JP2015231717A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate in which a rubber layer and a fluorine resin layer are firmly stuck without using adhesives and without applying surface treatment to each layer of the rubber layer and the fluorine resin layer, and having excellent heat resistance.SOLUTION: Provided is a laminate including : a rubber layer (A); and a fluororesin layer (B) laminated on the rubber layer (A). The rubber layer (A) is a layer formed of a rubber composition for vulcanization, the rubber composition for vulcanization comprises at least two kinds of age resistors (a3) selected from the group consisting of an aromatic secondary amine base age resistor, a bisphenol base age resistor, a benzimidazole base age resistor and a thiourea base age resistor, etc., the fluororesin layer (B) is a layer formed from a fluorine polymer composition, and the fluorine polymer composition includes a fluorine polymer (b1) having a polymerization unit derived from chlorotrifluoroethylene.

Description

The present invention relates to a laminate.

Conventionally, due to the recent increase in environmental awareness, the development of laws to prevent fuel volatilization has progressed. Especially in the automobile industry, there is a significant tendency to suppress fuel volatilization, especially in the United States, and there is a great need for materials with excellent fuel barrier properties. It is becoming.

In particular, in fuel transportation rubber hoses, laminated hoses with a fluororesin as a barrier layer (rubber other than the barrier layer) are used in order to improve fuel low permeability, but due to the recent strong demand for reducing environmental impact, The barrier layer requires one layer of low fuel permeability. Attempts have been made to secure low permeability by increasing the thickness of the barrier layer or by using a perhalogen fluororesin that is most excellent in low transmission. However, increasing the thickness of the barrier layer (fluorine resin) increases the weight of the hose and is also disadvantageous from the viewpoint of energy saving. Further, the bendability (flexibility) of the hose itself is impaired, and handling properties ( It is also disadvantageous from the viewpoint of assembly.

In addition, when using a perhalogen-based fluororesin as a barrier layer, it is difficult to adhere to the rubber of the outer and inner layers, which is the counterpart material, and surface treatment of the resin to improve adhesion, film or tape A process such as a wrapping method is required, which complicates the work process, significantly lowers productivity, and has a problem in practical use such as a significant increase in cost.

In order to improve the adhesion between the fluororesin layer and the rubber layer, for example, Patent Document 1 discloses a rubber layer formed from a rubber composition for vulcanization containing a specific additive and chlorotrifluoroethylene. A laminate comprising a fluororesin layer formed from a fluoropolymer composition containing a fluoropolymer having polymerized units has been proposed.

In Patent Documents 2 and 3, hydrogenated acrylonitrile butadiene rubber (H-NBR) and acrylic rubber (ACM) containing specific additives are peroxide vulcanized to impart heat resistance. A heat-resistant rubber vulcanization adhesion method and a heat-resistant fuel hose have been proposed which are firmly vulcanized and bonded.

Further, as in Patent Document 4, the heat resistance of the rubber composition layer is improved by blending EPDM (ethylene-propylene-diene terpolymer rubber) with NBR (acrylonitrile-butadiene rubber). A laminate is known in which a rubber composition layer and a fluororesin layer are directly bonded by vulcanization adhesion by containing a specific additive in the composition layer. However, there is a problem that the manufacturing process becomes complicated due to the process of blending rubber.

International Publication No. 2011/001756 JP 2003-286351 A Japanese Patent No. 3941022 Japanese Patent No. 3804386

In view of the current situation, the present invention is excellent in that the rubber layer and the fluororesin layer are firmly bonded without using an adhesive and without subjecting each of the rubber layer and the fluororesin layer to surface treatment. It aims at providing the laminated body which has heat resistance.

The present inventors have found that the above problem can be solved when the rubber layer constituting the laminate contains a specific amount of a specific anti-aging agent, and has completed the present invention.

That is, the present invention is a laminate comprising a rubber layer (A) and a fluororesin layer (B) laminated on the rubber layer (A), wherein the rubber layer (A) is a rubber for vulcanization. It is a layer formed from the composition, and the vulcanized rubber composition comprises unvulcanized rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7, 8-benzyl-1,8- Diazabicyclo (5.4.0) -7-undecenium chloride, 1,8-diazabicyclo (5.4.0) undecene-7 naphthoate, 1,8-diazabicyclo (5.4.0) undecene- 7 phenol salt, 1,8-diazabicyclo (5.4.0) undecene-7 orthophthalate, 1,8-diazabicyclo (5.4.0) undecene-7 formate, and 1,5- From the group consisting of diazabicyclo (4.3.0) nonene-5 At least 2 selected from the group consisting of at least one compound (a2) selected, an aromatic secondary amine antioxidant, a bisphenol antioxidant, a benzimidazole antioxidant, and a thiourea antioxidant An anti-aging agent comprising a combination of seeds (a3), magnesium oxide (a4), and silica (a5) is contained, and the fluororesin layer (B) is a layer formed from a fluoropolymer composition. The composition is a laminate characterized by containing a fluoropolymer (b1) having polymerized units derived from chlorotrifluoroethylene.

It is preferable that an anti-aging agent (a3) is 0.01-5 mass parts per 1 type with respect to 100 mass parts of unvulcanized rubber (a1).

The anti-aging agent (a3) is composed of at least two kinds selected from the group consisting of an aromatic secondary amine type anti-aging agent, a bisphenol type anti-aging agent and a benzimidazole type anti-aging agent. a3) is preferably 2 to 9 parts by mass in total with respect to 100 parts by mass of the unvulcanized rubber (a1).

Anti-aging agent (a3) is a combination of an aromatic secondary amine anti-aging agent and a bisphenol anti-aging agent, a combination of an aromatic secondary amine anti-aging agent and a benzimidazole anti-aging agent, bisphenol A combination of an anti-aging agent and a benzimidazole anti-aging agent, or a combination of an aromatic secondary amine anti-aging agent, a bisphenol anti-aging agent and a benzimidazole anti-aging agent, The secondary amine-based antioxidant is 0.1 to 5 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1), and the bisphenol-based antioxidant is 100 parts by mass of the unvulcanized rubber (a1). 0.1 to 3 parts by mass with respect to parts, and the benzimidazole anti-aging agent is 0.1 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). It is preferable.

The anti-aging agent (a3) is a combination of at least one anti-aging agent selected from the group consisting of an aromatic secondary amine anti-aging agent and a bisphenol anti-aging agent and a benzimidazole anti-aging agent. And at least one anti-aging agent selected from the group consisting of the aromatic secondary amine anti-aging agent and the bisphenol anti-aging agent is 100 parts by mass of the unvulcanized rubber (a1), It is 1-6 mass parts in total, and it is preferable that the said benzimidazole type anti-aging agent is 1-3 mass parts with respect to 100 mass parts of unvulcanized rubber (a1).

The unvulcanized rubber (a1) is preferably acrylonitrile-butadiene rubber or a hydride thereof.

The fluoropolymer (b1) is preferably a chlorotrifluoroethylene-tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer.

Since the laminate of the present invention has the above-described configuration, the rubber layer and the fluororesin layer are firmly bonded without using an adhesive and without subjecting the rubber layer and the fluororesin layer to surface treatment. , Has excellent heat resistance.

The laminate of the present invention comprises a rubber layer (A) and a fluororesin layer (B) laminated on the rubber layer (A).
Since the laminate of the present invention has a rubber layer (A) formed from a specific rubber composition for vulcanization, it contains a fluoropolymer (b1) having polymerized units derived from chlorotrifluoroethylene. The fluororesin layer (B) formed from the fluoropolymer composition and the rubber layer (A) are firmly bonded.
In addition, when laminating the fluororesin layer (B) and the rubber layer (A), there is no need for a special process for bonding because a chemically strong bond can be obtained during rubber vulcanization without a particularly complicated process. Therefore, molding can be performed at low cost and molding is also easy. Moreover, since it can shape | mold by a normal method like extrusion molding, thin film formation is also possible. Moreover, the usage-amount of the high cost fluororesin can be suppressed and a highly flexible laminated body can be shape | molded.

Hereinafter, each layer will be described.

(A) Rubber layer The rubber layer (A) is a layer formed from a rubber composition for vulcanization.

The rubber composition for vulcanization contains unvulcanized rubber (a1), compound (a2), anti-aging agent (a3), magnesium oxide (a4), and silica (a5) as essential components. As components, a vulcanizing agent (a6) and a metal salt (a7) may be included.

The unvulcanized rubber (a1) is preferably a non-fluorinated rubber because of its good cold resistance and excellent cost.

The non-fluorine rubber includes acrylonitrile-butadiene rubber (NBR) and its hydride (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), isoprene rubber ( IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, acrylic rubber, chlorinated polyethylene (CPE), ethylene propylene diene rubber (EPDM) and the like.
As the termonomer of the ethylene-propylene-teromer copolymer rubber, a monomer constituting a diene rubber such as natural rubber, butadiene rubber (BR), isoprene rubber, butyl rubber, chloroprene rubber is preferable.

