various purposes because it can satisfy various required characteristics depending on its layer structure.
[0271]
　The laminate of the present invention can be used for various purposes. The laminate of the present invention can be used as a member for, for example, an automobile, a motorbike, an industrial machine, a construction machine, or an agricultural machine. Specific examples of the member include industrial rolls, packings (for example, condenser packings), gaskets, belts (for example, heat insulating belts, copying machine belts, electric wires), hoses such as automobile hoses (for example, turbocharger hoses, etc.). Water hose, brake reservoir hose, radiator hose, air hose), anti-vibration rubber, anti-vibration material or anti-vibration material (for example, engine mount, motor mount), muffler hanger, cable (ignition cable, cab tire cable, high tension cable) ), Electric wire coating material (high-voltage electric wire coating material, low-voltage electric wire coating material, marine electric wire coating material), glass run channel, color skin material, paper feed roll, roofing sheet and the like.
[0272]
　Further, since the ethylene / α-olefin / non-conjugated polyene copolymer is excellent in moldability and cross-linking characteristics and can be obtained as a cross-linked product having excellent heat stability, it is possible to obtain a cross-linked product by having the layer (1). Can also be suitably used for applications that are expected to be used for a long period of time at high temperatures. When the ethylene / α-olefin / non-conjugated polyene copolymer is an ethylene / α-olefin / VNB copolymer, it is particularly excellent in fatigue resistance, so that it can be used for a long period of time under harsh conditions. It is preferable because it can withstand.
[0273]
　Among these, the laminate of the present invention is suitably used for interior / exterior parts for automobiles and applications requiring heat resistance. Applications of the laminate include, for example, a hose having the laminate of the present invention as at least a part thereof. The hose is not limited in its use, but is preferably used for any of automobiles, motorbikes, industrial machines, construction machines, and agricultural machines. More specifically, a turbocharger hose, a brake reservoir hose, a radiator hose and the like can be mentioned, and it is particularly preferable that the hose is used for an automobile turbocharger hose.
[0274]
　The hose of the present invention may have the laminate of the present invention as at least a part thereof, and may be a hose formed only from the laminate of the present invention.
[0275]
　The turbocharger hose of the present invention is preferably a layer or layer formed from a crosslinked product of a composition containing an ethylene / α-olefin / non-conjugated polyene copolymer in order to withstand severe operating conditions of high temperature and high pressure. It has a multi-layer structure having 2-1) or a layer (3-1) and a layer made of another material.
[0276]
　In the hose of the present invention, only one layer may be a crosslinked body, or two or more layers may be formed from a crosslinked body.
[0277]
　The method for manufacturing the turbocharger hose of the present invention is not particularly limited, and for example, an uncured turbocharger hose having a layered structure by extrusion molding, coextrusion molding, wrapping of a sheet-like material, or a combination thereof ( A method of obtaining a turbocharger hose (laminate) by molding the laminate) and heating it with steam or the like can be mentioned. The uncured turbocharger hose preferably has a high ability to retain its shape without shrinking or deforming.
Example
[0278]
　Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0279]
　The physical properties of the copolymers, copolymer compositions, halogen-containing polymers and the like used in Examples 1 to 20 and Comparative Example 1 were measured by the following methods.
[0280]
　(Measurement / evaluation method)
　(Composition of ethylene / α-olefin / non-conjugated polyene copolymer and B value)
　Mass fraction (mass percentage) of each constituent unit of ethylene / α-olefin / non-conjugated polyene copolymer ) And B value were determined by the measured values ​​by 13 C-NMR. The measured values ​​were measured using an ECX400P type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.) at a measurement temperature of 120 ° C., a measurement solvent: orthodichlorobenzene / deuterated benzene = 4/1, and an integration number of 8000 times. It was obtained by measuring the 13 C-NMR spectrum of the polymer .
[0281]
　(Ultimate viscosity [η])
　The ultimate viscosity [η] (dl / g) of ethylene / α-olefin / non-conjugated polyene copolymer is determined by using a fully automatic ultimate viscometer manufactured by Rigo Co., Ltd., and the temperature: 135. ℃, measurement solvent: Decalin was used for measurement.
[0282]
　(Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn))
　Weight average molecular weight (Mw) of ethylene / α-olefin / non-conjugated polyene copolymer, number average molecular weight (Mn), The molecular weight distribution (Mw / Mn) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). The measuring device and conditions are as follows. In addition, the molecular weight was calculated based on a conversion method by preparing a calibration line using a commercially available monodisperse polystyrene.
[0283]
　Equipment: Gel permeation chromatograph Alliance GP2000 type (manufactured by Waters),
　Analyzer: Emper2 (manufactured by Waters),
　Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (7.5 mm ID x 30 cm, Tosoh Co., Ltd.) ),
　Column temperature: 140 ° C.,
　Mobile phase: o-dichlorobenzene (containing 0.025% BHT),
　Detector: Differential refractometer (RI), Flow velocity: 1.0 mL / min,
　Injection volume: 400 μL ,
　Sampling time Interval: 1s,
　Column calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation),
　Molecular weight conversion: Old method EPR conversion / Calibration method considering viscosity.
[0284]
　(Adhesive strength)
　The adhesive strength (peeling strength) of the laminated body was measured by the following method.
[0285]
　The laminates obtained in Examples and Comparative Examples were subjected to a T-type peeling test at a measurement temperature: 23.0 ° C., a test speed: 200.0 mm / min, and a test piece width: 25.0 mm, and peel strength (N). / Cm) was measured.
[0286]
　[Production of ethylene / α-olefin / non-conjugated polyene copolymer]
　[Production example 1]
　Ethylene, propylene, 5-vinyl-2-norbornene were continuously used using a polymerizer having a volume of 300 L equipped with a stirring blade. The polymerization reaction of (VNB) was carried out at 87 ° C.
[0287]
　Using hexane (feed amount: 32.6 L / h) as the polymerization solvent, the ethylene feed amount was 3.6 kg / h, the propylene amount was 6.1 kg / h, and the VNB feed amount was 290 g / h. It was continuously supplied to the polymer so that the hydrogen feed amount was 6.3 NL / h.
[0288]
　Feed amount using di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride as the main catalyst while maintaining the polymerization pressure at 1.6 MPaG and the polymerization temperature at 87 ° C. It was continuously supplied to the polymerizer so as to be 0.0015 mmol / h. In addition, (C 6 H 5 ) 3 CB (C 6 F 5 ) 4 (CB-3) as a cocatalyst has a feed amount of 0.0075 mmol / h, and triisobutylaluminum (TIBA) as an organoaluminum compound has a feed amount of 20 mmol / h. Each was continuously supplied to the polymerizer so as to be.
[0289]
　In this way, a solution containing 15.2% by mass of an ethylene / propylene / VNB copolymer formed from ethylene, propylene and VNB was obtained. A small amount of methanol was added to the polymerization reaction solution extracted from the lower part of the polymer to stop the polymerization reaction, the ethylene / propylene / VNB copolymer was separated from the solvent by steam stripping treatment, and then the pressure was reduced at 80 ° C. for 24 hours. It was dry.
[0290]
　By the above operation, an ethylene / propylene / VNB copolymer (A-1) formed from ethylene, propylene and VNB was obtained at a rate of 4.7 kg / h.
[0291]
　The physical characteristics of the obtained copolymer (A-1) were measured by the method described above. The results are shown in Table 1.
[0292]
[Table 1]

　[Example 1] As
　the first step, the ethylene / propylene / VNB copolymer (A-1) 100 obtained in Production Example 1 was used using a BB-2 type Banbury mixer (manufactured by Kobe Steel Co., Ltd.). Knead the parts by mass for 30 seconds, then add 1 part by mass of stearic acid, 45 parts by mass of carbon black (Asahi # 60G, manufactured by Asahi Carbon Co., Ltd.), and carbon black (Asahi # 50G, manufactured by Asahi Carbon Co., Ltd.). 45 parts by mass of carbon black (Asahi # 15HS, Asahi Carbon Co., Ltd.) 40 parts by mass, paraffin-based process oil (Diana Process PS-430, manufactured by Idemitsu Kosan Co., Ltd.) 47 parts by mass, and aging 4 parts by mass of an inhibitor (Nocrack CD, manufactured by Ouchi Shinko Kagaku Co., Ltd.) was added, and the mixture was kneaded at 140 ° C. for 2 minutes. Then, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain the first-stage formulation.