The unvulcanized rubber (a1) is preferably a diene rubber, more preferably NBR or HNBR, from the viewpoints of cost, oil resistance, weather resistance, and extrusion moldability. NBR and HNBR may be used in combination.

The rubber composition for vulcanization may contain a resin in order to give the rubber layer (A) properties different from those of the unvulcanized rubber (a1). Examples of the resin include PVC, chlorinated polystyrene, chlorosulfonated polystyrene ethylene, and ethylene-vinyl acetate copolymer. For example, when the rubber composition for vulcanization contains NBR and PVC, ozone resistance can be improved. In this case, the compounding amount of PVC is preferably 10 to 70 parts by mass and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of NBR.

The compound (a2) was synthesized from 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride ( DBU-B), 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) naphthoate, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) phenol salt, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) orthophthalate, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) formate, and 1,5 -At least one compound selected from the group consisting of diazabicyclo (4.3.0) nonene-5 (DBN). By containing the compound (a2), the vulcanization characteristics of the rubber composition for vulcanization can be improved and the adhesion between the rubber layer (A) and the fluororesin layer (B) can be strengthened.

The compound (a2) is preferably at least one compound selected from the group consisting of DBU-B, DBU formate, and DBU phenol salt, and particularly preferably DBU formate.

It is also preferred that the compound (a2) essentially comprises DBU formate. DBU formate may be used alone, DBU formate and DBU-B, DBU formate and DBU phenol salt, DBU formate and DBU orthophthalate A combination of DBU formate and DBU, a combination of DBU formate and DBU naphthoate, or a combination of DBU formate and DBN is also preferred.

The compound (a2) is more than 0.1 parts by mass and 5 parts by mass or less with respect to 100 parts by mass of the unvulcanized rubber (a1).
The compound (a2) is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the unvulcanized rubber (a1). More preferably it is. When there is too little compound (a2), there exists a possibility that adhesive force may not be enough.
Further, from the viewpoint of reducing the compression set and rubber hardness after vulcanization and reducing the cost of rubber, the compound (a2) is 4 masses per 100 mass parts of the unvulcanized rubber (a1). Part or less, preferably 3 parts by weight or less.

The laminated body of this invention can improve the heat resistance of a rubber layer (A) because the rubber composition for vulcanization | cure contains an anti-aging agent (a3).
The anti-aging agent (a3) is a compound having a property of suppressing deterioration of the polymer caused by various causes, and is an aromatic secondary amine type anti-aging agent, bisphenol type anti-aging agent, benzimidazole type anti-aging agent And at least two selected from the group consisting of thiourea antioxidants. Among them, the antiaging agent (a3) is preferably at least two selected from the group consisting of an aromatic secondary amine type antiaging agent, a bisphenol type antiaging agent and a benzimidazole type antiaging agent. The amount of the anti-aging agent (a3) is such that the adhesion between the rubber layer (A) and the fluororesin layer (B) can be strengthened, and the heat resistance of the laminate can be improved. a1) It is preferable that it is 2-9 mass parts in total with respect to 100 mass parts, It is more preferable that it is 2-8 mass parts, It is still more preferable that it is 2-7 mass parts.
When the blending amount of the anti-aging agent (a3) is less than 2 parts by mass in total with respect to 100 parts by mass of the unvulcanized rubber (a1), the heat resistance of the laminate tends not to be sufficiently improved. When the blending amount of the anti-aging agent exceeds 9 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1), the adhesion between the rubber layer (A) and the fluororesin layer (B) is insufficient. Tend to be.
Moreover, it is preferable that an anti-aging agent (a3) is 0.01-5 mass parts per type with respect to 100 mass parts of unvulcanized rubber (a1).

The anti-aging agent (a3) is a combination of an aromatic secondary amine anti-aging agent and a bisphenol anti-aging agent, an aromatic secondary amine anti-aging agent and a benzimidazole anti-aging agent, or bisphenol It is also preferable to be an anti-aging agent and a benzimidazole anti-aging agent, or to be an aromatic secondary amine anti-aging agent, a bisphenol anti-aging agent and a benzimidazole anti-aging agent.

When a combination of an aromatic secondary amine antioxidant and a bisphenol antioxidant is used as the antioxidant (a3), the aromatic secondary amine antioxidant is added to an unvulcanized rubber (a1). ) It is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 5 parts by mass, still more preferably 1 to 5 parts by mass, and bisphenol-based aging with respect to 100 parts by mass. The inhibitor is preferably 0.1 to 3 parts by mass, more preferably 0.5 to 3 parts by mass, and 1 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). More preferably. The mass ratio of the aromatic secondary amine antioxidant and the bisphenol antioxidant is preferably 90/10 to 10/90, more preferably 30/70 or more, and 70/30 or less. It is more preferable that The total amount of the aromatic secondary amine antioxidant and the bisphenol antioxidant is preferably 2 to 8 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1).

When using a combination of an aromatic secondary amine anti-aging agent and a benzimidazole anti-aging agent as the anti-aging agent (a3), the aromatic secondary amine anti-aging agent is an unvulcanized rubber ( a1) It is preferable that it is 0.1-5 mass parts with respect to 100 mass parts, It is more preferable that it is 0.5-5 mass parts, It is still more preferable that it is 1-5 mass parts. The benzimidazole anti-aging agent is preferably 0.1 to 3 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). More preferably, it is -3 mass parts. The mass ratio of the aromatic secondary amine antioxidant and the benzimidazole antioxidant is preferably 90/10 to 10/90, more preferably 30/70 or more, and 70/30. The following is more preferable. The total amount of the aromatic secondary amine-based antioxidant and the benzimidazole-based antioxidant is preferably 2 to 8 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1).

When a combination of a bisphenol-based anti-aging agent and a benzimidazole-based anti-aging agent is used as the anti-aging agent (a3), the bisphenol-based anti-aging agent is 0 with respect to 100 parts by mass of the unvulcanized rubber (a1). 0.1 to 3 parts by mass, more preferably 0.5 to 3 parts by mass, still more preferably 1 to 3 parts by mass, and the benzimidazole anti-aging agent is an unvulcanized rubber. (A1) It is preferable that it is 0.1-3 mass parts with respect to 100 mass parts, It is more preferable that it is 0.5-3 mass parts, It is still more preferable that it is 1-3 mass parts. The mass ratio of the bisphenol-based antioxidant and the benzimidazole-based antioxidant is preferably 90/10 to 10/90, more preferably 30/70 or more, and 70/30 or less. More preferred. The total amount of the bisphenol-based antioxidant and the benzimidazole-based antioxidant is preferably 2 to 6 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1).

When using a combination of an aromatic secondary amine antioxidant, a bisphenol antioxidant and a benzimidazole antioxidant as the antioxidant (a3), an aromatic secondary amine antioxidant is used. It is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 5 parts by mass, and 1 to 5 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). Is more preferable, and the bisphenol-based anti-aging agent is preferably 0.1 to 3 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). Preferably, the amount is 1 to 3 parts by mass, and the benzimidazole anti-aging agent is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). .5-3 parts by mass More preferably, and more preferably 1 to 3 parts by weight.
Mass ratio of aromatic secondary amine antioxidant, bisphenol antioxidant and benzimidazole antioxidant (aromatic secondary amine antioxidant / bisphenol antioxidant / benzimidazole antioxidant) The agent is preferably 10 to 60/10 to 50/10 to 50, and more preferably 20 to 50/20 to 40/20 to 40.
Aromatic secondary amine type anti-aging agent, bisphenol type anti-aging agent and benzimidazole type anti-aging agent are 2 to 9 parts by mass in total with respect to 100 parts by mass of unvulcanized rubber (a1). Is preferred.

Since anti-aging agent (a3) improves heat resistance by combining a primary anti-aging agent and a secondary anti-aging agent, an aromatic secondary amine anti-aging agent that is a primary anti-aging agent and A combination of at least one anti-aging agent selected from the group consisting of bisphenol anti-aging agents and a benzimidazole anti-aging agent which is a secondary anti-aging agent is more preferable.
Here, the primary anti-aging agent is an anti-aging agent that supplements radicals and has an auto-oxidation-preventing action, and the secondary anti-aging agent is an anti-aging action that has an action of decomposing hydroperoxide into harmless ones. Refers to an agent.

As an anti-aging agent (a3), a combination of at least one anti-aging agent selected from the group consisting of an aromatic secondary amine anti-aging agent and a bisphenol anti-aging agent and a benzimidazole anti-aging agent When used, at least one type of anti-aging agent selected from the group consisting of aromatic secondary amine type anti-aging agents and bisphenol type anti-aging agents is 100 parts by mass of unvulcanized rubber (a1), The total amount is preferably 1 to 6 parts by mass, more preferably 1 to 5 parts by mass, and the benzimidazole-based antioxidant is 1 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). It is preferable that it is a mass part, and it is more preferable that it is 1-2 mass parts. The mass ratio of at least one anti-aging agent selected from the group consisting of an aromatic secondary amine anti-aging agent and a bisphenol anti-aging agent to the benzimidazole anti-aging agent is 90/10 to 10/90. It is preferable that it is 30/70 or more, and it is more preferable that it is 70/30 or less. At least one anti-aging agent selected from the group consisting of aromatic secondary amine-based anti-aging agents and bisphenol-based anti-aging agents and benzimidazole-based anti-aging agents are 100 parts by mass of unvulcanized rubber (a1). The total amount is preferably 2 to 9 parts by mass.