[0293]
　Next, as the second step, the formulation obtained in the first step is subjected to 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll. 1 part by mass of calcium hydroxide (NICC-5000, manufactured by Inoue Lime Industry Co., Ltd.), dialkyl peroxide (Perhexa 25B-40, Nikko). 3 parts by mass of (manufactured by Seiko Kagaku Co., Ltd.) and 3 parts by mass of a cross-linking aid (Trimethylolpropane-trimethacrylate) (High Cross M, manufactured by Seiko Kagaku Co., Ltd.) were added and kneaded for 10 minutes to obtain an uncrosslinked copolymer composition.
[0294]
　<< Preparation of 　Fluorine-based Polymer Composition Forming Layer (4) >>
　(Fluorine-Based Polymer Composition) As the
fluorine-based polymer composition, Daiel DC-2270F (manufactured by Daikin Industries: polyol cross-linked fluororubber compound) is used. Using.
[0295]
　Daiel DC-2270F is a composition containing a polyol-based cross-linking agent (bisphenol AF), a cross-linking accelerator (quaternary onium salt), a filler, and an acid-receiving agent in addition to the fluorine-based polymer.
[0296]
　<< Molding of Laminated Body and Evaluation of Adhesive Strength >>
　(Preparation of Laminated Body for T-Type Peeling Test) The
　above-mentioned copolymer composition and the above-mentioned fluorine-based polymer composition were separated into sheets. Next, 50 g of the uncrosslinked sheet (copolymer composition and fluorine-based polymer composition) dispensed v was individually sanded up and down with Lumilar (trade name) (stretched polyester (polyethylene terephthalate) film), and 120 Pre-molded with a 50-ton press at ° C. for 2 minutes to prepare an uncrosslinked sheet having t (thickness) = 1 mm and 20 cm square.
[0297]
　Next, the uncrosslinked sheet [layer (1)] obtained from the copolymer composition and the uncrosslinked sheet [layer (4)] obtained from the fluorine-based polymer composition after the pressing was performed. Was cut into the main press dimensions (15 cm × 15 cm × t = 1 mm) described later. After cutting, the upper and lower Lumirror films were peeled off, and then the respective uncrosslinked sheets were laminated. When stacking, the uncrosslinked sheet is stacked with the Lumirror film (t = 0.2 mm) sandwiched between a part of the uncrosslinked sheet (width 3 cm, length 15 cm: gripping margin during the peeling test). I matched it.
[0298]
　The laminated uncrosslinked sheet in which the Lumirror film is sandwiched in a part thereof is pressed (main press) at 180 ° C. for 10 minutes using a 100 ton press molding machine to obtain a crosslinked sheet (laminated body) having a thickness of 2 mm. Molded.
[0299]
　The Lumirror film was removed from the crosslinked sheet (laminated body), and the crosslinked sheet (laminated body) was subjected to a T-type peeling test by the method described above to measure the adhesive strength.
[0300]
　The results are shown in Table 2-1.
[0301]
　[Examples 2 to 20] A
　copolymer composition obtained by adding various compounding agents in the blending amounts shown in Table 1 in place of the copolymer composition forming the layer (1) used in Example 1. A laminate was prepared in the same manner as in Example 1, and a T-type peeling test was performed by the method described in Example 1 to measure the adhesive strength.
[0302]
　The compounding agents newly compounded in Examples 2 to 20 are the following compounding agents.
[0303]
　Hydrotalcite (DHT-4A (registered trademark), manufactured by Kyowa Chemical Industry Co., Ltd.), magnesium hydroxide (Kisuma (registered trademark) 5B, manufactured by Kyowa Chemical Industry Co., Ltd.), aluminum hydroxide (Heidilite (registered trademark)) ) H-42, Showa Denko Co., Ltd.), Di-cured beef fat alkyldimethylammonium chloride (Lipocard 2HT flakes (trade name), Lion Specialty Chemicals Co., Ltd.) and magnesium oxide (Kyowa Mag (registered trademark) 150) , Made by Kyowa Chemical Industry Co., Ltd.
[0304]
　The results are shown in Table 2-1 and Table 2-2.
[0305]
　[Comparative Example 1]
　Instead of the copolymer composition forming the layer (1) used in Example 1, the blending amount shown in Table 1 [does not blend the inorganic compound (E) such as calcium hydroxide]. A laminate was prepared in the same manner as in Example 1 except that it was used, and a T-type peeling test was performed by the method described in Example 1 to measure the adhesive strength.
[0306]
　The results are shown in Table 2-2.
[0307]
[Table 2-1]

[0308]
[Table 2-2]

　(Measurement / Evaluation Method) In the
　following production examples, Examples 21 to 26 and Comparative Example 2, the measurement and evaluation methods of each characteristic are as follows.