Examples of the aromatic secondary amine antioxidant include octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, phenyl-1-naphthylamine, N, N′-di-2--2- Naphthyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N ′-(1,3-dimethylbutyl) -p -Phenylenediamine, alkylated diphenylamine ("NOCRACK ODA, ODA-N" manufactured by Ouchi Shinsei Chemical Co., Ltd.), p- (p-toluenesulfonylamido) diphenylamine, N-phenyl-N '-(3-methacryloyloxy- 2-hydroxypropyl) -p-phenylenediamine and the like. Ruamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, phenyl-1-naphthylamine, N, N′-di-2-naphthyl-p-phenylenediamine, N, N′-diphenyl-p-phenylene Diamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, alkylated diphenylamine (manufactured by Ouchi Shinsei Chemical Co., Ltd. “ NOCRACK ODA, ODA-N "), p- (p-toluenesulfonylamido) diphenylamine, and N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine are preferred. Several of these may be mixed and used as a mixed anti-aging agent. As the kind to be mixed, a combination of phenyl-1-naphthylamine and N, N′-diphenyl-p-phenylenediamine is preferable.

Examples of the bisphenol antioxidant include 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), and 2,2 ′. -Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), butylated reaction product of p-cresol and dicyclopentadiene (Ouchi Emerging Chemical) "NOCLACK PBK" manufactured by Kogyo Co., Ltd.) and the like. 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-buty Denbisu (3-methyl -6-tert-butylphenol), p-cresol and dicyclopentadiene butylated reaction product (Ouchi Shinko Chemical Industrial Co., Ltd. "NOCRAC PBK") is preferable.

Examples of the benzimidazole anti-aging agent include 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and the like. Zinc of 2-mercaptobenzimidazole and 2-mercaptobenzimidazole A salt, 2-mercaptomethylbenzimidazole is preferred.

Examples of the thiourea anti-aging agent include 1,3-bis (dimethylaminopropyl) -2-thiourea, tributylthiourea, etc., and 1,3-bis (dimethylaminopropyl) -2-thiourea, Tributylthiourea is preferred.

Antiaging agent (a3) is, among others, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, 2-mercaptobenzimidazole and 4,4′-thiobis (3-methyl-6-tert-butylphenol) Particularly preferred are at least two compounds selected from the group consisting of:

The rubber composition for vulcanization further contains magnesium oxide (a4).
The blending amount of the magnesium oxide (a4) is preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1) from the viewpoint of adhesiveness and rubber physical properties. It is. The laminated body which has the specific structure of this invention will have the outstanding adhesiveness by containing magnesium oxide (a4).

The rubber composition for vulcanization further contains silica (a5).
As silica (a5), basic silica and acidic silica can be used, and it is preferable to use basic silica from the viewpoint of adhesiveness. Examples of basic silica include Carplex 1120 (manufactured by DSL Japan Co., Ltd.). Further, the blending amount of silica (a5) is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1) from the viewpoint of adhesiveness and rubber physical properties. The laminate having a specific structure of the present invention has excellent adhesiveness by containing silica (a5).

The vulcanizing rubber composition preferably further contains a vulcanizing agent (a6). As the vulcanizing agent (a6), conventionally known ones can be used according to the vulcanization system of the vulcanizing rubber composition. By vulcanizing the unvulcanized rubber (a1), mechanical strength such as tensile strength of the resulting rubber layer is improved, and good elasticity can be obtained.

The vulcanization systems that can be used in the present invention include sulfur vulcanization systems, polyamine vulcanization systems, polyol vulcanization systems, peroxide vulcanization systems, imidazole vulcanization systems, triazine vulcanization systems, oxazole vulcanization systems, thiazole vulcanization systems. Any of the vulcanization systems can be used, but when the unvulcanized rubber contains vulcanizable groups (cure sites), it is appropriately selected depending on the type of cure sites or the properties and applications to be applied to the vulcanized laminate. That's fine.

As the vulcanizing agent (a6), sulfur vulcanizing vulcanizing agent, polyamine vulcanizing vulcanizing agent, polyol vulcanizing vulcanizing agent, peroxide vulcanizing vulcanizing agent, imidazole vulcanizing agent can be used. Any of a vulcanizing vulcanizing agent, a triazine vulcanizing vulcanizing agent, an oxazole vulcanizing vulcanizing agent, and a thiazole vulcanizing vulcanizing agent may be employed, or they may be used alone or in combination.

For example, when the unvulcanized rubber (a1) is a diene-based non-fluorinated rubber (NBR, SBR, BR, etc.), a sulfur vulcanization system and a peroxide vulcanization system are usually employed. It is preferably at least one selected from the group consisting of a vulcanizing vulcanizing agent and a peroxide vulcanizing agent.

Examples of sulfur vulcanizing agents include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, sulfur chloride, sulfur dichloride, disulfide compounds, polysulfide compounds, and the like.

0.1-10 mass parts is preferable with respect to 100 mass parts of unvulcanized rubber (a1), and, as for the compounding quantity of a sulfur vulcanizing | curing type vulcanizing agent, 0.3-5 mass parts is more preferable. If the amount is too small, the adhesiveness is insufficient, and if the amount is too large, it tends to be too hard.

Preferred examples of the peroxide vulcanizing agent include organic peroxides that easily generate peroxy radicals in the presence of heat or a redox system.

Examples of organic peroxides include 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, and di-t-butyl. Peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxide Oxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoyl) Peroxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and the like. Of these, preferred are dialkyl compounds. In general, the type and blending amount are selected from the amount of active —O═O—, the decomposition temperature, and the like. A compounding quantity is 0.1-15 mass parts normally with respect to 100 mass parts of unvulcanized rubber, Preferably it is 0.3-5 mass parts.

The vulcanizing agent (a6) is preferably at least one selected from the group consisting of a sulfur vulcanizing vulcanizing agent and a peroxide vulcanizing vulcanizing agent. It is also preferable to use a sulfur vulcanizing agent and a peroxide vulcanizing agent in combination.
The addition amount of the vulcanizing agent (a6) is preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1).

The rubber composition for vulcanization preferably contains a thiazole vulcanization accelerator from the viewpoint of vulcanization speed control.
Examples of the thiazole vulcanization accelerator include N-oxydiethylene-2-benzothiazolylsulfenamide.
The addition amount of the thiazole vulcanization accelerator is preferably 0.3 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). .

The rubber composition for vulcanization preferably further contains a metal salt (a7).
The metal salt (a7) is preferably at least one selected from the group consisting of dithiocarbamic acid metal salts and thiazole metal salts.

Examples of the metal salt of dithiocarbamate include zinc salt of dimethyldithiocarbamate (ZnMDC), zinc salt of diethyldithiocarbamate (ZnEDC), zinc salt of dibutyldithiocarbamate (ZnBDC), iron salt of dimethyldithiocarbamate (FeMDC), ethylphenyl Zinc salt of dithiocarbamate (ZnEPDC), zinc salt of N-pentamethylenedithiocarbamate, zinc salt of dibenzyldithiocarbamate, sodium salt of dimethyldithiocarbamate (NaMDC), sodium salt of diethyldithiocarbamate (NaEDC), dibutyldithiocarbamate Sodium salt (NaBDC), dimethyldithiocarbamate copper salt (CuMDC), diethyldithiocarbamate copper salt (CuEDC), diethyldithiocarbamate Tellurium salts (TeEDC), and the like.
The dithiocarbamic acid metal salt is preferably a copper salt of dithiocarbamate, and examples thereof include a copper salt of dimethyldithiocarbamate (CuMDC) and a copper salt of diethyldithiocarbamate (CuEDC).
These may be used alone or in combination of two or more.

As the thiazole-based metal salt, a zinc salt of mercaptobenzothiazole (ZnMBT) is preferably used.

The compounding amount of the metal salt (a7) is preferably 0.01 to 3 parts by mass, more preferably 0.01 to 0.5 parts by mass, further preferably 100 parts by mass of the unvulcanized rubber (a1). It is 0.05-0.3 mass part.
When the blending amount of the metal salt (a7) is too small, the vulcanized rubber properties tend to be deteriorated, and when it is too large, the unvulcanized physical properties tend to be deteriorated.

Further, in the present invention, usual additives blended in a general vulcanizing rubber composition, for example, a filler, a processing aid, a plasticizer, a softening agent, a colorant, a stabilizer, an adhesive, depending on the purpose or necessity. Auxiliary agent, mold release agent, conductivity imparting agent, thermal conductivity imparting agent, surface non-adhesive agent, tackifier, flexibility imparting agent, heat resistance improver, flame retardant, ultraviolet absorber, oil resistance improver, foaming Various additives such as an agent, a scorch inhibitor, a lubricant, and an epoxy resin can be blended. Moreover, you may mix | blend 1 type (s) or 2 or more types of the usual vulcanizing agent and vulcanization accelerator different from the said thing. However, these additives are blended in such an amount that does not impair the adhesive force with the fluororesin layer (B) which is the object of the present invention.

Fillers include metal oxides such as calcium oxide, titanium oxide, and aluminum oxide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; magnesium carbonate, aluminum carbonate, calcium carbonate, barium carbonate, etc. Carbonates; silicates such as magnesium silicate, calcium silicate, sodium silicate, and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate, and barium sulfate; synthetic hydrotalcite, molybdenum disulfide, iron sulfide, sulfide Metal sulfides such as copper; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, quartz fine powder, zinc white, talc, mica powder, wax Lastite, carbon fiber, aramid fiber Various whiskers, glass fiber, organic reinforcing agents and organic fillers.
The content of the filler is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and more preferably 30 parts by mass or more with respect to 100 parts by mass of the unvulcanized rubber (a1). Further preferred.
From the viewpoint of cost, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 100 parts by mass or less with respect to 100 parts by mass of the unvulcanized rubber (a1). preferable.

As processing aids, higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; oleic acid Higher fatty acid esters such as ethyl, higher aliphatic amines such as stearylamine and oleylamine; petroleum waxes such as carnauba wax and ceresin wax; polyglycols such as ethylene glycol, glycerin and diethylene glycol; aliphatic hydrocarbons such as petroleum jelly and paraffin; Silicone oil, silicone polymer, low molecular weight polyethylene, phthalates, phosphates, rosin, (halogenated) dialkylamine, (halogenated) dialkylsulfone, surfactant And the like.

Examples of the plasticizer include an epoxy plasticizer, an ester plasticizer, an ether plasticizer, an adipic acid plasticizer, a phthalic acid plasticizer, and a sebacic acid plasticizer.
Examples of the plasticizer include dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), butyl benzyl phthalate, dibutoxyethyl phthalate, dibutyl adipate, di-2-ethylhexyl adipate (DOA), dibutoxyethyl adipate, Di-2-ethylhexyl azelate (DOZ), dibutyl sebacate (DBS), di-2-ethylhexyl sebacate (DOS), tri-2-ethylhexyl trimellitate (TOTM), epoxidized soybean oil (ESBO) and epoxy Fatty acid monoester, epoxidized linseed oil (ELSO), epoxyhexahydrophthalic acid di-2-ethylhexyl (E-PS), tricresyl phosphate (TCP), tri-2-ethylhexyl phosphate (TOP) and tributoxy Ethyl phosphate (TBXP), tris-chloro-ethyl phosphate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylhexoate, dibutyl carbitol adipate (TP-95), dibutyl carbitol formal (TP -90B), methylenebisbutylthioglycolate, adipic acid polyester, sebacic acid polyester, azelaic acid polyester, butyl oleate, diethylene glycol dibenzoate, acetyl tributyl citrate, chlorinated fatty acid ester, chlorinated paraffin, diundecyl phthalate (DUP) ) And tridecyl trimellitate (TDTM).
Preferred examples include dibutyl carbitol adipate (TP-95) and dibutyl carbitol formal (TP-90B).
The content of the plasticizer is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more with respect to 100 parts by mass of the unvulcanized rubber (a1).
From the viewpoint of cost, it is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 40 parts by mass or less with respect to 100 parts by mass of the unvulcanized rubber (a1). preferable.

Examples of the softening agent include lubricating oil, process oil, coal tar, castor oil, calcium stearate and the like.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and polyfunctional epoxy resin. Of these, bisphenol A type epoxy resin is preferable from the viewpoint of good chemical resistance and adhesion, and further, the formula (3):

An epoxy resin represented by the formula is particularly preferred. Here, in Formula (3), n is an average value, 0.1-3 are preferable, 0.1-0.5 are more preferable, 0.1-0.3 are further more preferable. When n is less than 0.1, the adhesive strength with the fluororesin (b) tends to decrease. On the other hand, when n exceeds 3, the viscosity of the epoxy resin itself increases, and uniform dispersion in the rubber composition for vulcanization tends to be difficult.

The content when the epoxy resin is blended is preferably 1 part by mass or more with respect to 100 parts by mass of the unvulcanized rubber (a1), from the viewpoint of further improving the adhesive force with the fluororesin (b). Part or more is more preferable, and 3 parts by mass or more is particularly preferable. From the viewpoint of preventing the rubber layer from becoming too hard, the amount is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less with respect to 100 parts by mass of the unvulcanized rubber (a1).

The vulcanized rubber composition comprises an unvulcanized rubber (a1), a compound (a2), an anti-aging agent (a3), and if necessary, magnesium oxide (a4), silica (a5), vulcanizing agent (a6). ), A thiazole vulcanization accelerator and other additives are kneaded.

The kneading can be performed using, for example, an open roll, a Banbury mixer, a pressure kneader, or the like at a temperature of 100 ° C. or lower.

The rubber composition for vulcanization preferably has an optimum vulcanization time (T ₉₀ ) of 18 minutes or less. More preferably, it is 15 minutes or less. The lower limit of T ₉₀ is not particularly limited, for example, at least 1 minute.
Since the rubber composition for vulcanization has the above configuration, the vulcanization time can be shortened and the productivity can be improved. _T90 is a value obtained by measuring the maximum torque value (MH) and the minimum torque value (ML) at 160 ° C., and is a value obtained by {(MH) − (ML)} × 0.9 + ML. . MH and ML are values measured according to JIS K 6300-2.

Next, the fluororesin layer (B) in the laminate of the present invention will be described.

(B) Fluororesin layer The fluororesin layer (B) is a layer formed from a fluoropolymer composition.

The fluoropolymer composition contains a fluoropolymer (b1) having polymerized units derived from at least chlorotrifluoroethylene (CTFE).

The fluoropolymer (b1) is preferably a fluororesin, more preferably at least one selected from the group consisting of polychlorotrifluoroethylene (PCTFE) and CTFE copolymer, and a CTFE copolymer. More preferably it is.

The CTFE copolymer includes polymerized units derived from CTFE (CTFE units), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE), and vinylidene fluoride (VdF). , Vinyl fluoride, hexafluoroisobutene, formula:
^{_{CH 2 = CX 1 (CF 2}} ) n X 2
(Wherein X ¹ is H or F, X ² is H, F or Cl, and n is an integer of 1 to 10), ethylene, propylene, 1-butene, 2-butene, chloride It is preferable to include a polymer unit derived from at least one monomer selected from the group consisting of vinyl and vinylidene chloride.

The CTFE copolymer is preferably a perhalopolymer, and more preferably includes a CTFE unit and a polymer unit derived from at least one monomer selected from the group consisting of TFE, HFP, and PAVE. More preferably, it is substantially composed of only these polymerized units. Further, from the viewpoint of low fuel permeation, it is preferable not to include a monomer having a CH bond such as ethylene, vinylidene fluoride, and vinyl fluoride. Although the perhalopolymer is usually difficult to adhere to rubber, according to the configuration of the present invention, even if the fluororesin layer is a layer made of perhalopolymer, the fluororesin layer (B) and the rubber layer (A) The adhesion between the layers is strong.

The CTFE copolymer preferably has 10 to 90 mol% of CTFE units based on the total monomer units.

As the CTFE copolymer, those containing a CTFE unit, a TFE unit and a monomer (α) unit derived from a monomer (α) copolymerizable therewith are particularly preferred.

The above-mentioned “CTFE unit” and “TFE unit” are a part derived from CTFE (—CFCl—CF ₂ —) and a part derived from TFE (—CF ₂ —CF ₂ —), respectively, in the molecular structure of the CTFE copolymer. Similarly, the “monomer (α) unit” is a portion formed by adding the monomer (α) to the molecular structure of the CTFE copolymer.

The monomer (α) is not particularly limited as long as it is a monomer copolymerizable with CTFE and TFE, and ethylene (Et), vinylidene fluoride (VdF), CF ₂ = CF-ORf ¹ (formula Rf ¹ is a perfluoro (alkyl vinyl ether) represented by a C 1-8 perfluoroalkyl group), CX ³ X ⁴ = CX ⁵ (CF ₂ ) _n X ⁶ (wherein X ³ , X ⁴ and X ⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ⁶ is a hydrogen atom, a fluorine atom or a chlorine atom; n is an integer of 1 to 10), a vinyl monomer represented by CF ₂ = An alkyl perfluorovinyl ether derivative represented by CF—OCH ₂ —Rf ² (wherein Rf ² is a C 1-5 perfluoroalkyl group) is exemplified. It is preferably at least one selected from the group consisting of vinyl monomers and alkyl perfluorovinyl ether derivatives, more preferably at least one selected from the group consisting of PAVE and HFP.

As the alkyl perfluorovinyl ether derivative, those in which Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

In the CTFE copolymer, the ratio of CTFE units to TFE units is 85 to 10 mol% of TFE units, preferably 20 to 90 mol% of CTFE units, with respect to 15 to 90 mol% of CTFE units. Yes, the TFE unit is 80 to 10 mol%. Moreover, what comprises 15-25 mol% of CTFE units and 85-75 mol% of TFE units is more preferable.