[0309]
　(T-type peeling test)
　The peeling strength of the laminated body was measured by the following method.
[0310]
　The laminates obtained in Examples and Comparative Examples were subjected to a T-type peeling test at a measurement temperature: 23.0 ° C., a test speed: 200.0 mm / min, and a test piece width: 80.0 mm, and the peel strength was measured. bottom.
[0311]
　The acrylic rubber (A), halogen-containing polymer (C), and the like used in Examples and Comparative Examples of the present invention are shown below.
[0312]

　<< 　Acrylic rubber (A) >> Nipol AR-12: Acrylic rubber
　containing alkyl acrylate as the main component of the skeleton, manufactured by Nippon Zeon Corporation (hereinafter referred to as ACM )
　<< Halogen-containing polymer (C) >>
　Daiel DC-2270F: Full compound, binary polyol vulcanization system, specific gravity 1.85, ML (1 + 10) 100 ° C.: Approx. 115, manufactured by Daikin Industries Co., Ltd.
　Daiel DC-2270F is also referred to as "polylate-based FKM".
[0313]
　[Example 21]
　<< Preparation of ACM composition forming layer (2-1) >> As
　the first step, 100 parts by mass of ACM was applied for 30 seconds using a BB-2 type Banbury mixer (manufactured by Kobe Steel). After kneading, 60 parts by mass of HAF carbon black (Asahi # 70G, manufactured by Asahi Carbon Co., Ltd.) and 1 part by mass of stearic acid were added thereto, and the mixture was kneaded at 140 ° C. for 2 minutes. Then, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain the first-stage formulation.
[0314]
　Next, as the second step, the formulation obtained in the first step is subjected to 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll). 5 parts by mass of calcium hydroxide (NICC-5000, manufactured by Inoue Lime Industry Co., Ltd.) 2 parts by mass of 4,4'-bis (α, α) -Dimethylbenzyl) diphenylamine (Nocrack CD, manufactured by Ouchi Shinko Kagaku Co., Ltd.), 1 part by mass of polyoxyethylene stearyl ether phosphate (Fuosphanol RL-210: manufactured by Toho Kagaku Kogyo Co., Ltd.), 0.5 Parts of (6-aminohexyl) carbamic acid (Diak No. 1: manufactured by DuPont), 2 parts by mass of 1,3-di-o-tolylguanidine (Noxeller DT, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) Was added and kneaded for 10 minutes to obtain an uncrosslinked rubber composition (rubber formulation) (composition containing ACM).
[0315]
　<< Preparation of 　Fluorine-based Polymer Composition Forming Layer (2-2) >>
　(Fluorine-Based Polymer Composition) As a
fluorine-based polymer composition, Daiel DC-2270F (manufactured by Daikin Industries: polyol cross-linked fluororubber compound) ) Was used. Daiel DC-2270F is a composition containing a polyol-based cross-linking agent (bisphenol AF), a cross-linking accelerator (quaternary onium salt), a filler, and an acid receiving agent in addition to fluororubber.
[0316]
　<< Preparation and Evaluation of Laminates >>
　( Preparation of Laminates for T-type Peeling Test)
　The composition containing the ACM and the fluorine-based polymer composition were separated into sheets. Next, 50 g of the unvulcanized rubber sheet (composition containing ACM and fluorine-based polymer composition) that had been dispensed was individually sanded up and down with Lumirror (trade name) (stretched polyester (polyethylene terephthalate) film). Each uncrosslinked sheet whose top and bottom were sanded with a lumirror film was pressed at 120 ° C. for 2 minutes using a 50 ton press molding machine to prepare an uncrosslinked sheet having t (thickness) = 1 mm and 20 cm square.
[0317]
　Next, the uncrosslinked sheet [layer (2-1)] obtained from the composition containing ACM and the uncrosslinked sheet [layer] obtained from the fluorine-based polymer composition after the pressing was performed. (2-2)] were cut into the main press dimensions (15 cm × 15 cm × t = 1 mm) described later. After cutting, the upper and lower Lumirror films were peeled off, and then the respective uncrosslinked sheets were laminated. When stacking, the uncrosslinked sheets were superposed with the Lumirror film sandwiched between a part of the uncrosslinked sheets (width 3 cm, length 15 cm: gripping margin during the peeling test).