The CTFE copolymer preferably has a total of CTFE units and TFE units of 90 to 99.9 mol% and monomer (α) units of 0.1 to 10 mol%. If the monomer (α) unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and fuel crack resistance are likely to be inferior, and if it exceeds 10 mol%, fuel low permeability, heat resistance, It tends to be inferior in mechanical properties.

The fluoropolymer (b1) is particularly preferably PCTFE or CTFE-TFE-PAVE copolymer. The CTFE-TFE-PAVE copolymer is a copolymer consisting essentially of CTFE, TFE and PAVE. Even more preferred is a CTFE-TFE-PAVE copolymer.
In the present invention, since the rubber layer (A) is a layer formed from a fluororubber composition for vulcanization having a limited composition, the fluororesin layer (B) has a PCTFE in which the dehydrofluorination reaction does not proceed. Even if it is a CTFE-TFE-PAVE copolymer, the adhesion between the rubber layer (A) and the fluororesin layer (B) is strong.

Examples of the PAVE include perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (butyl vinyl ether), among others, PMVE, It is preferably at least one selected from the group consisting of PEVE and PPVE.

The PAVE unit is preferably 0.5 mol% or more of the total monomer units, and preferably 5 mol% or less.

A structural unit such as a CTFE unit is a value obtained by performing ¹⁹ F-NMR analysis.

In the fluoropolymer (b1), at least one reactive functional group selected from the group consisting of a carbonyl group, a hydroxyl group, a heterocyclic group, and an amino group is introduced into the main chain terminal and / or side chain of the polymer. It may be a thing.

In the present specification, the “carbonyl group” is a carbon divalent group composed of a carbon-oxygen double bond, and is represented by —C (═O) —. The reactive functional group containing the carbonyl group is not particularly limited. For example, a carbonate group, a carboxylic acid halide group (halogenoformyl group), a formyl group, a carboxyl group, an ester bond (—C (═O) O—), an acid. Anhydride bond (—C (═O) O—C (═O) —), isocyanate group, amide group, imide group (—C (═O) —NH—C (═O) —), urethane bond (— NH-C (= O) O- ), a carbamoyl group _{(NH 2 -C (= O)} -), a carbamoyloxy group _{(NH 2 -C (= O)} O-), a ureido group _(NH 2 -C ₍₌ O) -NH-), oxamoyl group _{(NH 2 -C (= O)} -C (= O) -) , etc., can be mentioned those containing a carbonyl group as part of the chemical structure.

In the amide group, imide group, urethane bond, carbamoyl group, carbamoyloxy group, ureido group, oxamoyl group, etc., the hydrogen atom bonded to the nitrogen atom may be substituted with a hydrocarbon group such as an alkyl group, for example. .

The reactive functional group is easy to introduce, and since the fluoropolymer (b1) has moderate heat resistance and good adhesion at a relatively low temperature, an amide group, a carbamoyl group, a hydroxyl group, a carboxyl group Group, carbonate group, carboxylic acid halide group, and acid anhydride bond are preferable, and amide group, carbamoyl group, hydroxyl group, carbonate group, carboxylic acid halide group, and acid anhydride bond are more preferable.

Among these, those having a carbonate group and / or a carboxylic acid halide group described in WO99 / 45044 are particularly preferable.

The fluoropolymer (b1) may be composed of a polymer having a reactive functional group at either the main chain terminal or the side chain of the polymer, or the reactive functional group at both the main chain terminal and the side chain. It may consist of a polymer having When having a reactive functional group at the end of the main chain, it may be present at both ends of the main chain or only at one of the ends. When the reactive functional group also has an ether bond, it may further have the reactive functional group in the main chain.

The fluoropolymer (b1) is composed of a polymer having a reactive functional group at the main chain terminal because it does not significantly reduce mechanical properties and chemical resistance, or because it is advantageous in terms of productivity and cost. preferable.

The number of the reactive functional groups may be appropriately selected depending on the type and shape of the rubber layer to be laminated, the purpose and application of adhesion, the required adhesive force and the adhesion method between the adjacent layers, and the like.

The number of reactive functional groups at the main chain terminal and / or side chain terminal is preferably 3 to 800 per 1 × 10 ⁶ main chain carbon atoms. Adhesiveness may fall that it is less than 3 per 1 × 10 ⁶ main chain carbon atoms. A more preferred lower limit is 15, a further preferred lower limit is 30, and a particularly preferred lower limit is 120. The upper limit of the number of reactive functional groups at the terminal is more preferably, for example, 200 from the viewpoint of productivity.

The number of reactive functional groups at the end is such that the thickness of 0.25 to 0.30 mm obtained by compression molding the fluoropolymer (b1) powder at a molding temperature of 50 ° C. higher than its melting point and a molding pressure of 5 MPa. The film sheet is subjected to infrared absorption spectrum analysis using an infrared spectrophotometer, and the type of characteristic absorption of the reactive functional group is determined by comparison with the infrared absorption spectrum of a known film. It is the number calculated by.

Number of terminal groups (per 1 × 10 ⁶ carbon atoms in the main chain) = (l × K) / t
l: Absorbance K: Correction coefficient t: Film thickness (mm)
Table 1 shows correction coefficients for the terminal reactive functional groups.

The correction coefficient in Table 1 is a value determined from the infrared absorption spectrum of the model compound in order to calculate the terminal group per 1 × 10 ⁶ main chain carbon atoms.

As a method for introducing the reactive functional group into the terminal of the main chain and / or side chain, a method of introducing the reactive functional group-containing monomer (β) by copolymerization, having a reactive functional group, or A method of using the resulting compound as a polymerization initiator, a method of using a reactive functional group or a generated compound as a chain transfer agent, a method of introducing a reactive functional group into a fluoropolymer by a polymer reaction, a method of using these methods in combination Etc. can be exemplified.

When the reactive functional group is introduced by copolymerization, the reactive functional group-containing monomer (β) is a monomer that can be copolymerized with the monomer that gives the fluoropolymer (b1). If it has group, it will not restrict | limit in particular. Specifically, for example, the following can be exemplified.

Examples of the first monomer (β) include aliphatic unsaturated carboxylic acids described in International Publication No. 2005/100420. Unsaturated carboxylic acids have at least one polymerizable carbon-carbon unsaturated bond in one molecule, and at least one carbonyloxy group (—C (═O) —O—) in one molecule. What has is preferable.

The aliphatic unsaturated carboxylic acid may be an aliphatic unsaturated monocarboxylic acid or an aliphatic unsaturated polycarboxylic acid having two or more carboxyl groups. Examples of the aliphatic unsaturated monocarboxylic acid include unsaturated aliphatic monocarboxylic acids having 3 to 6 carbon atoms such as (meth) acrylic acid and crotonic acid.

Examples of the aliphatic unsaturated polycarboxylic acid include 3 to 3 carbon atoms such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid, maleic anhydride, itaconic anhydride, or citraconic anhydride. 6 unsaturated aliphatic polycarboxylic acids.

The second monomer (β) has the formula:
CX ⁷ ₂ = CY ^1- (Rf ⁴ ) _n -Z ¹
Wherein Z ¹ is the reactive functional group; X ⁷ and Y ¹ are the same or different and are a hydrogen atom or a fluorine atom; Rf ⁴ is an alkylene group having 1 to 40 carbon atoms; A fluorine-containing oxyalkylene group having 2 to 40 carbon atoms having an ether bond, or a fluorine-containing oxyalkylene group having 2 to 40 carbon atoms having an ether bond; n is 0 or 1) Saturated compounds are mentioned.

The content of the reactive functional group-containing monomer (β) unit introduced by copolymerization is preferably 0.05 mol% or more, and more preferably 0.1 mol% or more. If the amount is too large, gelation or vulcanization reaction is likely to occur during heating and melting, and therefore the upper limit of the functional group-containing monomer is preferably 5 mol%, and more preferably 3 mol%.

The fluoropolymer (b1) may have a heterocyclic group or an amino group at the main chain end or side chain end of the polymer.

The heterocyclic group is a group having a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring of the heterocyclic portion, and may be a saturated ring or an unsaturated ring. It may be a single ring or a condensed ring. Among the heterocyclic groups, an oxazolyl group is preferable.

An amino group is a monovalent functional group obtained by removing hydrogen from ammonia, primary or secondary amine. Specifically, for example, the formula:
-NR ⁴ R ⁵
(In the formula, R ⁴ and R ⁵ may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) Specific examples of the amino group include: NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —NH (CH ₂ CH ₃ ), —N (C ₂ H ₅ ) ₂ , —NH (C ₆ H ₅ ) and the like can be mentioned.

The fluoropolymer (b1) can be obtained by a conventionally known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization or bulk polymerization. In the polymerization, each condition such as temperature and pressure, a polymerization initiator and other additives can be appropriately set according to the composition and amount of the fluoropolymer (b1).

The melting point of the fluoropolymer (b1) is not particularly limited, but is preferably 160 to 270 ° C.

The melting point of the fluoropolymer (b1) is determined as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a DSC apparatus (manufactured by Seiko). MFR uses a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the weight (g) of the polymer flowing out in a unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 5 kg at each temperature. taking measurement.

Further, the molecular weight of the fluoropolymer (b1) is preferably in a range in which the obtained molded product can exhibit good mechanical properties, low fuel permeability, and the like. For example, when the melt flow rate (MFR) is used as an index of molecular weight, the MFR at an arbitrary temperature (for example, 297 ° C.) in the range of about 230 to 350 ° C. which is a general molding temperature range of fluoropolymer is 0.5 to It is preferable that it is 100 g / 10min.

Examples of the polymerization initiator include oil-soluble radical polymerization initiators typified by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP). Water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt and sodium salt can be used. Among these, di-n-propyl peroxydicarbonate (NPP) is preferable.

As the chain transfer agent, a water-soluble alcohol having 1 to 4 carbon atoms, a hydrocarbon having 1 to 4 carbon atoms, and a fluoride having 1 to 4 carbon atoms in terms of good dispersibility and uniformity in the reaction system. It is preferably at least one selected from the group consisting of hydrocarbons and persulfates. The chain transfer agent may be at least one selected from the group consisting of methane, ethane, n-butane, isobutane, methanol, n-propyl alcohol, HFC-134a, HFC-32, DSP, APS, and KPS. More preferably, it is more preferably at least one selected from the group consisting of n-propyl alcohol, methanol and isobutane.

In the present invention, the fluororesin layer (B) may contain one kind of these fluoropolymers (b1), or may contain two or more kinds.

When the laminate is used as a material around the fuel, the fluororesin layer (B) in the laminate of the present invention preferably has a fuel permeability coefficient of 10 g · mm / m ² / day or less, and 1.0 g · mm. / M ² / day or less is more preferable, and 0.5 g · mm / m ² / day or less is more preferable.

The fuel permeability coefficient is obtained by incorporating a sheet obtained from the resin to be measured into a fuel permeability coefficient measuring cup charged with an isooctane / toluene / ethanol mixed solvent in which isooctane, toluene and ethanol are mixed at a volume ratio of 45:45:10. It is a value calculated from the mass change measured at 60 ° C.

In the present invention, when the fluoropolymer (b1) has a specific reactive functional group at its terminal, the adhesion to the rubber layer (A) is improved. Therefore, it is possible to provide a molded article (for example, a fuel tank) having excellent impact resistance and strength.

In addition, when the fluoropolymer (b1) is a perhalopolymer, chemical resistance and low fuel permeability are more excellent. A perhalopolymer is a polymer in which halogen atoms are bonded to all the carbon atoms constituting the main chain of the polymer.

The fluororesin layer (B) is further blended with various fillers such as inorganic powder, glass fiber, carbon powder, carbon fiber, and metal oxide within a range that does not impair the performance depending on the purpose and application. It may be.

For example, in order to further reduce fuel permeability, smectite lamellar viscous minerals such as montmorillonite, beidellite, saponite, nontronite, hectorite, saconite, and stevensite, and fine layered minerals with high aspect ratio such as mica are used. It may be added.

In order to impart conductivity, a conductive filler may be added. The conductive filler is not particularly limited, and examples thereof include conductive single powders or conductive single fibers such as metals and carbons; powders of conductive compounds such as zinc oxide; surface conductive powders. When blending the conductive filler, it is preferable to prepare a pellet in advance by melt-kneading.

The conductive single powder or conductive single fiber is not particularly limited, and examples thereof include metal powders such as copper and nickel; metal fibers such as iron and stainless steel; carbon black, carbon fiber, and Japanese Patent Laid-Open No. 3-174018. Examples thereof include carbon fibrils.

The surface conductive treatment powder is a powder obtained by conducting a conductive treatment on the surface of a nonconductive powder such as glass beads or titanium oxide.

The method for the surface conductive treatment is not particularly limited, and examples thereof include metal sputtering and electroless plating.

Among the conductive fillers, carbon black is preferably used because it is advantageous in terms of economy and prevention of electrostatic charge accumulation.

The volume resistivity of the fluoropolymer composition formed by blending a conductive filler is preferably 1 × 10 ⁰ to 1 × 10 ⁹ Ω · cm. A more preferred lower limit is 1 × 10 ² Ω · cm, and a more preferred upper limit is 1 × 10 ⁸ Ω · cm.

Moreover, you may mix | blend a heat stabilizer, a reinforcing agent, a ultraviolet absorber, a pigment, and other arbitrary additives other than a filler.

The laminate of the present invention can be produced by laminating the rubber layer (A) and the fluororesin layer (B). In the laminate of the present invention, the rubber layer (A) may be laminated on both sides of the fluororesin layer (B), or the fluororesin layer (B) may be laminated on both sides of the rubber layer (A). Good.

The rubber layer (A) and the fluororesin layer (B) are laminated by forming the rubber layer (A) and the fluororesin layer (B) separately and then laminating them by means such as pressure bonding. Either a method of simultaneously molding and laminating the resin layer (B) or a method of applying the fluororesin layer (B) to the rubber layer (A) may be used.

In the method of forming the rubber layer (A) and the fluororesin layer (B) separately and then laminating them by means of pressure bonding or the like, it is possible to adopt a molding method of each of the fluoropolymer molding method and the rubber composition for vulcanization. .

Molding of the rubber layer (A) can be carried out in various forms such as sheet and tube by heat compression molding, transfer molding, extrusion molding, injection molding, calendar molding, coating, etc. A shaped molded body can be obtained.

The fluororesin layer (B) can be formed by a method such as heat compression molding, melt extrusion molding, injection molding, or coating (including powder coating). For molding, commonly used fluoropolymer molding machines such as injection molding machines, blow molding machines, extrusion molding machines, and various coating devices can be used to produce laminates of various shapes such as sheets and tubes. Is possible. Of these, the melt extrusion molding method is preferred because of its excellent productivity.

Further, as will be described later, when another polymer layer (C) is laminated on the fluororesin layer (B), a molding method such as multilayer extrusion molding, multilayer blow molding, multilayer injection molding or the like can be applied. It can be set as multilayer molded articles, such as a hose and a multilayer tank.

The rubber layer (A) and the fluororesin layer (B) are simultaneously molded and laminated. The vulcanized rubber composition for forming the rubber layer (A) and the fluoropolymer (for forming the fluororesin layer (B) ( Using b1), a method of laminating simultaneously with molding by a method such as a multilayer compression molding method, a multilayer transfer molding method, a multilayer extrusion molding method, a multilayer injection molding method, or a doubling method can be mentioned. In this method, since the rubber layer (A) and the fluororesin layer (B) can be laminated at the same time, a step of closely adhering the rubber layer (A) and the fluororesin layer (B) is not particularly necessary. It is suitable for obtaining strong adhesion in the vulcanization process.
By such a method, an unvulcanized laminate in which the unvulcanized rubber layer (A) and the fluororesin layer (B) are laminated is obtained.

The laminate of the present invention is preferably obtained by vulcanizing an unvulcanized laminate obtained by the above-described method. The laminate obtained by vulcanizing the above-mentioned unvulcanized laminate is obtained by vulcanizing and bonding the rubber layer (A) and the fluororesin layer (B) and having strong adhesiveness.

For the vulcanization treatment, conventionally known vulcanization methods and conditions for vulcanizing rubber compositions can be employed. For example, a method of vulcanizing an unvulcanized laminate for a long time, a heat treatment as a pretreatment for a non-vulcanized laminate for a relatively short time (vulcanization is also occurring), and then vulcanizing over a long time. There is a method of performing sulfuration. Of these methods, a method in which the unvulcanized laminate is subjected to heat treatment as a pretreatment in a relatively short time and then vulcanized over a long time is obtained by pretreatment by the rubber layer (A) and the fluororesin layer (B). ) And the rubber layer (A) has already been vulcanized in the pretreatment and the shape is stabilized, so various methods for holding the laminate in subsequent vulcanization can be selected. This is preferable.

The conditions for the vulcanization treatment are not particularly limited and can be performed under normal conditions, but at 130 to 260 ° C. for 10 minutes to 80 hours, steam, press, oven, air bath, infrared, microwave, The treatment is preferably performed using lead vulcanization or the like. More preferably, it is performed at 160 to 230 ° C. for 20 minutes to 80 hours.

The heating conditions for the pretreatment are not particularly limited, but the treatment may be performed at 100 to 170 ° C. for 30 seconds to 1 hour using steam, press, oven, air bath, infrared ray, microwave, lead vulcanization, etc. preferable.

In the obtained laminate, the rubber layer (A) and the fluororesin layer (B) are vulcanized and bonded, and a strong interlayer adhesive force is generated.

The laminate of the present invention may have a two-layer structure of a rubber layer (A) and a fluororesin layer (B), or (A)-(B)-(A) or (B)-(A)-(B). Such a three-layer structure may be used. Further, it may have a multilayer structure of three or more layers in which polymer layers (C) other than the rubber layer (A) and the fluororesin layer (B) are bonded.