[0318]
　The laminated uncrosslinked sheet in which the Lumirror film is sandwiched in a part thereof is pressed (main press) at 180 ° C. for 10 minutes using a 100 ton press molding machine to obtain a crosslinked sheet (laminated body) having a thickness of 2 mm. It was adjusted.
[0319]
　The Lumirror film was removed from the crosslinked sheet (laminated body), and a T-type peeling test was performed on the crosslinked sheet (laminated body) by the method described above.
[0320]
　The results are shown in Table 3.
[0321]
　[Examples 22 to 26]
　Instead of the ACM composition forming the layer (2-1) used in Example 21, the ACM composition obtained by adding various compounding agents in the blending amounts shown in Table 3 is used. A laminate was prepared in the same manner as in Example 21 except for the above, and a T-type peeling test was conducted by the method described in Example 21.
[0322]
　Kisma 5B blended in the ACM composition of layer (2-1) in Example 26 is a trade name of magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd.
[0323]
　The results are shown in Table 3.
[0324]
　[Comparative Example 2]
　Instead of the ACM composition forming the layer (2-1) used in Example 21, the blending amount shown in Table 3 [inorganic compound (B) such as calcium hydroxide is not blended] is used. A laminate was prepared in the same manner as in Example 21 except that it was used, and a T-type peeling test was conducted by the method described in Example 21.
[0325]
　The results are shown in Table 3.
[0326]
[Table 3]

　(Measurement / Evaluation Method) In the
　following production examples, Examples 27 to 32 and Comparative Example 3, the measurement and evaluation methods of each characteristic are as follows.
[0327]
　(T-type peeling test)
　The peeling strength of the laminated body was measured by the following method.
[0328]
　The laminates obtained in Examples and Comparative Examples were subjected to a T-type peeling test at a measurement temperature: 23.0 ° C., a test speed: 200.0 mm / min, and a test piece width: 80.0 mm, and the peel strength was measured. bottom.
[0329]
　The epichlorohydrin rubber (A), halogen-containing polymer (C), and the like used in Examples and Comparative Examples of the present invention are shown below.
[0330]

　<< Epichlorohydrin 　rubber (A) >> Epichromer H: Epichlorohydrin rubber, Osaka Soda Co., Ltd. (hereinafter referred to as ECO
　)
　<< Halogen-containing polymer (C) >>
　Daiel DC-2270F: Full compound , Binary polyol vulcanization system, specific gravity 1.85, ML (1 + 10) 100 ° C.: Approx. 115, manufactured by Daikin Industries, Ltd.
　Daiel DC-2270F is also referred to as "polypolymer-based FKM".
[0331]
　[Example 27]
　<< Preparation of ECO composition forming layer (3-1) >> As
　the first step, 100 parts by mass of ECO was applied for 30 seconds using a BB-2 type Banbury mixer (manufactured by Kobe Steel). Kneaded, then 40 parts by mass of MAF carbon black (Seast 116, manufactured by Tokai Carbon Co., Ltd.), 1 part by mass of nickel dibutyldithiocarbamate (Nocrack NBC, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) , 5 parts by mass of heavy calcium carbonate (Whiten SB (red), manufactured by Shiraishi Calcium Co., Ltd.) and 1 part by mass of stearic acid were added and kneaded at 140 ° C. for 2 minutes. Then, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain the first-stage formulation.
[0332]
　Next, as the second step, the compound obtained in the first step is subjected to 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll). 5 parts by mass of calcium hydroxide (NICC-5000, manufactured by Inoue Lime Industry Co., Ltd.) 3 parts by mass of di-cured beef fat alkyldimethylammonium chloride (lipo) Card 2HT flakes, manufactured by Lion Specialty Chemicals Co., Ltd., 1.2 parts by mass 2,4,6-trimercapto-S-triazine (Noxeller TCA, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.), 0. 5 parts by mass of tetramethylthiuram disulfide (Noxeller TT, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) was added and kneaded for 10 minutes to obtain an uncrosslinked composition (composition containing ECO).
[0333]
　<< Preparation of 　Fluorine-based Polymer Composition Forming Layer (3-2) >>
　(Fluorine-Based Polymer Composition) As a
fluorine-based polymer composition, Daiel DC-2270F (manufactured by Daikin Industries: polyol cross-linked fluororubber compound) ) Was used. Daiel DC-2270F is a composition containing a polyol-based cross-linking agent (bisphenol AF), a cross-linking accelerator (quaternary onium salt), a filler, and an acid-receiving agent in addition to the fluorine-based polymer.
[0334]
　<< Preparation and Evaluation of Laminates >>
　( Preparation of Laminates for T-type Peeling Test)
　The composition containing the ECO and the fluorine-based polymer composition were separated into sheets. Next, 50 g of the uncrosslinked sheet (composition containing ECO and fluorine-based polymer composition) separated was individually sanded up and down with a rubber mirror (trade name) (stretched polyester (polyethylene terephthalate) film) at 120 ° C. Premolded with a 50-ton press for 2 minutes to prepare an unvulcanized rubber sheet having t (thickness) = 1 mm and 20 cm square.
[0335]
　Next, after the pressing, the unvulcanized sheet [layer (3-1)] obtained from the composition containing ECO and the uncrosslinked sheet obtained from the fluorine-based polymer composition [ The layer (3-2)] was cut into the main press dimensions (15 cm × 15 cm × t = 1 mm) described later. After cutting, the upper and lower rumirrors were peeled off, and then the respective uncrosslinked sheets were overlapped. When stacking, the uncrosslinked sheet is stacked with the Lumirror film (t = 0.2 mm) sandwiched between a part of the uncrosslinked sheet (width 3 cm, length 15 cm: gripping margin during the peeling test). I matched it.
[0336]
　The laminated uncrosslinked sheet in which the Lumirror film is sandwiched in a part thereof is pressed (main press) at 180 ° C. for 10 minutes using a 100 ton press molding machine to obtain a crosslinked sheet (laminated body) having a thickness of 2 mm. It was adjusted.
[0337]
　The Lumirror film was removed from the crosslinked sheet (laminated body), and a T-type peeling test was performed on the crosslinked sheet (laminated body) by the method described above.
[0338]
　The results are shown in Table 4.
[0339]
　[Examples 28 to 32]
　Instead of the ECO composition forming the layer (3-1) used in Example 27, an ECO composition obtained by adding various compounding agents in the blending amounts shown in Table 4 is used. A laminate was prepared in the same manner as in Example 27 except for the above, and a T-type peeling test was conducted by the method described in Example 27.
[0340]
　The results are shown in Table 4.
[0341]
　[Comparative Example 3]
　Instead of the ECO composition forming the layer (3-1) used in Example 27, the blending amount shown in Table 3 [inorganic compound (B) such as calcium hydroxide is not blended] is used. A laminate was prepared in the same manner as in Example 27 except that it was used, and a T-type peeling test was conducted by the method described in Example 27.
[0342]
　The results are shown in Table 4.
[0343]
[Table 4]

The scope of the claims
[Claim 1]
　A laminate comprising a layer (A) and a layer (B).
　Layer (A): A layer containing one or more polymers selected from the following polymers:
　ethylene / α-olefin / non-conjugated polyene copolymer, ethylene / carboxylic acid copolymer, acrylic rubber, and epichlorohydrin rubber. Rubber
　layer (B): A layer
　acrylic rubber containing one or more polymers selected from the following polymers , and a halogen-containing polymer.
[Claim 2]
　At least one layer in which the layer (A) is selected from the following layers (1) and (2), and at least one in which the layer (B) is selected from the following layers (3) and (4). A laminate containing one type of layer,
　selected from at least one layer (A), layer (3), and layer (4) of at least one type of layer selected from the layer (1) and layer (2). The laminate according to claim 1, wherein at least one layer (B) of at least one layer to be formed is in direct contact with or is in contact with each other via an adhesive layer.
　Layer (A)
　Layer (1): Ethylene / α-olefin / non-conjugated polyene copolymer, the ethylene / α-olefin / non-conjugated polyene copolymer: From Group 2 element and Group 13 element with respect to 100 parts by mass A layer comprising a copolymer composition containing 0.1 to 30 parts by mass of an inorganic compound (E) containing at least one selected element and a hydroxyl group.
　Layer (2): A layer made of an ethylene / carboxylic acid copolymer.
　Layer (B)
　Layer (3): A layer made of acrylic rubber.
　Layer (4): A layer made of a halogen-containing polymer.
[Claim 3]
　2. The layer (1) further contains 0.2 parts by mass or more and 10 parts by mass or less of an onium salt with respect to 100 parts by mass of an ethylene / α-olefin / non-conjugated polyene copolymer. The laminate described in.