The polymer layer (C) may be a rubber layer (C1) other than the rubber layer (A), a resin layer (C2) other than the fluororesin layer (B), a fiber reinforced layer, or the like. Further, the rubber layer (A) and / or the fluororesin layer (B) may be further laminated via the polymer layer (C).

Examples of the material for the rubber layer (C1) include rubbers other than the rubber used as the rubber layer (A) directly bonded to the fluororesin layer (B), and may be fluororubber or non-fluororubber. Specific examples include those listed as examples of the unvulcanized rubber (a1).

In addition, you may mix | blend a vulcanizing agent (a6) and another compounding agent also in the unvulcanized rubber composition which forms a rubber layer (C1).

As the material of the resin layer (C2), fluororesin (excluding the fluororesin layer (B)), polyamide resin, polyolefin resin, vinyl chloride resin, polyurethane resin, polyester resin, polyaramid resin, polyimide resin, Polyamideimide resin, polyphenylene oxide resin, polyacetal resin, polycarbonate resin, acrylic resin, styrene resin, acrylonitrile / butadiene / styrene resin (ABS), cellulose resin, polyetheretherketone resin (PEEK), polysulfone resin, polyether Resins with excellent mechanical strength such as sulfone resin (PES) and polyetherimide resin, resins made of ethylene / vinyl alcohol copolymer, polyphenylene sulfide resin, polybutylene naphthalate resin, poly Chi terephthalate resins, polyphthalamide (PPA), such as fuel or gas permeability is low resin (hereinafter sometimes referred to low permeability resin) and the like. Of these, polyamide resins are preferred from the viewpoint of good moldability and adhesiveness. When the laminate is subjected to a vulcanization treatment, it is desirable that the melting point of the resin is higher than the temperature of the heat treatment.

The laminate of the present invention preferably has an adhesive strength of 5 N / cm or more, more preferably 10 N / cm or more, and further preferably 15 N / cm or more.

The said adhesive strength is based on the method as described in JIS-K-6256 (adhesion test method of crosslinked rubber) using the autograph (AGS-J 5kN by Shimadzu Corp.) about the said laminated body, for example. Then, a peel test is performed at 25 ° C. at a tensile speed of 50 mm / min, the adhesive strength is measured, and the average value of the obtained N = 3 data can be calculated.

From the viewpoint of heat resistance of the laminate, the rubber layer obtained by the vulcanization treatment has a tensile elongation at break change rate (ΔEb) before and after the heat resistance test (vulcanized rubber aging test) described in JIS K6257, − It is preferably 70% or less, more preferably −65% or less, and further preferably −60% or less.

The rate of change in tensile elongation at break (ΔEb) is determined by, for example, the method of the tensile test (vulcanized rubber tensile test) described in JIS K6251 before and after the vulcanized rubber aging test for the rubber layer obtained by the vulcanization treatment. It can be determined by conducting a tensile test of the vulcanized rubber.

Next, the layer structure of the laminate of the present invention will be described.

(1) A two-layer basic structure of rubber layer (A) -fluororesin layer (B). As described above, conventionally, in order to laminate the fluororesin layer (B) and the rubber layer (A), an interlayer ( Fluorine resin layer-rubber layer) is not sufficiently bonded, making the process complicated, such as surface treatment on the resin side, separate application of adhesive between layers, and winding and fixing a tape-like film However, vulcanization adhesion occurs by vulcanization without assembling such a complicated process, and chemically strong adhesion is obtained.

(2) There are three-layer structures (A)-(B)-(A) and (A)-(B)-(C1) of rubber layer-fluorine resin layer (B) -rubber layer. When sealing performance is required, it is desirable to arrange rubber layers on both sides in order to maintain the sealing performance, for example, in joints such as fuel pipes. The inner and outer rubber layers may be the same type or different types.

Further, the fuel pipe has a (A)-(B)-(C1) type structure, a non-fluororubber layer is provided as the rubber layer (A), a fluororubber layer is provided as the rubber layer (C1), and the fluororubber layer (C1). By using as the inner layer of the pipe, chemical resistance and low fuel permeability are improved.

(3) There are three-layer structures (B)-(A)-(B) and (B)-(A)-(C2) of resin layer-rubber layer (A) -resin layer.
The inner and outer rubber layers may be the same type or different types.

The shape is stabilized by arranging the resin layers on both sides. Moreover, it is suitable when chemical resistance is important. Further, when different mechanical characteristics are required on each side, the (B)-(A)-(C2) type may be used.

(4) Three-layer structure of resin layer (C2) -fluorine resin layer (B) -rubber layer (A)

(5) Three-layer structure of fluororesin layer (B) -rubber layer (A) -rubber layer (C1)

(6) Four-layer structure or more In addition to the three-layer structure of (2) to (5), any rubber layer (A) or (C1), resin layer (B) or (C2) is laminated depending on the purpose. May be. In addition, a layer such as a metal foil may be provided, or an adhesive layer may be interposed other than between the rubber layer (A) and the fluororesin layer (B).

Furthermore, it can be laminated with the polymer layer (C) to form a lining body.

In addition, what is necessary is just to select the thickness of each layer, a shape, etc. suitably according to a use purpose, a use form, etc.

The laminate of the present invention is excellent in low fuel permeability, heat resistance, oil resistance, fuel oil resistance, LLC resistance, steam resistance, and can withstand use under severe conditions. It can be used for various purposes.

For example, automotive engine engines, main motion systems, valve systems, lubrication / cooling systems, fuel systems, intake / exhaust systems, drive system transmission systems, chassis steering systems, brake systems, etc. Gaskets that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance, and non-contact and contact type packings (self-sealing) such as basic electrical parts, control system electrical parts, and equipped electrical parts (Packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.), etc., and suitable characteristics as bellows, diaphragm, hose, tube, electric wire, etc.

Specifically, it can be used for the applications listed below.

Engine body cylinder head gasket, cylinder head cover gasket, oil pan packing, gaskets such as general gaskets, seals such as O-rings, packing, timing belt cover gaskets, hoses such as control hoses, anti-vibration rubber for engine mounts, hydrogen Sealing material for high pressure valves in storage systems.

Shaft seals such as crankshaft seals and camshaft seals for main motion systems.

Valve stem seals for engine valves, etc.

Engine oil cooler hose, oil return hose, seal gasket, etc. for lubrication / cooling engine oil cooler, water hose around radiator, vacuum pump oil hose for vacuum pump, etc.

Fuel system, fuel pump oil seal, diaphragm, valve, etc. Filler (neck) hose, fuel supply hose, fuel return hose, fuel hose such as vapor (evaporation) hose, fuel tank in-tank hose, filler seal, tank Carburettors such as packing, in-tank fuel pump mount, fuel piping tube main body and connector O-ring, fuel injector injector cushion ring, injector seal ring, injector O-ring, pressure regulator diaphragm, check valves, etc. Needle valve petals, acceleration pump pistons, flange gaskets, control hoses, etc., composite air control (CAC) valve seats, diaphragms, etc.

Inlet / exhaust manifold manifold manifold packing, exhaust manifold packing, EGR diaphragm, control hose, emission control hose, BPT diaphragm, AB valve afterburn prevention valve seat, etc. Throttle body packing, turbocharger turbo oil hose (supply), turbo oil hose (return), turbo air hose, intercooler hose, turbine shaft seal etc.

Transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses, AT transmission oil hoses, ATF hoses, O-rings, packings, etc.

Steering power steering oil hose, etc.

Brake oil seals, O-rings, packings, brake oil hoses, etc. Master back atmospheric valves, vacuum valves, diaphragms, etc. Master cylinder piston cups (rubber cups), caliper seals, boots, etc.

Tubes for harness exterior parts such as electric wire (harness) insulators and sheaths for basic electrical components.

Coating materials for various sensor wires for control system electrical components.

Car equipment air conditioner O-rings, packing, cooler hoses, exterior wiper blades, etc.

In addition to automobiles, for example, oil, chemical, heat, steam, or weather resistant packings, O-rings, hoses, other sealing materials, diaphragms, valves, chemicals, etc. Similar packings in plants, O-rings, seals, diaphragms, valves, hoses, rolls, tubes, chemical coatings, linings, similar packings in food plant equipment and food equipment (including household products), O- Rings, hoses, sealing materials, belts, diaphragms, valves, rolls, tubes, similar packings in nuclear power plant equipment, O-rings, hoses, sealing materials, diaphragms, valves, tubes, similar packings in general industrial parts, O-ring, hose, sealing material, diaphragm Is suitable valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, the application to a roll blade PPC copying machine. For example, the backup rubber material of PTFE diaphragm has a problem that it is worn out or torn during use because of its poor sliding property, but by using the laminate of the present invention, this problem can be improved and suitable. Can be used for

In addition, in food rubber seal material applications, there is a problem that flavoring or rubber fragments are mixed into food in conventional rubber seal materials, but by using the laminate of the present invention, this problem can be improved and preferably Can be used. When using solvents in pharmaceutical and chemical applications, there is a problem that rubber materials swell in the solvent, but by using the laminate of the present invention, chemical resistance, low elution, and low flavoring can be achieved by coating the resin. This problem is ameliorated. In the general industrial field, for the purpose of improving the strength, slipperiness, chemical resistance, and permeability of rubber materials, it can be suitably used for rubber rolls, O-rings, packing, sealing materials, and the like. In particular, it can be preferably used for packing of lithium ion batteries because both chemical resistance and sealing can be maintained at the same time. In addition, it can be suitably used in applications where slidability with low friction is required.