[Claim 4]
　The layer (2) contains 0.2 parts by mass or more of the onium salt per 100 parts by mass of the ethylene-carboxylic acid copolymer, and at least one element selected from Group 2 and Group 13 elements and a hydroxyl group. The laminate according to claim 2, wherein the inorganic compound is contained in an amount of 7 parts by mass or more per 100 parts by mass of the ethylene / carboxylic acid copolymer.
[Claim 5]
　The layer (2) contains an onium salt of 0.2 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the ethylene-carboxylic acid copolymer and at least one element selected from Group 2 and Group 13 elements. The laminate according to claim 2, wherein the inorganic compound containing a hydroxyl group is contained in an amount of 7 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the ethylene / carboxylic acid copolymer.
[Claim 6]
　The laminate according to any one of claims 2 to 5, wherein the layer (1) and the layer (4) are directly adhered to each other.
[Claim 7]
　Claims 2 to 2, wherein at least one layer (A) selected from the layer (1) and the layer (2) and the layer (3) are adhered to each other via an adhesive layer. 5. The laminate according to any one of 5.
[Claim 8]
　The laminate according to any one of claims 2 to 7, wherein the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the following requirements (I) to (III).
　Requirement (I): The molar ratio (ethylene / α-olefin) of the structural unit derived from ethylene to the structural unit derived from α-olefin is 40/60 to 99.9 / 0.1.
　Requirement (II): The constituent unit derived from the non-conjugated polyene is 0.07 to 10% by mass in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer.
　Requirement (III): The ultimate viscosity [η] measured in decalin at 135 ° C. is 1.0 to 4.0 dl / g.
[Claim 9]
　The laminate according to any one of claims 2 to 8, wherein the ethylene / α-olefin / non-conjugated polyene copolymer has a structural unit derived from 5-vinyl-2-norbornene (VNB).
[Claim 10]
　The laminate according to any one of claims 2 to 9, wherein the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the following requirement (IV).
　Requirement (IV): The B value represented by the following formula (i) is 1.20 or more.
　　B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] ... (i)
[Here, [E], [X] and [Y] are , Respectively, show the mole fractions of ethylene, α-olefin, and non-conjugated polyene, and [EX] shows the ethylene-α-olefin diad chain fraction. ]
[Claim 11]
　The layer (A) according to claim 1 is the following layer (2-1), the layer (B) is the following layer (2-2), and the layer (2-1) and the following layer (2-2). ) Is directly joined to the laminated body according to claim 1.
　Layer (2-1): Acrylic rubber (A), and (A): Inorganic compound containing at least one element selected from Group 2 element and Group 13 element and a hydroxyl group with respect to 100 parts by mass. A layer composed of a composition containing 1 to 30 parts by mass of (B).
　Layer (2-2): Halogen-containing polymer (C) [However, the acrylic rubber of layer (2-1) is excluded. ] A layer consisting of.
[Claim 12]
　The laminate according to claim 11, wherein the halogen-containing polymer (C) is a fluorine-based polymer.
[Claim 13]
　The laminate according to claim 12, wherein the halogen-containing polymer (C) of the layer (2-2) is crosslinked with a polyol-based crosslinking agent.
[Claim 14]
　The layer (A) according to claim 1 is the following layer (3-1), the layer (B) is the following layer (3-2), and the layer (3-1) and the following layer (3-2). ) Is directly joined to the laminated body according to claim 1.
　Layer (3-1): Epichlorohydrin rubber (A), said (A): Inorganic compound containing at least one element selected from Group 2 element and Group 13 element and a hydroxyl group with respect to 100 parts by mass. A layer composed of a composition containing 1 to 30 parts by mass of (B) and 0.2 parts by mass or more and 10 parts by mass or less of an onium salt.
　Layer (3-2): Halogen-containing polymer (C) [However, the epichlorohydrin rubber of layer (1) is excluded. ] A layer consisting of.
[Claim 15]
　The laminate according to claim 14, wherein the halogen-containing polymer (C) is a fluorine-based polymer.
[Claim 16]
　The laminate according to claim 15, wherein the halogen-containing polymer (C) of the layer (3-2) is crosslinked with a polyol-based crosslinking agent.
[Claim 17]
　A hose having at least a part of the laminate according to any one of claims 1 to 16.
[Claim 18]
　The hose according to claim 17, which is used for any of automobiles, motorbikes, industrial machines, construction machines, and agricultural machines.
[Claim 19]
　The hose according to claim 18, which is used for an automobile turbocharger hose.