Among these, the laminate of the present invention is particularly preferably used for fuel piping from the viewpoint of heat resistance and low fuel permeability. That is, this invention is also fuel piping which consists of the said laminated body.

The fuel pipe made of the laminate of the present invention can be produced by an ordinary method and is not particularly limited. Further, the fuel pipe of the present invention includes a corrugated tube.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Hereinafter, the fluororesin used in Examples and Comparative Examples and the measuring method thereof will be described.

(1) Polymer composition
^It was measured by ¹⁹ F-NMR analysis.

(2) Using a melting point Seiko type DSC apparatus, 10 ° C./min. The melting peak when the temperature was raised at a speed of was recorded, and the temperature corresponding to the maximum value was taken as the melting point.

(3) MFR (Melt Flow Rate)
Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the weight (g) of the polymer flowing out in a unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under various temperatures and 5 kg load was measured.

(4) Measurement of fuel permeability coefficient of a single layer Each resin pellet was put into a mold having a diameter of 120 mm, set in a press machine heated to 300 ° C., melt-pressed at a pressure of about 2.9 MPa, A 0.15 mm sheet was obtained. Put the obtained sheet into a SUS316 transmission coefficient measuring cup made of SUS316 with an inner diameter of 40 mmφ and a height of 20 mm containing 18 mL of CE10 (fuel obtained by mixing 10% by volume of ethanol in a 50:50 volume ratio of isooctane and toluene) The mass change at 60 ° C. was measured up to 1000 hours. The fuel permeability coefficient (g · mm / m ² / day) was calculated from the change in mass per hour, the surface area of the sheet in the wetted part, and the thickness of the sheet.

Hereinafter, the fluororesins in Examples and Comparative Examples are shown in Table 2 below.

(Rubber compositions A to N and a to f for vulcanization)
The materials shown in Table 3 or 4 below were kneaded using an 8-inch open roll to obtain sheet-shaped rubber compositions A to N and a to f having a thickness of about 3 mm. In addition, each numerical value of Table 3 and Table 4 shows a mass part.
Further, for the rubber compositions A to N and a to f for vulcanization, a maximum torque value (M _H ) at 160 ° C. using a curast meter type II (model number: JSR curast meter, manufactured by JSR). ) And the minimum torque value (M _L ) were measured, and the optimum vulcanization time (T ₉₀ ) was determined. Table 5 shows the measurement results. _{Incidentally, T 90 is} - a _{{(M H) (M L} )} × 0.9 + M L become time, _{M H} and _{M L} is the value measured according to JIS K 6300-2.

(Examples 1-14 and Comparative Examples 1-6)
A sheet of the rubber composition for vulcanization shown in Table 3 or Table 4 having a thickness of about 3 mm and a sheet of fluororesin (1) having a thickness of 120 μm are overlapped, and a fluorine resin film having a width of about 10 to 15 mm at one end. (Thickness 10 μm, product name Polyflon PTFE M731 skive film manufactured by Daikin Industries, Ltd.) was sandwiched between both sheets, and then inserted into a mold with a metal spacer so that the resulting sheet had a thickness of 2 mm, A sheet-like laminate was obtained by pressing at 160 ° C. for 45 minutes. The obtained laminate was cut into strips each having a width of 10 mm, a length of 40 mm, and 3 sets, and a fluororesin sheet was peeled off to prepare a test piece for gripping. About this test piece, according to the method as described in JIS-K-6256 (adhesion test method of crosslinked rubber) using an autograph (manufactured by Shimadzu Corporation, AGS-J 5 kN), and 50 mm / 25 ° C. A peel test was performed at a tensile rate of min, the adhesive strength was measured, and the average value of the obtained data of N = 3 was calculated and used as the adhesive strength. Moreover, the peeling mode was observed and evaluated according to the following criteria. The results obtained are shown in Table 6.

(Adhesion evaluation)
A: The rubber layer or fluororesin layer vulcanized at the interface of the laminate was destroyed, and it was impossible to peel off at the interface.
X: Peeled relatively easily at the interface of the laminate.

(Heat aging test of vulcanized rubber)
A vulcanized rubber sheet having a thickness of 2 mm was obtained by pressing the vulcanized rubber composition sheet shown in Table 3 or Table 4 having a thickness of about 3 mm at 160 ° C. for 45 minutes.
Six sets of the obtained vulcanized rubber sheets were cut into JIS No. 4 size to prepare test pieces.
About this test piece, in accordance with the method of the heat resistance test (vulcanized rubber aging test) described in JIS K6257, heat aging of vulcanized rubber was performed using an electric furnace under the conditions of a test temperature of 121 ° C. and a test time of 168 hours. A test was conducted.

(Tensile test of vulcanized rubber)
The test pieces before and after the heat aging test of the vulcanized rubber are subjected to a tensile test of the vulcanized rubber according to the method of the tensile test (vulcanized rubber tensile test) described in JIS K6251 to aging the vulcanized rubber. The tensile breaking elongation change rate (ΔEb) before and after the test was determined.

The laminate of the present invention has excellent fuel low permeability, heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance. The engine body, main motion system, and valve train for automobile engines System, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, etc. Gaskets that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance, and non-contact type and contact type packings (self-seal packing, piston ring, split ring type packing, mechanical seal, oil seal Etc.) can be used for seals, bellows, diaphragms, hoses, tubes, electric wires, etc.

Claims (6)

A laminate comprising a rubber layer (A) and a fluororesin layer (B) laminated on the rubber layer (A),
The rubber layer (A) is a layer formed from a vulcanizing rubber composition, and the vulcanizing rubber composition is
Unvulcanized rubber (a1),
1,8-diazabicyclo (5.4.0) undecene-7,8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride, 1,8-diazabicyclo (5.4. 0) naphthoate salt of undecene-7, phenol salt of 1,8-diazabicyclo (5.4.0) undecene-7, orthophthalate salt of 1,8-diazabicyclo (5.4.0) undecene-7, , 8-diazabicyclo (5.4.0) undecene-7 formate and at least one compound (a2) selected from the group consisting of 1,5-diazabicyclo (4.3.0) nonene-5 ,
An anti-aging agent (a3) comprising at least two kinds selected from the group consisting of an aromatic secondary amine type anti-aging agent, a bisphenol type anti-aging agent, a benzimidazole type anti-aging agent and a thiourea type anti-aging agent,
Magnesium oxide (a4), and
Containing silica (a5),
The fluororesin layer (B) is a layer formed from a fluoropolymer composition, and the fluoropolymer composition contains a fluoropolymer (b1) having polymerized units derived from chlorotrifluoroethylene. Laminated body. The anti-aging agent (a3) is composed of at least two kinds selected from the group consisting of an aromatic secondary amine type anti-aging agent, a bisphenol type anti-aging agent and a benzimidazole type anti-aging agent. The laminate according to claim 1, wherein a3) is 2 to 9 parts by mass in total with respect to 100 parts by mass of the unvulcanized rubber (a1). Anti-aging agent (a3) is a combination of an aromatic secondary amine anti-aging agent and a bisphenol anti-aging agent, a combination of an aromatic secondary amine anti-aging agent and a benzimidazole anti-aging agent, bisphenol Consisting of a combination of an anti-aging agent and a benzimidazole anti-aging agent, or a combination of an aromatic secondary amine anti-aging agent, a bisphenol anti-aging agent and a benzimidazole anti-aging agent,
The aromatic secondary amine anti-aging agent is 0.1 to 5 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1),
The bisphenol-based anti-aging agent is 0.1 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1),
The laminate according to claim 1 or 2, wherein the benzimidazole-based antioxidant is 0.1 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). The anti-aging agent (a3) is a combination of at least one anti-aging agent selected from the group consisting of an aromatic secondary amine anti-aging agent and a bisphenol anti-aging agent and a benzimidazole anti-aging agent. Become
At least one type of anti-aging agent selected from the group consisting of the aromatic secondary amine type anti-aging agent and the bisphenol type anti-aging agent is a total of 100 parts by mass of the unvulcanized rubber (a1). 1 to 6 parts by mass,
The laminate according to claim 1, 2 or 3, wherein the benzimidazole-based anti-aging agent is 1 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). The laminate according to claim 1, 2, 3, or 4, wherein the unvulcanized rubber (a1) is acrylonitrile-butadiene rubber or a hydride thereof. The laminate according to claim 1, 2, 3, 4 or 5, wherein the fluoropolymer (b1) is a chlorotrifluoroethylene-tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer.