JP2017056599A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of not only preventing fuel from permeating to the thickness direction of the laminate but also of preventing fuel from permeating to the length direction of the laminate, while excelling in all of a rubber adhesive property, fuel resistance and flexibility.SOLUTION: There is provided a laminate 11 comprising: a layer (A) 11a comprising a cross-linked fluororubber (a) and a fluororesin (a); a layer (B) 11b comprising a rubber (b); a layer (C) 11c comprising a fluororesin (c) having a fuel permeability coefficient of 5.0 g mm/m/day or less; and a layer (D) 11d comprising a rubber (d) (excluding a fluororubber). In the layer (A) 11a of the laminate 11, the cross-linked fluororubber (a) is obtained by dynamically subjecting an uncross-linked fluororubber (a) to cross-linking treatment in the presence of the fluororesin (a) under melting condition of the fluororesin (a).SELECTED DRAWING: Figure 1

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 transport rubber hoses, laminated hoses with fluororesin as a barrier layer (rubber other than the barrier layer) are used to improve fuel permeation resistance. Due to the recent strong demand for reducing environmental impact, One layer of low fuel permeability due to the barrier layer is required. 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.

Under such circumstances, Patent Document 1 includes a fluororubber layer (A), a rubber layer (B), a fluororesin layer (C), and a rubber layer (D). A laminated body characterized in that a rubber layer (B), a fluororesin layer (C), and a rubber layer (D) are laminated in this order has been proposed.

JP 2014-226853 A

The laminate described in Patent Document 1 is excellent in all of rubber adhesiveness, fuel resistance, and flexibility. As for the fuel barrier property, the permeation of fuel in the thickness direction of the laminate can be suppressed at a high level. However, in order to further reduce the transpiration of the fuel, a technique for suppressing the permeation of the fuel in the length direction of the laminated body is required.

In view of the above situation, the present invention is excellent in all of rubber adhesion, fuel resistance, and flexibility, and can not only suppress the permeation of fuel in the thickness direction of the laminate, but also the length of the laminate. It is an object of the present invention to provide a laminate that can suppress fuel permeation in the vertical direction.

The present inventors have found that the above-mentioned problem can be solved brilliantly by combining four layers having different forming materials, and have completed the present invention.

The present invention includes a layer (A) composed of a crosslinked fluororubber (a) and a fluororesin (a), a layer (B) composed of a rubber (b), and a fuel permeability coefficient of 5.0 g · mm / m ² / day or less. A laminate comprising a layer (C) made of a fluororesin (c) and a layer (D) made of a rubber (d) (excluding fluororubber).

In the layer (A), the crosslinked fluororubber (a) dynamically crosslinks the uncrosslinked fluororubber (a) in the presence of the fluororesin (a) under the melting condition of the fluororesin (a). It is preferable that it was obtained by.

In the layer (A), it is preferable that the fluororesin (a) forms a continuous layer and the crosslinked fluororubber (a) forms a dispersed phase.

The layer (A) is a step of obtaining a composition (a1) containing an uncrosslinked fluororubber (a) and a crosslinking agent (a), and the composition (a1) and the fluororesin (a) are made of the fluororesin (a). It is manufactured by a manufacturing method including a step of obtaining a composition (a2) by kneading at a temperature equal to or higher than the melting point, and a step of forming the composition (a2), and the fuel permeation of the composition (a2) The coefficient is preferably 10.0 g · mm / m ² / day or less.

The layer (A) is a step of obtaining a composition (a1) containing an uncrosslinked fluororubber (a) and a crosslinking agent (a), and the composition (a1) and the fluororesin (a) are made of the fluororesin (a). Bending elasticity of the composition (a2) produced by a production method comprising a step of obtaining a composition (a2) by kneading at a temperature equal to or higher than the melting point and a step of molding the composition (a2) The rate is preferably 1000 MPa or less.

The flexural modulus of the fluororesin (c) is preferably 1000 MPa or less.

The laminate of the present invention preferably has an initial interlayer adhesion strength of 5 N / cm or more between all layers.

The above-mentioned laminate which is a hose is also one aspect of the present invention.

The above-described laminate that is a fuel pipe hose is also one aspect of the present invention.

The laminate of the present invention is excellent in all of rubber adhesion, fuel resistance, and flexibility, and moreover, fuel permeation in the thickness direction of the laminate and in the length direction of the laminate. Both fuel permeations are very small.

It is a schematic diagram which shows the permeation | transmission mechanism of the fuel from the conventional laminated body. It is a schematic diagram which shows the permeation | transmission mechanism of the fuel from the conventional laminated body.

Hereinafter, the present invention will be specifically described.

The laminate of the present invention includes layers (A) to (D), and the layer (A) is a layer made of a crosslinked fluororubber and a fluororesin.

FIG. 1 shows a laminated structure of the laminated body described in Patent Document 1. This laminate has a structure in which a fluororubber layer 11a, a rubber layer 11b, a fluororesin layer 11c, and a rubber layer 11d are laminated in this order, and has a fuel barrier property, rubber adhesion, fuel resistance, and flexibility. Excellent in properties. However, the fuel barrier property can sufficiently suppress the permeation of fuel in the A direction, but there is room for improvement in suppressing the permeation of fuel in the B direction. In particular, rubber is difficult to be molded thinner than resin, and the rubber layer 11b is likely to be thick, and the fuel permeability is poor, so that it is not easy to suppress the fuel permeation in the B direction. It was issued.
For example, when the laminated body is used as a fuel pipe hose, as shown in FIG. 2, the laminated body 11 is inserted into the iron pipe 13 and positioned with the stopper 13a, and then the laminated body 11 is used. Is used by caulking the outer periphery thereof with a sleeve member 12. The fuel that has permeated in the B direction of the laminated body 11 may be discharged to the outside from the end of the laminated body that is located around the iron pipe 13, and it is required to suppress the permeation thereof.

If the fluororubber layer 11a and the rubber layer 11b are made of fluororesin, there is a high possibility that fuel in the A direction and the B direction can be suppressed. However, when the laminate is used as a fuel pipe hose, it has also been found that since the fluororesin is inferior in flexibility and sealing performance, fuel leakage from the hose and iron pipe is likely to occur. It was.

The layered product of the present invention solves a plurality of above-mentioned problems simultaneously. Since the laminate of the present invention includes a layer made of a cross-linked fluororubber and a fluororesin, the laminate has sufficient flexibility, and the fuel does not easily permeate not only in the A direction but also in the B direction. Therefore, when used as a fuel piping tube, the transpiration of fuel from the fuel supply system of the automobile can be greatly reduced.

Since the laminated body of the present invention can suppress the permeation of fuel in the length direction to the maximum, the layer (A) is the innermost layer, and the layer (B) and the layer (C) are sequentially formed on the layer (A). ) And layer (D) are preferably laminated.

Next, materials constituting each layer will be described.

1. Layer (A) The layer (A) comprises a crosslinked fluororubber (a) and a fluororesin (a).

The crosslinked fluororubber (a) is obtained by dynamically crosslinking the uncrosslinked fluororubber (a) in the presence of the fluororesin (a) and under the melting conditions of the fluororesin (a). Is preferred.

The dynamic crosslinking treatment means that the uncrosslinked fluororubber (a) is dynamically crosslinked simultaneously with melt kneading using a Banbury mixer, a pressure kneader, an extruder, or the like. Among these, an extruder such as a twin screw extruder is preferable because a high shear force can be applied. By dynamically crosslinking, the phase structure of the fluororesin (a) and the crosslinked fluororubber (a) can be controlled.

The term “crosslinking treatment under melting conditions” means that the crosslinking treatment is performed at a temperature equal to or higher than the melting point of the fluororesin (a). The temperature of the crosslinking treatment is preferably not less than the melting point of the fluororesin (a), more preferably 330 ° C. or less, and further preferably 324 ° C. or less. As long as the temperature is equal to or higher than the melting point of the fluororesin (a), it may be 120 ° C. or higher, 130 ° C. or higher, or higher than 140 ° C. If the temperature is too low, the fluororesin (a) and the crosslinked fluororubber (a) may not be sufficiently dispersed with each other. If the temperature is too high, the uncrosslinked fluororubber (a) may be thermally deteriorated. .

The crosslinked fluororubber (a) is obtained by dynamically crosslinking the uncrosslinked fluororubber (a) in the presence of the fluororesin (a) and the crosslinking agent (a) under the melting condition of the fluororesin (a). More preferably, it is obtained. In addition to the fluororesin (a) and the crosslinking agent (a), it is also preferred to use a crosslinking accelerator (a).

In the layer (A), the fluororesin (a) may form a continuous layer and the cross-linked fluororubber (a) may form a dispersed phase, or the fluororesin (a) and the cross-linked fluororubber (a) may be combined. Although a continuous phase structure may be formed, it is preferable that the fluororesin (a) forms a continuous layer and the crosslinked fluororubber (a) forms a dispersed phase. In addition, the co-continuous phase of the fluororesin (a) and the cross-linked fluororubber (a) is part of a structure in which the fluororesin (a) forms a continuous phase and the cross-linked fluororubber (a) forms a dispersed phase. It may contain a structure.

Even when the uncrosslinked fluororubber (a) originally formed a matrix, if the uncrosslinked fluororubber (a) is changed to the crosslinked fluororubber (a) by the crosslinking reaction, the crosslinked fluororubber (a) is not yet used. Since the melt viscosity is higher than that of the crosslinked fluororubber (a), the crosslinked fluororubber (a) forms a dispersed phase, or the fluororesin (a) and the crosslinked fluororubber (a) form a co-continuous phase structure. Become.

The mass ratio of the crosslinked fluororubber (a) to the fluororesin (a) (crosslinked fluororubber (a) / fluororesin (a)) is preferably 95/5 to 5/95, and 70/30 to 7 / 93 is more preferable, and 50/50 to 10/90 is still more preferable. If the amount of the cross-linked fluororubber (a) is too large, fuel permeation may not be sufficiently suppressed, and if the amount of the cross-linked fluororubber (a) is too small, the laminate may have poor flexibility.

The average dispersed particle size of the cross-linked fluororubber (a) is preferably 0.01 to 30 μm, and more preferably 0.1 to 10 μm.

The average dispersed particle size can be confirmed by using any one of atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), or a combination thereof. For example, when AFM is used, the difference obtained from the surface information of the fluororesin (a) in the continuous phase and the cross-linked fluororubber (a) in the dispersed phase is obtained as a light / dark image. Can be priced. The binarization position is set to the center level divided by gradation, whereby an image with a clear contrast can be obtained, and the crosslinked rubber particle diameter of the dispersed phase can be read. When SEM is used, contrast should be emphasized or the brightness or darkness adjustment or both adjustments should be applied to the image so that the cross-linked fluororubber (a) in the dispersed phase will be clear from the image obtained by the reflected electron image. As in AFM, the crosslinked rubber particle diameter of the dispersed phase can be read. In the case of TEM, the cross-linked rubber particle diameter of the dispersed phase can be read as in AFM and SEM by adjusting the contrast of the obtained image and / or adjusting the brightness and darkness as in SEM. These may be selected more easily for each thermoplastic polymer composition.

The fluororesin (a) is preferably a melt processable fluororesin. Melt processability means that the polymer can be melted and processed using conventional processing equipment such as extruders and injection molding machines. Therefore, the melt processable fluororesin usually has a melt flow rate of 0.01 to 500 g / 10 min.

More preferably, the fluororesin (a) has a melt flow rate (MFR) of 1 to 500 g / 10 min. MFR is a method based on ASTM D1238, using a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and a measurement temperature determined by the type of fluororesin (a) (for example, 372 for PFA and FEP). ° C, 297 ° C for ETFE, 297 ° C for copolymers with CTFE units, 265 ° C for VdF / TFE copolymers), load (eg PFA, FEP, ETFE, CTFE units) The mass of the polymer (g / 10 minutes) flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes in the case of a copolymer having a VdF / TFE copolymer (5 kg).

The melting point of the fluororesin (a) is preferably 100 to 323 ° C, and more preferably 140 to 323 ° C. The melting point is 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 differential scanning calorimeter [DSC].

Examples of the fluororesin (a) include tetrafluoroethylene [TFE] / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA], TFE / hexafluoropropylene [HFP] copolymer [FEP], ethylene / TFE copolymer At least one selected from the group consisting of a polymer [ETFE], a polymer having a chlorotrifluoroethylene [CTFE] unit, polyvinylidene fluoride [PVdF], and vinylidene fluoride [VdF] / TFE copolymer It is preferable that These are all melt-processable fluororesins.

As fluororesin (a), PFA, FEP, polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene [CTFE] / TFE / PAVE copolymer, ethylene / CTFE copolymer, PVdF, ETFE, and VdF More preferred is at least one selected from the group consisting of / TFE copolymers, and even more preferred is ETFE.

As the _{PAVE, CF 2 = CF-ORf} 4 ( wherein, Rf ⁴ represents. A perfluoroalkyl group having 1 to 5 carbon atoms) is preferably a perfluoro (alkyl vinyl ether) represented by.

Although it does not specifically limit as said PFA, The copolymer whose molar ratio (TFE unit / PAVE unit) of a TFE unit and a PAVE unit is 70/30 or more and less than 99/1 is preferable. A more preferable molar ratio is 70/30 or more and 98.9 / 1.1 or less, and a still more preferable molar ratio is 80/20 or more and 98.9 / 1.1 or less. When there are too few TFE units, there exists a tendency for a mechanical physical property to fall, and when too much, melting | fusing point becomes high too much and there exists a tendency for a moldability to fall. The PFA may be a copolymer composed only of TFE units and PAVE units, or the monomer units derived from monomers copolymerizable with TFE and PAVE are 0.1 to 10 mol%. It is also preferred that the copolymer has a total of 90 to 99.9 mol% of TFE units and PAVE units. Monomers copolymerizable with TFE and PAVE include HFP, CZ ³ Z ⁴ = CZ ⁵ (CF ₂ ) _n Z ⁶ (wherein Z ³ , Z ⁴ and Z ⁵ are the same or different and are hydrogen represents an atom or fluorine atom, ^{Z 6} represents a hydrogen atom, a fluorine atom or a chlorine atom, a vinyl monomer n is represented by the representative.) the integer from 2 to 10, _and, CF 2 = CF-OCH Examples thereof include alkyl perfluorovinyl ether derivatives represented by _2- Rf ⁷ (wherein Rf ⁷ represents a perfluoroalkyl group having 1 to 5 carbon atoms).

The PFA preferably has a melting point of 180 or more and less than 323 ° C, more preferably 230 to 320 ° C, and still more preferably 280 to 320 ° C.

The PFA preferably has a melt flow rate (MFR) of 1 to 500 g / 10 minutes.

The PFA preferably has a thermal decomposition starting temperature of 380 ° C. or higher. The thermal decomposition start temperature is more preferably 400 ° C. or higher, and still more preferably 410 ° C. or higher.

Although it does not specifically limit as FEP, The copolymer whose molar ratio (TFE unit / HFP unit) of a TFE unit and a HFP unit is 70/30 or more and less than 99/1 is preferable. A more preferable molar ratio is 70/30 or more and 98.9 / 1.1 or less, and a still more preferable molar ratio is 80/20 or more and 98.9 / 1.1 or less. When there are too few TFE units, there exists a tendency for a mechanical physical property to fall, and when too much, melting | fusing point becomes high too much and there exists a tendency for a moldability to fall. The FEP may be a copolymer consisting only of TFE units and HFP units, or the monomer units derived from monomers copolymerizable with TFE and HFP are 0.1 to 10 mol%. It is also preferred that the copolymer has a total of 90 to 99.9 mol% of TFE units and HFP units. Examples of monomers copolymerizable with TFE and HFP include PAVE and alkyl perfluorovinyl ether derivatives.

The FEP preferably has a melting point of less than 150 to 323 ° C, more preferably 200 to 320 ° C, and still more preferably 240 to 320 ° C.

The FEP preferably has an MFR of 1 to 500 g / 10 minutes.

The FEP preferably has a thermal decomposition starting temperature of 360 ° C. or higher. The thermal decomposition starting temperature is more preferably 380 ° C. or higher, and further preferably 390 ° C. or higher.

The ETFE is preferably a copolymer having a molar ratio of TFE units to ethylene units (TFE units / ethylene units) of 20/80 or more and 90/10 or less. A more preferable molar ratio is 37/63 or more and 85/15 or less, and a further preferable molar ratio is 38/62 or more and 80/20 or less. ETFE may be a copolymer composed only of TFE units and ethylene units, or may be a copolymer composed of TFE, ethylene, and monomers copolymerizable with TFE and ethylene.

As a copolymerizable monomer, the following formula CH ₂ = CX ⁵ Rf ³ , CF ₂ = CFRf ³ , CF ₂ = CFORf ³ , CH ₂ = C (Rf ³ ) ₂
(Wherein, X ⁵ represents a hydrogen atom or a fluorine atom, and Rf ³ represents a fluoroalkyl group which may contain an ether bond), among which CF ₂ = CFRf ³ , A fluorine-containing vinyl monomer represented by CF ₂ = CFORf ³ and CH ₂ = CX ⁵ Rf ³ is preferred, and HFP, CF ₂ = CF-ORf ⁴ (wherein Rf ⁴ is a perfluoroalkyl having 1 to 5 carbon atoms) It represents a group. perfluoro (alkyl vinyl ether represented by)), and Rf ³ is more preferably a fluorine-containing vinyl monomer represented by _CH 2 = ^CX 5 Rf ³ is a fluoroalkyl group having 1 to 8 carbon atoms. The monomer copolymerizable with TFE and ethylene may be an aliphatic unsaturated carboxylic acid such as itaconic acid or itaconic anhydride. The monomer copolymerizable with TFE and ethylene is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 5 mol%, further preferably from 0.2 to 4 mol%, based on the fluoropolymer. preferable.

The ETFE is preferably a copolymer containing an ethylene unit, a TFE unit and an HFP unit (hereinafter also referred to as “ethylene / TFE / HFP copolymer”). The ethylene / TFE / HFP copolymer preferably contains 30 to 70 mol% of ethylene units, 20 to 55 mol% of TFE units, and 1 to 30 mol% of HFP units. The ethylene / TFE / HFP copolymer may also contain monomer units (excluding HFP units) copolymerizable with the TFE and ethylene described above, and the amount thereof is based on the fluorine-containing polymer. 0.1-10 mol% is preferable, 0.1-5 mol% is more preferable, 0.2-4 mol% is still more preferable.

The ETFE preferably has a melting point of 140 to 323 ° C, more preferably 160 to 320 ° C, and still more preferably 195 to 320 ° C.

The ETFE preferably has an MFR of 1 to 500 g / 10 minutes.

The ETFE preferably has a thermal decomposition starting temperature of 330 ° C. or higher. The thermal decomposition starting temperature is more preferably 340 ° C. or higher, and further preferably 350 ° C. or higher.

The VdF / TFE copolymer preferably contains 40 to 90% by mass of VdF units and 10 to 60% by mass of TFE units. More preferably, the VdF / TFE copolymer contains 70 to 90% by mass of VdF units and 10 to 30% by mass of TFE units.

The VdF / TFE copolymer may be a copolymer composed only of TFE units and TFE units, but a copolymer containing VdF units, TFE units, and HFP units (hereinafter referred to as “VdF / TFE / HFP copolymer”). It is also preferred that it be referred to as “polymer”.

The VdF / TFE / HFP copolymer preferably contains 10 to 75% by mass of VdF units, 24 to 85% by mass of TFE units and 1 to 20% by mass of HFP units, and 10 to 70% by mass of VdF units and TFE units. More preferably, it contains 25 to 80% by mass and 3 to 15% by mass of HFP units, more preferably 15 to 60% by mass of VdF units, 30 to 78% by mass of TFE units and 4 to 12% by mass of HFP units.

The VdF / TFE copolymer includes monomer units such as perfluoro (alkyl vinyl ether) such as perfluoro (methyl vinyl ether) and non-fluorine monomers such as ethylene and propylene in addition to the monomer units described above. May further be included.

The VdF / TFE / HFP / PAVE copolymer may contain 2 to 30% by mass of VdF units, 50 to 95% by mass of TFE units, 2 to 15% by mass of HFP units, and 0.01 to 3% of PAVE units. Preferably, it contains VdF units 4 to 20% by mass, TFE units 60 to 90% by mass, HFP units 3 to 12% by mass, and PAVE units 0.05 to 2%, more preferably VdF units 5 to 15% by mass, More preferably, it contains 70 to 88% by mass of TFE units, 4 to 10% by mass of HFP units, and 0.1 to 1.5% of PAVE units.

The VdF / TFE copolymer preferably has an MFR of 1 to 500 g / 10 minutes.

The VdF / TFE copolymer preferably has a melting point of 150 to 270 ° C, more preferably 160 to 270 ° C.

Examples of commercially available products applicable as the VdF / TFE copolymer include THV815, THV500G, THV400G, THV610G (manufactured by 3M) and the like.

The polymer having the CTFE unit is preferably at least one selected from the group consisting of polychlorotrifluoroethylene [PCTFE] and a CTFE copolymer, PCTFE, CTFE / TFE copolymer, and ethylene. More preferably, it is at least one selected from the group consisting of / CTFE copolymers.

The CTFE copolymer includes CTFE units, TFE, HFP, PAVE, VdF, vinyl fluoride, hexafluoroisobutene, a formula: CH ₂ = CX ¹ (CF ₂ ) _n X ² (where 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, vinyl chloride, and vinylidene chloride And a unit derived from at least one monomer selected from the group consisting of:

The CTFE copolymer includes an ethylene / CTFE copolymer, and a copolymer containing CTFE units and units derived from at least one monomer selected from the group consisting of TFE, HFP, and PAVE. More preferred is at least one selected from the group consisting of coalescence.

The ethylene / CTFE copolymer (ECTFE) is a copolymer containing an ethylene unit and a CTFE unit, wherein the ethylene unit is 46 to 52 mol% based on the total of the ethylene unit and the CTFE unit, and the CTFE. The unit is preferably 54 to 48 mol%. ECTFE may be a binary copolymer consisting only of ethylene units and CTFE units, or may be a polymerization based on monomers (for example, fluoroalkyl vinyl ether (PAVE) derivatives) copolymerizable with ethylene and CTFE. It may contain a unit.
The content of polymerized units based on monomers copolymerizable with ethylene and CTFE is 0.01 to 5 with respect to the total of ethylene units, CTFE units and polymerized units based on the copolymerizable monomers. It is preferable that it is mol%.

The ECTFE preferably has an MFR of 0.01 to 100 g / 10 min. MFR is measured at a temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM 3275-81.

As said CTFE copolymer, what contains the monomer ((alpha)) unit derived from a CTFE unit, a TFE unit, and the monomer ((alpha)) copolymerizable with these is especially preferable.

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) (PAVE) represented by 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), An alkyl perfluorovinyl ether derivative represented by CF ₂ = CF—OCH ₂ —Rf ² (wherein Rf ² is a C 1-5 perfluoroalkyl group) is exemplified. Preferably, it is at least one selected from the group consisting of AVE, the above vinyl monomer, and an alkyl perfluorovinyl ether derivative, more preferably at least one selected from the group consisting of PAVE and HFP. .

The PAVE is preferably perfluoro (alkyl vinyl ether) represented by CF ₂ = CF-ORf ⁴ (wherein Rf ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms). Fluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (butyl vinyl ether), etc., among them, the group consisting of PMVE, PEVE and PPVE More preferably, it is at least one selected from more.

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 with respect to 15 to 90 mol% of CTFE units, and more preferably 20 to 90 mol of CTFE units. %, And TFE units are 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 PAVE unit is preferably 0.5 mol% or more, more preferably 5 mol% or less of the total monomer units.

The content of each monomer unit of the copolymer described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

The crosslinked fluororubber (a) is preferably obtained by crosslinking the uncrosslinked fluororubber (a). The uncrosslinked fluororubber (a) is preferably at least one selected from the group consisting of perfluororubber, partially fluorinated rubber and fluorine-containing thermoplastic elastomer, more preferably partially fluorinated rubber. .
The uncrosslinked fluororubber (a) preferably has a Mooney viscosity ML _{(1 + 10)} of 10 to 100, for example. The Mooney viscosity ML _{(1 + 10)} can be measured according to ASTM D-1646 at 121 ° C. using a Mooney viscometer MV2000E type manufactured by ALPHA TECHNOLOGIES.

Examples of the perfluoro rubber include a TFE / PAVE copolymer, a TFE / HFP / PAVE copolymer, and the like.

Partially fluorinated rubbers include vinylidene fluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE) / propylene (Pr) fluorine rubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluorine rubber. , Ethylene / hexafluoropropylene (HFP) fluorine rubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluorine rubber Etc. Especially, it is preferable that it is at least 1 sort (s) selected from the group which consists of vinylidene fluoride type | system | group fluorine rubber and tetrafluoroethylene / propylene type fluorine rubber.

The vinylidene fluoride-based fluororubber is preferably a copolymer composed of 45 to 85 mol% of vinylidene fluoride and 55 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. . More preferably, it is a copolymer comprising 50 to 80 mol% of vinylidene fluoride and 50 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.

Examples of at least one other monomer copolymerizable with the vinylidene fluoride include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], fluoroalkyl vinyl ether, chlorotrifluoroethylene [CTFE], trifluoroethylene, Trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, general formula (A): CH ₂ = CFRf ⁶¹ (wherein Rf ⁶¹ is a straight chain having 1 to 12 carbon atoms) Or a branched fluoroalkyl group), a general formula (B): CH ₂ ═CH— (CF ₂ ) _n —X ² (wherein X ² is H or F, and n is 3 to 3). Is an integer of 10.) and gives a crosslinking site. Monomers monomers, ethylene, propylene, and a non-fluorinated monomer such as an alkyl vinyl ether. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether and CTFE. As the fluoroalkyl vinyl ether, perfluoro (alkyl vinyl ether) represented by CF ₂ = CF—ORf ⁴ (wherein Rf ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms) is preferable.

Specific examples of the vinylidene fluoride-based fluororubber are represented by VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, VdF / general formula (A). Fluoromonomer rubber, VdF / fluoromonomer / TFE rubber represented by general formula (A), VdF / perfluoro (methyl vinyl ether) [PMVE] rubber, VdF / PMVE / TFE rubber, VdF / PMVE / Examples include TFE / HFP rubber. As the fluoromonomer rubber represented by VdF / general formula (A), VdF / CH ₂ = CFCF ₃ rubber is preferable, and as the fluoromonomer / TFE rubber represented by VdF / general formula (A), VdF / TFE / CH ₂ ═CFCF ₃ rubber is preferable.

The VdF / CH ₂ = CFCF ₃ rubber is preferably a copolymer comprising VdF 40 to 99.5 mol% and CH ₂ = CFCF ₃ 0.5 to 60 mol%, and VdF 50 to 85 mol%. , and _is more preferably a copolymer consisting of CH ₂ = CFCF 3 20~50 mol%.

The tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer composed of 45 to 70 mol% tetrafluoroethylene, 55 to 30 mol% propylene, and 0 to 5 mol% of a fluoromonomer providing a crosslinking site. .

The fluorine-containing thermoplastic elastomer is not particularly limited as long as it comprises at least one elastomeric polymer segment (S1) and at least one non-elastomeric polymer segment (S2). From the viewpoint of excellent compatibility with the resin (a), at least one of the elastomeric polymer segment (S1) and the non-elastomeric polymer segment (S2) is preferably a fluorine-containing polymer segment, and both of them are fluorine-containing. A polymer segment is preferred.

The elastomeric polymer segment (S1) imparts flexibility to the polymer and has a glass transition point of 25 ° C. or lower, preferably 0 ° C. or lower. As the structural unit, for example, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, general formula (3):
^{_{CF 2 = CFO (CF 2 CFX}} 4 O) p - (CF 2 CF 2 CF 2 O) q -Rf 4 (3)
(Wherein X ⁴ is a fluorine atom or —CF ₃ , Rf ⁴ is a perfluoroalkyl group having 1 to 5 carbon atoms, p is an integer of 0 to 5, and q is an integer of 0 to 5) Perhaloolefins such as perfluorovinyl ether represented by: Fluorine-containing single quantities such as vinylidene fluoride, trifluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and vinyl fluoride Non-fluorine monomers such as ethylene, propylene and alkyl vinyl ether.

As a monomer which gives a crosslinking site, for example, general formula (4):
CX ⁵ ₂ = CX ⁵ -Rf ⁵ CHR ¹ X ⁶ (4)
(Wherein X ⁵ is a hydrogen atom, fluorine atom or —CH ₃ , Rf ⁵ is a fluoroalkylene group, perfluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group, and R ¹ is a hydrogen atom. Or —CH ₃ , X ⁶ is an iodine atom or a bromine atom), or an iodine or bromine-containing monomer represented by the general formula (5):
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 7 (5)
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, X ⁷ is a cyano group, a carboxyl group, an alkoxycarbonyl group, or a bromine atom) These can be used alone or in any combination.

Next, as the structural unit of the non-elastomeric polymer segment (S2), tetrafluoroethylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), hexafluoropropylene, general formula (6):
CF ₂ = CF (CF ₂ ) _r X ⁸ (6)
(Wherein, r is an integer of 1 to 10, X ⁸ is a fluorine atom or a chlorine atom), perhaloolefins such as perfluoro-2-butene; vinylidene fluoride, vinyl fluoride , Trifluoroethylene, general formula (7):
^{_{CH 2 = CX 9 - (CF}} 2) s -X 9 (7)
(Wherein X ⁹ is a hydrogen atom or a fluorine atom, s is an integer of 1 to 10), a partially fluorinated olefin such as CH ₂ ═C (CF ₃ ) ₂ ; ethylene, propylene, chloride Examples thereof include non-fluorine monomers such as vinyl, vinyl ether, carboxylic acid vinyl ester, and acrylic acid.

Among these, the elastomeric polymer segment (S1) is a copolymer of tetrafluoroethylene, vinylidene fluoride and hexafluoropropylene, and the non-elastomeric polymer segment (S2) is composed of tetrafluoroethylene and ethylene. A fluorine-containing thermoplastic elastomer that is a copolymer is preferred, and the elastomeric polymer segment (S1) is tetrafluoroethylene / vinylidene fluoride / hexafluoropropylene = 0-35 / 40-90 / 5-50 mol%, And the non-elastomeric polymer segment (S2) is more preferably a fluorine-containing thermoplastic elastomer having tetrafluoroethylene / ethylene = 20-80 / 80-20 mol%.

It is important that the fluorine-containing thermoplastic elastomer is a fluorine-containing multi-segmented polymer in which the elastomeric polymer segment (S1) and the non-elastomeric polymer segment (S2) are bonded in the form of a block or graft in one molecule. Fluorine-containing thermoplastic elastomer
(1) a diblock polymer comprising one elastomeric polymer segment (S1) and one non-elastomeric polymer segment (S2), one of which is a fluorine-containing polymer segment, and / or (2) More preferably, it is composed of one elastomeric polymer segment (S1) and two non-elastomeric polymer segments (S2), and at least one of them is composed of a triblock polymer that is a fluorine-containing polymer segment,
(1) a diblock polymer comprising one elastomeric polymer segment (S1) and one non-elastomeric polymer segment (S2), both of which are fluorine-containing polymer segments, and / or (2) It is particularly preferred that it is composed of one elastomeric polymer segment (S1) and two non-elastomeric polymer segments (S2), and they are composed of a triblock polymer that is a fluorine-containing polymer segment.

As the fluorine-containing thermoplastic elastomer, various known methods can be used to connect the elastomeric polymer segment (S1) and the non-elastomeric polymer segment (S2) in the form of blocks or grafts to form a fluorine-containing multi-segment polymer. Among them, a method for producing a block-type fluorine-containing multi-segmented polymer disclosed in Japanese Patent Publication No. 58-4728 and a graft-type fluorine-containing multi-element disclosed in JP-A-62-34324 can be used. A method for producing a segmented polymer can be preferably employed.

In particular, since the segmentation rate (blocking rate) is high and a homogeneous and regular segmented polymer can be obtained, Japanese Patent Publication No. 58-4728, collection of polymer articles (Vol. 49, No. 10, 1992). A block-type fluorine-containing multi-segmented polymer synthesized by the so-called iodine transfer polymerization method described above is preferred.

As a preferable production method of the fluorine-containing thermoplastic elastomer, a known iodine transfer polymerization method can be given as a production method of the fluororubber. For example, the perhaloolefin and, if necessary, a monomer that provides a curing site are stirred under pressure in an aqueous medium in the presence of an iodine compound, preferably a diiodine compound, substantially in the absence of oxygen. However, a method of carrying out emulsion polymerization in the presence of a radical initiator can be mentioned. Representative examples of the diiodine compound used include, for example, the general formula (8)
R ² I _x Br _y (8)
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ² is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro And a hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom). The iodine or bromine thus introduced functions as a crosslinking point.

When the elastomeric polymer segment (S1) of the fluorine-containing thermoplastic elastomer is produced by the iodine transfer polymerization method, the number average molecular weight is such that flexibility is imparted to the whole fluorine-containing multi-segmented polymer, elasticity is given, and the machine From the viewpoint of imparting physical properties, it is preferably 3,000 to 750,000, and more preferably 5,000 to 300,000.

The terminal portion of the elastomeric polymer segment (S1) thus obtained is a perhalo type and has an iodine atom that serves as a starting point for block copolymerization of the non-elastomeric polymer segment (S2).

Next, the block copolymerization of the non-elastomeric polymer segment (S2) to the elastomeric polymer segment (S1) is carried out following the emulsion polymerization of the elastomeric polymer segment (S1), and the monomer is changed to the non-elastomeric polymer segment (S2). Can be done by changing The number average molecular weight of the non-elastomeric polymer segment (S2) is preferably 1,000 to 1,200,000, more preferably 3,000 to 600,000.

In addition, the polymer molecule of only the elastomeric polymer segment (S1) to which the non-elastomeric polymer segment (S2) is not bonded to the fluorine-containing thermoplastic elastomer is the sum of the segments and polymer molecules in the fluorine-containing thermoplastic elastomer. It is preferable that it is 20 weight% or less with respect to quantity, More preferably, it is 10 weight% or less.

It is preferable that the uncrosslinked fluororubber (a) has an iodine atom or a bromine atom in the molecule because crosslinking using an organic peroxide is possible.

When the uncrosslinked fluororubber (a) contains a crosslinkable group (cure site), the crosslinking system of the uncrosslinked fluororubber (a) is appropriately selected depending on the type of the cure site or the use of the molded product to be obtained. do it. As the crosslinking system, any of a polyol crosslinking system, an organic peroxide crosslinking system, and a polyamine crosslinking system can be employed.

Here, when it is crosslinked by a polyol crosslinking system, it has a carbon-oxygen bond at the crosslinking point, has a small compression set, good moldability, and excellent sealing properties. Is preferred.

When crosslinked by an organic peroxide crosslinking system, since it has a carbon-carbon bond at the crosslinking point, a polyol crosslinking system having a carbon-oxygen bond at the crosslinking point and a polyamine having a carbon-nitrogen double bond Compared to the cross-linking system, it is characterized by excellent chemical resistance and steam resistance.

When crosslinked by polyamine crosslinking, it has a carbon-nitrogen double bond at the crosslinking point and is characterized by excellent dynamic mechanical properties. However, compression set tends to increase as compared with the case of crosslinking using a polyol crosslinking system or an organic peroxide crosslinking system.

Therefore, in the present invention, it is preferable to use a polyol crosslinking type or organic peroxide crosslinking type crosslinking agent, and it is more preferable to use a polyol crosslinking type crosslinking agent from the viewpoint of excellent sealing properties as described above.

The crosslinking agent (a) can be appropriately selected depending on the type of uncrosslinked fluororubber (a) and the melt-kneading conditions. As the crosslinking agent (a), a polyamine-based, polyol-based or organic peroxide-based crosslinking agent can be used.

Examples of the polyamine crosslinking agent include polyamine compounds such as hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, and 4,4′-bis (aminocyclohexyl) methanecarbamate. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.

As the polyol crosslinking agent, a compound conventionally known as a crosslinking agent for fluororubber can be used. For example, a polyhydroxy compound, particularly a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance.

The polyhydroxy aromatic compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane. (Hereinafter referred to as bisphenol AF), resorcin, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4 ′ -Dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2 , 2-Bis (4-hydroxyphenyl) Tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 Examples include ', 5,5'-tetrabromobisphenol A. These polyhydroxy aromatic compounds may be an alkali metal salt, an alkaline earth metal salt or the like, but when the copolymer is coagulated using an acid, it is preferable not to use the metal salt.

The organic peroxide crosslinking agent may be any organic peroxide that can easily generate a peroxy radical in the presence of heat or a redox system. For example, 1,1-bis (t-butylperoxide) Oxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α -Bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) -hexyne-3, benzoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate -Bonate etc. can be given. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 are preferable.

Among these, a polyhydroxy compound is preferable from the viewpoint that the compression set such as a molded article to be obtained is small, moldability is good, and sealing properties are excellent, and a polyhydroxy aromatic compound is more preferable because of excellent heat resistance. Preferably, bisphenol AF is more preferable.

In the polyol crosslinking system, a crosslinking accelerator is usually used in combination with the polyol crosslinking agent. When a crosslinking accelerator is used, the crosslinking reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.

An onium compound is generally used as a crosslinking accelerator for a polyol crosslinking system. The onium compound is not particularly limited, and examples thereof include ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and monofunctional amine compounds. Of these, quaternary ammonium salts and quaternary phosphonium salts are preferred.

The quaternary ammonium salt is not particularly limited. For example, 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 hydroxide, 8-methyl-1,8-diazabicyclo [5 , 4,0] -7-Undecenium methyl sulfate, 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 hydroxide, 8-eicosyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-tetracosyl-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-phenethyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8- (3- Phenylpropyl) -1,8-diazabicyclo [5,4,0] -7-undecenium chloride and the like. Among these, DBU-B is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl. Examples thereof include -2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and among these, benzyltriphenylphosphonium chloride (BTPPC) is preferable from the viewpoint of crosslinkability and physical properties of the crosslinked product.

Further, as a crosslinking accelerator, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a chlorine-free crosslinking accelerator disclosed in JP-A-11-147891 can also be used.

Examples of the organic peroxide crosslinking accelerator include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N′-m-phenylenebismaleimide, dipropargyl terephthalate. , Diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3,5 -Triazine-2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N, N, N ', N'-tetraallylphthala N, N, N ′, N′-tetraallylmalonamide, trivinylisocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl phosphite Etc. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

As a compounding quantity of a crosslinking agent (a), it is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of uncrosslinked fluororubber (a), More preferably, it is 0.3-5 mass parts. .

The melt viscosity ratio (fluororesin (a) / uncrosslinked fluororubber (a)) between the fluororesin (a) and the uncrosslinked fluororubber (a) is preferably 0.1 to 1.5, more preferably. Is 0.2 to 1.2, particularly preferably 0.3 to 1.1. When the melt viscosity ratio is within the above range, it is easy to produce a layer (A) in which the crosslinked fluororubber (a) is highly dispersed in the fluororesin (a). The melt viscosity is a value of a melt flow rate measured under a condition of 297 ° C. and a load of 5000 g.

The layer (A) preferably has conductivity in order to prevent static charge from accumulating and igniting. From this point of view, the layer (A) preferably contains a conductive material such as carbon black or acetylene black. The conductive material is preferably 0.01 to 20% by mass, more preferably 1 to 18% by mass, and still more preferably 5 to 15% by mass with respect to the layer (A).

The layer (A) is a step of obtaining a composition (a1) containing an uncrosslinked fluororubber (a) and a crosslinking agent (a), and the composition (a1) and the fluororesin (a) are mixed with the melting point of the fluororesin (a). It can manufacture by the manufacturing method including the process of obtaining a composition (a2) by knead | mixing at the above temperature, and the process of shape | molding a composition (a2).

The kneading for obtaining the composition (a2) can be performed by using a Banbury mixer, a pressure kneader, an extruder or the like. In this kneading, the uncrosslinked fluororubber (a) is dynamically crosslinked to obtain a composition (a2) containing the crosslinked fluororubber (a) and the fluororesin (a).

In addition, in order to remove moisture and the like adhering to the surface of the obtained composition (a2), and to obtain a stable molded product without poor appearance, the method for producing the layer (A) includes the composition (a2 It is preferable to include a step of heat-drying the composition (a2) before the step of forming the composition (a2) after the step of obtaining a).
The heat drying temperature is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and particularly preferably 90 ° C. or higher.
The temperature for the heat drying is preferably 40 ° C. or lower, more preferably 140 ° C. or lower, more preferably 125 ° C. or lower, and 110 ° C. or lower than the melting point of the fluororesin (a). It is particularly preferred.

The MFR of the composition (a2) is preferably 0.5 to 30 g / 10 minutes, and more preferably 1 to 25 g / 10 minutes. If the MFR is too small, the fluidity is small and the moldability may be reduced.

The fuel permeability coefficient of the composition (a2) is preferably 10.0 g · mm / m ² / day or less. When the fuel permeability coefficient is 10.0 g · mm / m ² / day or less, excellent low fuel permeability is exhibited in the B direction shown in FIG.
The fuel permeability coefficient is preferably 8.0 g · mm / m ² / day or less, more preferably 6.0 g · mm / m ² / day or less, and 5.0 g · mm / m ² / day. It is more preferably not more than day, particularly preferably not more than 3.0 g · mm / m ² / day.
The fuel permeability coefficient is a SUS316 fuel permeability coefficient measuring cup made of SUS316 with an inner diameter of 40 mmφ and a height of 20 mm charged with 18 mL of an isooctane / toluene / ethanol mixed solvent in which isooctane, toluene and ethanol are mixed at a volume ratio of 45:45:10. Is a value calculated from a change in mass measured at 60 ° C. by incorporating a sheet (diameter 45 mm, thickness 120 μm) prepared from the composition to be measured by the following method.
(Sheet production method)
Each of the resin pellets was put into a mold having a diameter of 120 mm, set in a press machine heated to 300 ° C., and melt-pressed at a pressure of about 2.9 MPa to obtain a sheet having a thickness of 0.12 mm.

The flexural modulus of the composition (a2) is preferably 1000 MPa or less. When the flexural modulus is 1000 MPa or less, the excellent sealability of the laminate is exhibited.
The flexural modulus is preferably 800 MPa or less, more preferably 600 MPa or less, still more preferably 400 MPa or less, and particularly preferably 300 MPa or less.
The bending elastic modulus is a value measured by using a universal testing machine manufactured by Orientec Co., Ltd. at a bending speed of 2 mm / min at room temperature according to JIS K6911.
(Measurement sample preparation method)
The resin pellet was set in an injection molding machine heated to 300 ° C. to obtain a test piece having a length of 80.0 mm, a width of 10.0 mm, and a thickness of 4.0 mm.

Molding of the composition (a2) can be performed by a known method. For example, when a laminate including layers (A) to (D) is produced by a coextrusion molding method, the layers are extruded simultaneously with the materials constituting the layers (B) to (D) and formed into a desired shape. be able to.

2. Layer (B) The layer (B) is made of rubber (b).

The rubber (b) is preferably obtained by vulcanizing the unvulcanized rubber (b1).

As the unvulcanized rubber (b1), uncrosslinked fluororubber (a) or non-fluorinated rubber can be used, but non-fluorinated rubber is preferred.

Specific examples of the unvulcanized rubber (b1) include, for example, acrylonitrile-butadiene rubber (NBR) or a hydride thereof (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural Examples thereof include diene rubbers such as rubber (NR) and isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, and acrylic rubber.

The unvulcanized rubber (b1) is preferably a diene rubber, an epichlorohydrin rubber (ECO), or an acrylic rubber from the viewpoint of good heat resistance, oil resistance, weather resistance, and extrusion moldability. More preferred is acrylonitrile-butadiene rubber (NBR) or epichlorohydrin rubber (ECO).

The acrylic rubber is, for example, a polymer composed of polymerized units based on an acrylate ester, and may be a copolymer composed of polymerized units based on two or more acrylate esters, or one or two or more types of acrylate rubbers. It may be a copolymer comprising polymerized units based on an acrylate ester and polymerized units based on a monomer copolymerizable with the acrylate ester. As the acrylic rubber, for example, an unvulcanized acrylic rubber described in JP 2014-111379 A can be used.

The layer (B) made of rubber (b) is preferably formed from a vulcanized rubber composition containing unvulcanized rubber (b1).

Examples of the rubber composition for vulcanization include, for example, JP 2012-125015 A, International Publication No. 2011/001756, JP 2010-89479 A, JP 2012-61644 A, JP 2012-81682 A. Japanese Patent Application No. 2010-254309, Japanese Patent Application No. 2011-45942, Japanese Patent Application No. 2011-229997, Japanese Patent Application No. 2011-275417, Japanese Patent Application No. 2012-22052, Japanese Patent Application No. 2012-199719 Rubber composition for use.

The rubber composition for vulcanization contains unvulcanized rubber (b1), compound (b2), magnesium oxide (b3), and silica (b4) as essential components, and further includes a vulcanizing agent (b5) as optional components. ) And a metal salt (b6).
In particular, when the rubber composition for vulcanization contains the vulcanizing agent (b5) and the metal salt (b6) in addition to the unvulcanized rubber (b1) and the compound (b2), it adheres more firmly to the adjacent layer. To do. Moreover, it is also preferable that an epoxy resin (b7) is included.

The rubber composition for vulcanization may contain a resin in order to give the layer (B) properties different from those of the unvulcanized rubber (b1). Examples of the resin include PVC, chlorinated polystyrene, chlorosulfonated polystyrene ethylene, ethylene-vinyl acetate copolymer, and the like. 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 with respect to 100 parts by mass of NBR.

Compound (b2) includes 1,8-diazabicyclo (5.4.0) undecene-7 salt (DBU salt), 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt), 1 , 8-diazabicyclo (5.4.0) undecene-7 (DBU) and at least one selected from the group consisting of 1,5-diazabicyclo (4.3.0) -nonene-5 (DBN) A compound is preferred. By including the compound (b2), the vulcanization characteristics of the rubber composition for vulcanization can be improved.

As DBU salt and DBN salt, DBU or DBN carbonate, long chain aliphatic carboxylate, aromatic carboxylate, orthophthalate, p-toluenesulfonate, phenol salt, phenol resin salt, naphthoate Octylate, oleate, formate, phenol novolac resin salt, etc., and 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride (DBU-B), It is preferably at least one compound selected from the group consisting of naphthoate, orthophthalate, phenol salt, and formate.

More specifically, the compound (b2) is obtained from 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) 0.0) Orthophthalic acid salt of undecene-7 and at least one compound selected from the group consisting of 1,8-diazabicyclo (5.4.0) undecene-7 formate.

As the compound (b2), 1,8-diazabicyclo (5.4.0) undecene-7, 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride, 1,8 A phenol salt of diazabicyclo (5.4.0) undecene-7, an orthophthalate of 1,8-diazabicyclo (5.4.0) undecene-7, and 1,8-diazabicyclo (5.4.0) More preferably, it is at least one compound selected from the group consisting of undecene-7 formate. More preferably, 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride, 1,8-diazabicyclo (5.4.0) undecene-7 formate, and 1 , 8-diazabicyclo (5.4.0) undecene-7, at least one compound selected from the group consisting of phenol salts.

In addition, the compound (b2) is at least one compound selected from the group consisting of DBU-B, DBU phenol salt, DBU orthophthalate and DBU formate. is there.

It is preferable that a compound (b2) exceeds 0.3 mass part with respect to 100 mass parts of unvulcanized rubber (b1), and is 5 mass parts or less. The compound (b2) is more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the unvulcanized rubber (b1). If the amount of the compound (b2) is too small, the adhesive force may not be sufficient. Further, the compound (b2) is more preferably 4 parts by mass or less, still more preferably 3.5 parts by mass or less, relative to 100 parts by mass of the unvulcanized rubber (b1), and 3 parts by mass or less. It is particularly preferred that

The rubber composition for vulcanization preferably contains magnesium oxide (b3). The blending amount of magnesium oxide (b3) is preferably 3 to 20 parts by mass, particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (b1) from the viewpoint of adhesiveness and rubber physical properties. . The laminate having a specific structure of the present invention can have excellent adhesiveness by making magnesium oxide (b3) essential.

The rubber composition for vulcanization preferably contains silica (b4). As silica (b4), basic silica or acidic silica can be used, and from the viewpoint of adhesiveness, it is preferable to use basic silica. Examples of basic silica include Carplex 1120 (manufactured by DSL Japan Co., Ltd.). Moreover, from a viewpoint of adhesiveness and rubber physical property, 10-100 mass parts is preferable with respect to 100 mass parts of unvulcanized rubber (b1), Most preferably, it is 15-70 mass parts. The laminate having a specific structure of the present invention can have excellent adhesiveness by making silica (b4) essential.

A conventionally well-known thing can be used for a vulcanizing agent (b5) according to the vulcanization system of the rubber composition for vulcanization | cure. By vulcanizing the unvulcanized rubber (b1), mechanical strength such as tensile strength of the obtained vulcanized 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 (b5), a sulfur vulcanizing vulcanizing agent, a polyamine vulcanizing vulcanizing agent, a polyol vulcanizing vulcanizing agent, a peroxide vulcanizing vulcanizing agent, an imidazole vulcanizing agent are used in accordance with the vulcanizing system. 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 (b1) 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.

The compounding amount of the sulfur vulcanizing vulcanizing agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (b1). If the amount is too small, the adhesiveness is insufficient, and if the amount is too large, it tends to be too hard.

As the peroxide vulcanizing agent, an organic peroxide that easily generates a peroxy radical in the presence of heat or a redox system is preferable.

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 rubbers, Preferably it is 0.3-5 mass parts.

The vulcanizing agent (b5) is preferably at least one selected from the group consisting of a sulfur vulcanizing vulcanizing agent and a peroxide vulcanizing vulcanizing agent, and more preferably a sulfur vulcanizing vulcanizing agent. Preferably, the addition amount is preferably 0.5 to 5 parts by mass, particularly preferably 1.0 to 3 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (b1).

The metal salt (b6) is preferably at least one selected from the group consisting of carbamic acid metal salts and thiazole metal salts.

Examples of the carbamic acid metal salt include zinc salt of dimethyldithiocarbamate (ZnMDC), zinc salt of diethyldithiocarbamate (ZnEDC), zinc salt of dibutyldithiocarbamate (ZnBDC), iron salt of dimethyldithiocarbamate (FeMDC), Zinc salt of ethylphenyldithiocarbamate (ZnEPDC), zinc salt of N-pentamethylenedithiocarbamate, zinc salt of dibenzyldithiocarbamate, sodium salt of dimethyldithiocarbamate (NaMDC), sodium salt of diethyldithiocarbamate (NaEDC), dibutyl Examples include sodium salt of dithiocarbamate (NaBDC), copper salt of dimethyldithiocarbamate (CuMDC), tellurium salt of diethyldithiocarbamate (TeEDC), and the like. These may be used alone or in combination of two or more. Among these, ZnMDC, ZnEDC, or ZnBDC is preferably used in terms of adhesion and rubber properties.

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

The compounding amount of the metal salt (b6) is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and particularly preferably 0.05 to 100 parts by mass of the unvulcanized rubber (a1). ˜2 parts by mass. If the blending amount of the metal salt (b6) is too small, the physical property of the vulcanized rubber tends to deteriorate, and if it is too large, the unvulcanized physical property tends to deteriorate.

The rubber composition for vulcanization preferably does not contain an amine compound because it inhibits the vulcanization characteristics or impairs the physical properties of the rubber.

Further, in the present invention, as necessary or necessary, conventional additives blended in a general vulcanizing rubber composition, such as fillers, processing aids, plasticizers, softeners, anti-aging agents, colorants, Stabilizer, adhesion aid, 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 Various additives such as an improver, a foaming 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 above-mentioned thing.

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, organic fillers and the like.

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 plasticizers include phthalic acid derivatives and sebacic acid derivatives, softeners such as lubricating oil, process oil, coal tar, castor oil, calcium stearate, and anti-aging agents such as phenylenediamines and phosphates, Examples include quinolines, cresols, phenols, and dithiocarbamate metal salts.

Examples of the epoxy resin (b7) 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 (1):

An epoxy resin represented by the formula is particularly preferred. Here, in Formula (1), n is an average value, 0.1-3 are preferable, 0.1-0.5 are more preferable, and 0.1-0.3 are further more preferable. When n is less than 0.1, the adhesive strength with the layer (C) tends to decrease. On the other hand, when n exceeds 3, the viscosity of the epoxy resin itself becomes high and uniform dispersion in the vulcanizing rubber composition tends to be difficult.

The content when the epoxy resin is blended is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the unvulcanized rubber, from the viewpoint of further improving the adhesive strength with the adjacent layer. 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.

The vulcanized rubber composition comprises unvulcanized rubber (b1), compound (b2), magnesium oxide (b3), and silica (b4), and if necessary, vulcanizing agent (b5), metal salt (b6). In addition, it is prepared by kneading other additives.

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, More preferably, it is 13 minutes or less, Most preferably, it is 11 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. T ₉₀ is a value obtained by measuring the maximum torque value (M _H ) and the minimum torque value (M _L ) at 160 ° C., and {(M _H ) − (M _L )} × 0.9 + M _L This is the value obtained by. M _H and _{M L} is the value measured according to JIS K 6300-2.

When the unvulcanized rubber (b1) is epichlorohydrin rubber, the rubber composition for vulcanization includes, as essential components, epichlorohydrin rubber (b1-1), compound (b2-1), magnesium oxide (b3-1), silica ( b4-1) and an epoxy resin (b7-1), and further contains at least one of zinc oxide (b8) and a vulcanizing agent (b5-1) as optional components, or epichlorohydrin rubber (b1) -1), compound (b2-1), epoxy resin (b7-1), and water-carrying substance (b9) are preferably included. In particular, when the rubber composition for vulcanization contains the vulcanizing agent (b5-1) in addition to the epichlorohydrin rubber (b1-1) and the compound (b2-1), it can be bonded to an adjacent layer with high adhesive strength. .

The epichlorohydrin rubber (b1-1) is not particularly limited as long as it is an unvulcanized rubber having polymerized units based on epichlorohydrin, and may be a unipolymer consisting essentially of polymerized units based on epichlorohydrin, It may be a binary or higher polymer composed of a polymer unit based on epichlorohydrin and a polymer unit based on a monomer other than epichlorohydrin.

As another monomer other than epichlorohydrin, for example, at least one monomer selected from the group consisting of ethylene oxide, propylene oxide, and allyl glycidyl ether is preferable. The rubber composition for vulcanization is preferably a polymer having a polymer unit based on epichlorohydrin and a polymer unit based on ethylene oxide, a polymer unit based on epichlorohydrin, a polymer unit based on ethylene oxide, and allyl glycidyl. More preferred is a polymer having polymerized units based on ether.

Examples of the epichlorohydrin rubber (b1-1) include epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-allyl glycidyl ether copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymer, epichlorohydrin-propylene oxide. At least one polymer selected from the group consisting of a copolymer, an epichlorohydrin-propylene oxide-allyl glycidyl ether copolymer, and an epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymer is preferred. More preferably, it is at least one polymer selected from the group consisting of epichlorohydrin-ethylene oxide copolymer and epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymer. These can be used alone or in admixture of two or more.

Compound (b2-1) includes 1,8-diazabicyclo (5.4.0) undecene-7 salt (DBU salt), 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt). 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) and 1,5-diazabicyclo (4.3.0) -nonene-5 (DBN). A seed compound is preferred.

Compound (b2-1) is a p-toluenesulfonic acid salt of 1,8-diazabicyclo (5.4.0) undecene-7, a phenol of 1,8-diazabicyclo (5.4.0) undecene-7. Salt, 1,8-diazabicyclo (5.4.0) undecene-7 phenol resin salt, 1,8-diazabicyclo (5.4.0) undecene-7 orthophthalate, 1,8-diazabicyclo (5. 4.0) undecene-7 formate, 1,8-diazabicyclo (5.4.0) undecene-7 octylate, 1,5-diazabicyclo (4.3.0) -nonene-5 p- Toluenesulfonate, phenol salt of 1,5-diazabicyclo (4.3.0) -nonene-5, phenol resin salt of 1,5-diazabicyclo (4.3.0) -nonene-5, 1,5- Diazabicik (4.3.0) -Nonene-5 orthophthalate, 1,5-diazabicyclo (4.3.0) -nonene-5 formate, and 1,5-diazabicyclo (4.3.0) -Preferably, it is at least one compound selected from the group consisting of nonene-5 octylate. By including a compound (b2-1), the vulcanization | cure characteristic of the rubber composition for vulcanization | cure can be improved, and adhesiveness can be improved.

Compound (b2-1) is a p-toluenesulfonate salt of 1,8-diazabicyclo (5.4.0) undecene-7, a phenol salt of 1,8-diazabicyclo (5.4.0) undecene-7, Phenol resin salt of 1,8-diazabicyclo (5.4.0) undecene-7, orthophthalate of 1,8-diazabicyclo (5.4.0) undecene-7, 1,8-diazabicyclo (5.4. It is preferably at least one compound selected from the group consisting of 0) undecene-7 formate and 1,8-diazabicyclo (5.4.0) undecene-7 octylate.

From the viewpoint of improving adhesiveness, the compound (b2-1) is an octylate of 1,8-diazabicyclo (5.4.0) undecene-7 or 1,8-diazabicyclo (5.4.0). ) More preferred is a phenolic resin salt of undecene-7.

Moreover, it is one of the preferable forms that the rubber composition for vulcanization further contains a phosphonium salt. In addition to the compound (b2-1), the adhesiveness can be further improved by using a phosphonium salt in combination.

Specifically, for example, the compound (b2-1) is a phenol salt of 1,8-diazabicyclo (5.4.0) undecene-7, 1,8-diazabicyclo (5.4.0) undecene-7. Selected from the group consisting of orthophthalate, 1,8-diazabicyclo (5.4.0) undecene-7 formate, and 1,8-diazabicyclo (5.4.0) undecene-7 octylate It is preferable that the rubber composition for vulcanization further contains a phosphonium salt.

In addition, as the compound (b2-1), 1,8-diazabicyclo (5.4.0) undecene-7 octylate or 1,8-diazabicyclo (5.4.0) undecene-7 phenol It is preferable to make the resin salt essential.

It is preferable that a compound (b2-1) is 0.5 to 5 mass parts with respect to 100 mass parts of epichlorohydrin rubber (b1-1) from a viewpoint with favorable adhesiveness. More preferably, it is 1 part by mass or more and 4 parts by mass or less. In addition, the compound (b2-1) is used in an amount of 1 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the epichlorohydrin rubber (b1-1) because the adhesiveness is good and the vulcanization characteristics are good. It is preferable that

The rubber composition for vulcanization preferably contains magnesium oxide (b3-1). The blending amount of magnesium oxide (b3-1) is preferably 3 to 20 parts by mass, particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of epichlorohydrin rubber (b1-1) from the viewpoint of adhesiveness and rubber physical properties. It is. The laminate having a specific structure of the present invention has excellent adhesiveness by making magnesium oxide (b3-1) essential.

The rubber composition for vulcanization preferably contains silica (b4-1). As silica (b4-1), basic silica and acidic silica can be used, and basic silica is preferably used from the viewpoint of adhesiveness. Examples of basic silica include Carplex 1120 (manufactured by DSL Japan Co., Ltd.). Moreover, from a viewpoint of adhesiveness and a rubber physical property, 5-40 mass parts is preferable with respect to 100 mass parts of epichlorohydrin rubber (b1-1), Most preferably, it is 10-25 mass parts. The laminate having the specific structure of the present invention has excellent adhesiveness by making silica (b4-1) essential.

The rubber composition for vulcanization preferably contains an epoxy resin (b7-1). As an epoxy resin (b7-1), the thing similar to the epoxy resin (b7) mentioned above is mentioned.

An epoxy resin (b7-1) is 0.1-5 mass parts with respect to 100 mass parts of epichlorohydrin rubber (b1-1) from the point which improves the adhesive force of a layer (B) and a layer (C) more. Is preferable, and 0.3-3 mass parts is more preferable. From the viewpoint of improving the adhesive strength, although depending on the amount of compound (b2-1), magnesium oxide (b3-1), silica (b4-1), etc. added to the rubber composition for vulcanization. The epoxy resin (b7-1) preferably exceeds 0.5 parts by mass with respect to 100 parts by mass of the epichlorohydrin rubber (b1-1). Exceeding 1 part by mass is one of the preferred forms.

Further, in the rubber composition for vulcanization, the sum of the compound (b2-1) and the epoxy resin (b7-1) may exceed 2 parts by mass with respect to 100 parts by mass of the epichlorohydrin rubber (b1-1). One of the preferred forms.

The rubber composition for vulcanization preferably further contains zinc oxide (b8). The blending amount of zinc oxide (b8) is preferably 3 to 20 parts by mass, particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of epichlorohydrin rubber (b1-1) from the viewpoint of adhesiveness and rubber physical properties. . The laminated body which has the specific structure of this invention will have more excellent adhesiveness by including a zinc oxide (b8).

The rubber composition for vulcanization preferably contains a vulcanizing agent (b5-1). A conventionally well-known thing can be used for a vulcanizing agent according to the vulcanization | cure system of the rubber composition for vulcanization | cure. By vulcanizing the epichlorohydrin rubber (b1-1), mechanical strength such as tensile strength of the obtained vulcanized rubber layer is improved, and good elasticity can be obtained.

As the vulcanizing agent (b5-1), known vulcanizing agents utilizing the reactivity of chlorine atoms, for example, polyamine type vulcanizing agents, thiourea type vulcanizing agents, thiadiazole type vulcanizing agents, mercaptotriazine type vulcanizing agents. Agents, pyrazine vulcanizing agents, quinoxaline vulcanizing agents, bisphenol vulcanizing agents and the like.

Examples of known vulcanizing agents that utilize the reactivity of chlorine atoms include polyamine vulcanizing agents such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, cumenediamine, N, N′-dicinnamylidene-1,6-hexanediamine, ethylenediamine carbamate, hexamethylenediamine carbamate and the like can be mentioned.

Examples of the thiourea vulcanizing agent include ethylene thiourea, 1,3-diethylthiourea, 1,3-dibutylthiourea, and trimethylthiourea.

Examples of thiadiazole-based vulcanizing agents include 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole-5-thiobenzoate, and the like.

Examples of mercaptotriazine-based vulcanizing agents include 2,4,6-trimercapto-1,3,5-triazine, 1-methoxy-3,5-dimercaptotriazine, 1-hexylamino-3,5-dimercaptotriazine 1-diethylamino-3,5-dimercaptotriazine, 1-cyclohexaneamino-3,5-dimercaptotriazine, 1-dibutylamino-3,5-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine 1-phenylamino-3,5-dimercaptotriazine and the like.

Examples of the pyrazine-based vulcanizing agent include 2,3-dimercaptopyrazine derivatives. Examples of 2,3-dimercaptopyrazine derivatives include pyrazine-2,3-dithiocarbonate, 5-methyl-2,3- Examples include dimercaptopyrazine, 5-ethylpyrazine-2,3-dithiocarbonate, 5,6-dimethyl-2,3-dimercaptopyrazine, 5,6-dimethylpyrazine-2,3-dithiocarbonate and the like.

Examples of quinoxaline-based vulcanizing agents include 2,3-dimercaptoquinoxaline derivatives, and examples of 2,3-dimercaptoquinoxaline derivatives include quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3. -Dithiocarbonate, 6-ethyl-2,3-dimercaptoquinoxaline, 6-isopropylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithiocarbonate and the like.

Examples of the bisphenol vulcanizing agent include 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone (bisphenol S), 1,1-cyclohexylidene-bis (4-hydroxybenzene), 2-chloro- 1,4-cyclohexylene-bis (4-hydroxybenzene), 2,2-isopropylidene-bis (4-hydroxybenzene) (bisphenol A), hexafluoroisopropylidene-bis (4-hydroxybenzene) (bisphenol AF) And 2-fluoro-1,4-phenylene-bis (4-hydroxybenzene).

In the rubber composition for vulcanization, known vulcanization accelerators and retarders can be used as they are together with the vulcanizing agent in the present invention. Examples of vulcanization accelerators used in combination with known vulcanizing agents utilizing the reactivity of chlorine atoms include primary, secondary, tertiary amines, organic acid salts of these amines or their adducts, guanidine accelerators, Examples include thiuram accelerators and dithiocarbamic acid accelerators. Examples of the retarder include N-cyclohexanethiophthalimide, zinc salts of dithiocarbamic acids, and the like.

Examples of vulcanization accelerators include primary, secondary and tertiary amines, which are preferably primary, secondary or tertiary amines of aliphatic or cyclic fatty acids having 5 to 20 carbon atoms. Representative examples of amines are n-hexylamine, octylamine, dibutylamine, tributylamine, hexamethylenediamine and the like.

Examples of the organic acid that forms a salt with an amine include carboxylic acid, carbamic acid, 2-mercaptobenzothiazole, and dithiophosphoric acid. Examples of the substance that forms an adduct with the amine include alcohols and oximes. Specific examples of the organic acid salt or adduct of amine include n-butylamine / acetate, hexamethylenediamine / carbamate, dicyclohexylamine salt of 2-mercaptobenzothiazole, and the like.

Examples of guanidine accelerators include diphenyl guanidine and ditolyl guanidine.

Specific examples of the thiuram vulcanization accelerator include tetramethyl thiuram disulfide, tetramethyl thiuram monosulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide and the like.

Examples of the dithiocarbamic acid accelerator include pentamethylenedithiocarbamic acid piperidine salt.

The amount of vulcanization accelerator or retarder used in combination with a known vulcanizing agent utilizing the reactivity of chlorine atoms is preferably 0 to 10 parts by weight, more preferably 100 parts by weight of the rubber component. Is 0.1 to 5 parts by weight.

Further, when the epichlorohydrin rubber (b1-1) is a polymer having a double bond such as an epichlorohydrin-allyl glycidyl ether copolymer or an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, a nitrile rubber Known vulcanizing agents, vulcanization accelerators, vulcanization retarders, vulcanization accelerating aids, crosslinking auxiliaries and the like that are usually used for vulcanization of these can be used. Examples of vulcanizing agents include sulfur, morpholine disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N'-dimethyl-N, N'-diphenylthiuram disulfide, dipentanemethylenethiuram tetrasulfide, dipenta Sulfur-based vulcanizing agents such as methylene thiuram tetrasulfide and dipentamethylene thiuram hexasulfide, tert-butyl hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, tert-butyl peroxide, 1,3-bis ( tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, benzoyl peroxide, tert-butylperoxybenzene Examples include peroxide vulcanizing agents such as benzoates, resin vulcanizing agents such as alkylphenol formaldehyde resins, quinone dioxime vulcanizing agents such as p-quinonedioxime and pp'-dibenzoylquinonedioxime. Can do. These vulcanizing agents can be used alone or in admixture of two or more. Examples of vulcanization accelerators, vulcanization retarders, vulcanization accelerators, and crosslinking assistants include aldehyde ammonia accelerators, aldehyde amine accelerators, thiourea accelerators, guanidine accelerators, and thiazole accelerators. Various vulcanization accelerators such as accelerators, sulfenamide accelerators, thiuram accelerators, dithiocarbamate accelerators, xanthogen sun salt accelerators, N-nitrosodiphenylamine, phthalic anhydride, N-cyclohexylthiophthalimide Vulcanization retarders such as zinc oxide, stearic acid, zinc stearate, etc., vulcanization accelerators, quinonedioxime crosslinking assistants, methacrylate crosslinking assistants, allyl crosslinking assistants, maleimide crosslinking assistants, etc. And various crosslinking aids.

From the viewpoint of the heat resistance of the epichlorohydrin rubber (b1-1) and the adhesion between the layer (A) and the layer (B), the vulcanizing agent may be a thiourea vulcanizing agent, a quinoxaline vulcanizing agent, a sulfur vulcanizing agent. At least one vulcanizing agent (b5-1) selected from the group consisting of a vulcanizing agent, a peroxide-based vulcanizing agent, and a bisphenol-based vulcanizing agent is preferable, a thiourea-based vulcanizing agent, a quinoxaline-based vulcanizing agent, And at least one vulcanizing agent selected from the group consisting of bisphenol-based vulcanizing agents, more preferably quinoxaline-based vulcanizing agents. These vulcanizing agents can be used alone or in admixture of two or more.

The rubber composition for vulcanization preferably contains 0.1 to 10 parts by weight of the vulcanizing agent (b5-1) with respect to 100 parts by weight of epichlorohydrin rubber (b1-1). More preferably, it is 0.5 to 5 parts by weight. If the vulcanizing agent is less than 0.1 part by weight, the crosslinking effect may be insufficient. If it exceeds 10 parts by weight, the molded product obtained by molding the laminate of the present invention becomes too rigid. Therefore, there is a possibility that practical rubber physical properties cannot be obtained.

In addition to at least one vulcanizing agent selected from the group consisting of thiourea-based vulcanizing agents, quinoxaline-based vulcanizing agents, and bisphenol-based vulcanizing agents, the rubber composition for vulcanization further includes a peroxide-based vulcanizing agent. It is also one of the preferable forms to contain a sulfurizing agent. As the peroxide vulcanizing agent, dicumyl peroxide is preferable. The peroxide-based vulcanizing agent is preferably 1 part by mass or more and more preferably 2 parts by mass or more with respect to 100 parts by mass of epichlorohydrin rubber (b1-1). Moreover, it is preferable that it is 5 mass parts or less. For example, in the rubber composition for vulcanization, when the content of the compound (b2-1) or the epoxy resin (b7) is small, good adhesiveness may not be obtained, but a peroxide vulcanizing agent is contained. By doing, even if it is a case where content of a compound (b2-1) or an epoxy resin (b7) is small, adhesiveness with a layer (A) or a layer (C) can be made favorable.

The rubber composition for vulcanization may further contain an acid acceptor. Examples of acid acceptors include group II metal oxides (except magnesium oxide), hydroxides, carbonates, carboxylates, silicates, borates, phosphorous acid. Salts, periodic table group (IV) metal oxides, basic carbonates, basic carboxylates, basic phosphites, basic sulfites, and the following general formula (2):
_{Mg x Zn y Al z (OH} ) 2 (x + y) +3 z-2 CO 3 · wH 2 O (2)
(X and y are real numbers of 0 to 10, where x + y = 1 to 10, z is a real number of 1 to 5, and w is a real number of 0 to 10), and general Formula (C):
[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (C)
(Wherein X is an inorganic or organic anion, n is the valence of anion X, and m is a number of 3 or less).

Specific examples of the acid acceptor include magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate, calcium phosphite, Examples thereof include tin oxide and basic tin phosphite.

Furthermore, examples of the synthetic hydrotalcite represented by the general formula (2) include Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ .wH ₂ O. Further, the following general formula (D) included in the general formula (2):
_{Mg x Al y (OH) 2x} + 3y-2 CO 3 · wH 2 O (D)
(Where x is 1 to 10, y is 1 to 10, and w is a positive integer). More specifically, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ , Mg ₄ Al ₂ (OH) ₁₂ CO _{3 · 3.5H 2 O, Mg 6 Al} 2 (OH) 16 CO 3 · 4H 2 O, Mg 3 Al 2 (OH) may be mentioned ₁₀ CO ₃ · 1.7H ₂ O and the like.

Furthermore, for the Li-Al-based clathrate compound represented by the general formula (C), and include _[Al 2 Li _{(OH) 6] 2} CO ₃ · _{H 2} O or the like.

The anion species of the Li-Al inclusion compound include carbonic acid, sulfuric acid, perchloric acid, phosphoric acid oxyacid, acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid. Examples include acids, succinic acid, p-oxybenzoic acid, salicylic acid, and picric acid. These acid acceptors can be used alone or in admixture of two or more.

Of the acid acceptors, from the viewpoint of the heat resistance of the epihalohydrin rubber, preferably used acid acceptors are metal oxides, metal hydroxides, and inorganic microporous crystals. These acid acceptors are blended in such an amount that does not impair the adhesive force with the layer (A) or the layer (C).

The rubber composition for vulcanization preferably does not contain an amine compound because it may impair the vulcanization characteristics or impair the physical properties of the rubber.

The rubber composition for vulcanization also preferably contains a water-carrying substance (b9).
The water-carrying substance (b9) is preferably at least one selected from water-absorbing substances and water-containing substances.

Examples of the water-absorbing substance of the water-carrying substance (b9) include a water-absorbing substance formed by absorbing a polyether compound, a metal compound or the like. The water absorption to the compound is carried out in contact with moisture (for example, impregnation) and is not particularly limited.

Examples of the polyether compound include polyethylene oxide and polyethylene glycol.

Examples of the metal compound include metal oxides, hydroxides, carbonates, hydrochlorides, sulfides, sulfates, silicates, and synthetic hydrotalsides.

Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, iron hydroxide, copper hydroxide, and manganese hydroxide.
Examples of the metal oxide include aluminum oxide, calcium oxide, magnesium oxide, titanium oxide, and copper oxide.
Examples of the metal carbonate include aluminum carbonate, calcium carbonate, magnesium carbonate, barium carbonate, and copper carbonate.
Examples of the metal hydrochloride include aluminum chloride, calcium chloride, magnesium chloride, and copper chloride.
Examples of the metal sulfide include zinc sulfide, calcium sulfide, magnesium sulfide, copper sulfide, and zinc sulfide.
Examples of the metal sulfate include calcium sulfate, barium sulfate, aluminum sulfate, sodium sulfate, and copper sulfate.
Examples of the metal silicate include aluminum silicate, calcium silicate, magnesium silicate, sodium silicate, and copper silicate.

From the viewpoint of improving adhesiveness, the water-absorbing substance of the water-carrying substance (b9) is preferably a compound having a water absorption retention of 5% by mass or more. More preferably, it is a compound having a water absorption retention of 10% by mass or more. The water absorption retention is a ratio of the amount of water retained by the water absorption material, and is calculated from the following.
Water absorption retention rate (mass%) = (water content (mass) retained by the water absorption material) / water absorption material (mass)) × 100.

Examples of the water-containing substance of the water-carrying substance (b9) include metal salt hydrates.
Metal salt hydrates include calcium, aluminum, zinc, manganese, lanthanum, titanium, zirconium, iron, cobalt, nickel, magnesium, copper, silicic acid, boric acid, phosphoric acid, hydrochloric acid, hydrogen sulfide, sulfuric acid, nitric acid, carbonic acid, etc. Inorganic acid salt hydrates, organic acid salt hydrates such as benzoic acid, phthalic acid, maleic acid, succinic acid, salicylic acid, citric acid and other carboxylic acids. Preferably, a metal salt selected from calcium acetate, aluminum sulfate, sodium sulfate, calcium sulfate, magnesium sulfate, zinc sulfate, manganese sulfate, copper sulfate, lanthanum sulfate, titanium sulfate, zirconium sulfate, iron sulfate, cobalt sulfate and nickel sulfate Preferably, it is a hydrate of a sulfate and / or acetate of a metal selected from calcium, magnesium, sodium and copper, and includes calcium sulfate dihydrate and sodium sulfate decahydrate. Copper (II) sulfate pentahydrate is more preferable, and calcium sulfate dihydrate and sodium sulfate decahydrate are particularly preferable.

The compounding amount of the water-carrying substance (b9) is 0.1 to 80 parts by mass, preferably 0.5 to 70 parts by mass, more preferably 1 to 50 parts per 100% by mass of the epichlorohydrin rubber (b1-1). Part by mass, particularly preferably 1 to 20 parts by mass. Within these ranges, a sufficient adhesive effect can be obtained, and the mechanical properties of the vulcanizate are not impaired, which is preferable.

The rubber composition for vulcanization may also contain a copper salt.
As the copper salt, an organic copper salt is preferable. Organic copper salts include copper salts of saturated carboxylic acids such as formic acid, acetic acid, butyric acid and stearic acid, copper salts of unsaturated carboxylic acids such as oleic acid and linoleic acid, and aromatic carboxylic acids such as salicylic acid, benzoic acid and phthalic acid. Copper salt of acid, copper salt of dicarboxylic acid such as oxalic acid, succinic acid, adipic acid, maleic acid, fumaric acid, copper salt of hydroxy acid such as lactic acid, citric acid, copper salt of carbamic acid, copper dimethyldithiocarbamate, Copper salts such as thiocarbamic acid such as copper diethyldithiocarbamate, copper dibutyldithiocarbamate, copper N-ethyl-N-phenyldithiocarbamate, copper N-pentamethylenedithiocarbamate, copper dibenzyldithiocarbamate, and sulfonic acid. As the organic copper salt, a copper salt of a saturated carboxylic acid, a copper salt of an unsaturated carboxylic acid, a copper salt of an aromatic carboxylic acid, or a copper salt of thiocarbamic acid is preferable, and stearic acid copper, dimethyldithiocarbamic acid copper, diethyldithiocarbamic acid Copper and copper dibutyldithiocarbamate are more preferable.

From the viewpoint of improving adhesiveness, the compounding amount of the copper salt is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of epichlorohydrin rubber (b1-1). More preferably, it is 0.1-2 mass parts. Within these ranges, a sufficient adhesive effect can be obtained, and the mechanical properties of the vulcanizate are not impaired, which is preferable.

The rubber composition for vulcanization may further contain a resin other than the epoxy resin in order to give the layer (B) a property different from that of the epichlorohydrin rubber (b1-1). Examples of the resin include polymethyl methacrylate (PMMA) resin, polystyrene (PS) resin, polyurethane (PUR) resin, polyvinyl chloride (PVC) resin, ethylene-vinyl acetate (EVA) resin, and styrene-acrylonitrile (AS) resin. , Polyethylene (PE) resin, chlorinated polystyrene, chlorosulfonated polystyrene ethyl and the like. In this case, the compounding amount of the resin is preferably 1 to 50 parts by mass with respect to 100 parts by mass of epichlorohydrin rubber (b1-1).

Further, in the present invention, as necessary or necessary, conventional additives blended in a general vulcanizing rubber composition, such as fillers, processing aids, plasticizers, softeners, anti-aging agents, colorants, Stabilizer, adhesion aid, 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 Various additives such as an improver, a foaming agent, a scorch inhibitor, and a lubricant 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 above-mentioned thing. However, these additives are blended in such an amount that does not impair the adhesive force with the layer (A) and the layer (C).

Examples of the filler, processing aid, and plasticizer include those described above.

The rubber composition for vulcanization includes epichlorohydrin rubber (b1-1), compound (b2-1), magnesium oxide (b3-1), silica (b4-1), and epoxy resin (b7-1). For example, it is prepared by kneading zinc oxide (b8), vulcanizing agent (b5-1) and other additives.

The kneading can be performed, for example, using an open roll, a Banbury mixer, a pressure kneader, or the like at a temperature of 150 ° C. or lower.

3. Layer (C) The layer (C) is made of a fluororesin (c) having a fuel permeability coefficient of 5.0 g · mm / m ² / day or less.

The fuel permeability coefficient is preferably 3.0 g · mm / m ² / day or less, more preferably 1.0 g · mm / m ² / day or less, and 0.5 g · mm / m ² / day. More preferably, it is not more than day. Although a minimum is not specifically limited, 0.01 g * mm / m < ² > / day may be sufficient. When the fuel permeation coefficient of the layer (c) is within the above range, fuel permeation in the thickness direction of the laminate can be suppressed, and the laminate can be thinned.

The fuel permeation coefficient was measured using a fuel permeation coefficient measuring cup (fluororesin (c)) in a cup of isooctane / toluene / ethanol mixed solvent in which isooctane, toluene and ethanol were mixed at a volume ratio of 45:45:10. It is a value calculated from a change in mass measured at 60 ° C. by incorporating a sheet (diameter: 45 mm, thickness: 120 μm) obtained from the above.
(Sheet production method)
Each of the resin pellets was put into a mold having a diameter of 120 mm, set in a press machine heated to 300 ° C., and melt-pressed at a pressure of about 2.9 MPa to obtain a sheet having a thickness of 0.12 mm.

The fluororesin (c) is preferably at least one selected from the group consisting of the PCTFE, the CTFE copolymer, and the VdF / TFE copolymer, the CTFE copolymer, and It is more preferable that it is at least one selected from the group consisting of the VdF / TFE copolymer, and it is more preferable that it be a CTFE copolymer. These fluororesins are as already described.

The fluororesin (c) preferably has a flexural modulus of 1000 MPa or less. When the flexural modulus is 1000 MPa or less, the excellent sealability of the laminate is exhibited. The flexural modulus is preferably 800 MPa or less, more preferably 700 MPa or less, and further preferably 650 MPa or less.
The bending elastic modulus is a value measured by using a universal testing machine manufactured by Orientec Co., Ltd. at a bending speed of 2 mm / min at room temperature according to JIS K6911.
(Measurement sample preparation method)
The resin pellet was set in an injection molding machine heated to 300 ° C. to obtain a test piece having a length of 80.0 mm, a width of 10.0 mm, and a thickness of 4.0 mm.

4). Layer (D) The layer (D) is preferably made of rubber (d) and rubber (d) (excluding fluoro rubber).

The rubber (d) is preferably obtained by vulcanizing the unvulcanized rubber (d1).

Specific examples of the unvulcanized rubber (d1) include, for example, acrylonitrile-butadiene rubber (NBR) or a hydride thereof (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural Examples thereof include diene rubbers such as rubber (NR) and isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, and acrylic rubber.

The unvulcanized rubber (d1) is preferably a diene rubber, an epichlorohydrin rubber (ECO), or an acrylic rubber from the viewpoint of good heat resistance, oil resistance, weather resistance, and extrusion moldability. Acrylonitrile-butadiene rubber (NBR), epichlorohydrin rubber (ECO), or acrylic rubber is more preferable, and epichlorohydrin rubber (ECO) or acrylic rubber is more preferable.

The layer (D) made of rubber (d) is preferably formed from a vulcanized rubber composition containing unvulcanized rubber (d1).

Examples of the rubber composition for vulcanization include, for example, JP 2012-125015 A, International Publication No. 2011/001756, JP 2010-89479 A, JP 2012-61644 A, JP 2012-81682 A. Japanese Patent Application No. 2010-254309, Japanese Patent Application No. 2011-45942, Japanese Patent Application No. 2011-229997, Japanese Patent Application No. 2011-275417, Japanese Patent Application No. 2012-22052, Japanese Patent Application No. 2012-199719 Rubber composition for use.

The rubber composition for vulcanization contains unvulcanized rubber (d1), compound (d2), magnesium oxide (d3), and silica (d4) as essential components, and further includes a vulcanizing agent (d5) as optional components. ) And a metal salt (d6).
In particular, when the rubber composition for vulcanization contains a vulcanizing agent (d5) and a metal salt (d6) in addition to the unvulcanized rubber (d1) and the compound (d2), it adheres more firmly to the adjacent layer. To do.

The above (d1) to (d6) are the same as (b1) to (b6) described above.

5. Regarding the laminate The laminate of the present invention preferably has an interlayer initial adhesive strength of 5 N / cm or more among all the layers. When the interlayer initial adhesive strength is 5 N / cm or more, there is an advantage that when the hose is vulcanized in a specific shape, displacement does not easily occur and peeling does not occur when an impact is applied.
The laminated body of this invention can make interlayer initial stage adhesive strength into the said range by having the said structure. The interlayer initial adhesive strength is more preferably 10 N / cm or more, and further preferably 15 N / cm or more.
The initial adhesion strength between layers is in accordance with JIS-K-6256 (vulcanized rubber adhesion test method), a peel test is performed at 25 ° C. at a tensile rate of 50 mm / min, and the adhesion strength is measured. 3 is a value obtained by calculating an average value of the three data.

The laminated body of this invention can be manufactured by laminating | stacking layer (A)-(D). A method of producing a laminate in which the layer (B) is laminated on the layer (A), the layer (C) is laminated on the layer (B), and the layer (D) is laminated on the layer (C) is preferable. .

Lamination of these layers can be carried out by a known method such as a method in which each layer is separately molded and then laminated by means such as pressure bonding, and a method in which layers (A) and (B) are simultaneously molded and laminated. it can. Moreover, you may perform formation of a layer (C) by apply | coating the composition for forming the layer which consists of a fluororesin (c) to a layer (B) or a layer (D).

Molding of the layer (B) or the layer (D) can be carried out by subjecting the rubber composition for vulcanization to a heat compression molding method, a transfer molding method, an extrusion molding method, an injection molding method, a calendar molding method, a coating method, It can be set as a molded body having various shapes such as a sheet shape and a tube shape.

The layer (C) 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.

Moreover, it can be set as multilayer molded articles, such as a multilayer tube, a multilayer hose, a multilayer tank, by molding methods, such as multilayer extrusion molding, multilayer blow molding, and multilayer injection molding.

In addition, as a method of simultaneously molding and laminating a plurality of layers, the materials for forming the layers (A) to (D) are made of a multilayer compression molding method, a multilayer transfer molding method, a multilayer extrusion molding method, a multilayer injection molding. And a method of laminating simultaneously with molding by a method such as a doubling method. In this method, since each layer can be laminated simultaneously, a step of closely adhering these layers is not particularly necessary, and it is suitable for obtaining strong adhesion in a subsequent vulcanization step.

The layer (B) and the layer (D) may be unvulcanized, but a strong interlayer adhesion can be obtained by vulcanizing the unvulcanized laminate including the layers (A) to (D). It is done.

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, heat-treating the unvulcanized laminate as a pretreatment in a relatively short time (vulcanization has also occurred), and then vulcanizing for a long time. There is a way to do it. Among these, the method of subjecting the unvulcanized laminate to a heat treatment as a pretreatment in a relatively single time and then vulcanizing it over a long period of time makes it possible to easily obtain adhesion between the respective layers. Since the layers (B) and (D) have already been vulcanized and the shape is stabilized, it is preferable because various methods for holding the laminate in the subsequent vulcanization can be selected.

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.

As described above, the layered body is preferably a layer (A), a layer (B), a layer (C), and a layer (D) stacked in this order.
The laminate is preferably a hose or tube in which the layer (A) is the innermost layer and the layer (D) is the outermost layer. By adopting such a configuration, more excellent fuel barrier properties, flexibility, adhesiveness, and fuel resistance can be exhibited.
The laminate of the present invention may have other layers.

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, particularly the vulcanized laminate, is excellent in low fuel permeability, heat resistance, oil resistance, fuel oil resistance, LLC resistance, steam resistance, and under severe conditions. And 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. Because it has chemical resistance, low elution and low fragrance properties, in the medical and chemical fields, oil, chemical, heat, steam or weather resistant seals, lids, belts, rolls, hoses, tubes, Applicable to films, coatings, linings, joints, containers, etc. 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, packings, 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.

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

Among these, the laminate is particularly preferably used as a tube or a hose. That is, the laminate is preferably a tube or a hose.
Among the tubes or hoses, a fuel piping tube or hose is preferable in terms of heat resistance, flexibility, and low fuel permeability, and can be suitably used as a fuel piping tube or hose for automobiles.

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

Each numerical value of the examples was measured by the following method.

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

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

MFR (Melt Flow Rate)
Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the mass (g) of the polymer flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm per unit time (10 minutes) was measured.

Mooney viscosity Measured at 121 ° C. according to ASTM D-1646 using Mooney viscometer MV2000E type manufactured by ALPHA TECHNOLOGIES.

Fuel permeability coefficient (fluorine materials (1) and (2), fluororesins (3) to (6))
Composition to be measured in a fuel permeability coefficient measuring cup made of SUS316 having an inner diameter of 40 mmφ and a height of 20 mm charged with 18 mL of an isooctane / toluene / ethanol mixed solvent in which isooctane, toluene and ethanol are mixed at a volume ratio of 45:45:10. To a value calculated from a change in mass measured at 60 ° C. by incorporating a sheet (diameter: 45 mm, thickness: 120 μm) prepared by the following method. The sheet | seat used for a measurement was produced with the following method.
(Sheet production method)
Each pellet made of each material was put into a 120 mm diameter mold, set in a press machine heated to 300 ° C., and melt-pressed at a pressure of about 2.9 MPa to obtain a sheet having a thickness of 0.12 mm. .

Fuel permeation amount of laminated body The above measurement sheet is changed to the laminated body obtained in the examples and comparative examples, and the fuel that permeates only from the trunk portion of the hose and the fuel that permeates only from the end portion are measured. The fuel permeation amount of the laminate was measured.

Bending elastic modulus This is a value measured using a universal testing machine manufactured by Orientec Co., Ltd. at a bending speed of 2 mm / min at room temperature in accordance with JIS K6911. The test piece was produced by the following method.
(Test piece preparation method)
The pellet made of each material was set in an injection molding machine heated to 300 ° C. to obtain a test piece having a length of 80.0 mm, a width of 10.0 mm, and a thickness of 4.0 mm.

Interlayer initial adhesive strength JIS-K-6256 (vulcanized rubber adhesion test method), peel test was conducted at 25 ° C. at a tensile rate of 50 mm / min, and the adhesive strength was measured. It is the value which calculated the average value of data. The evaluation criteria (◯, x) in Table 1 are as follows.
○: Interlayer initial adhesive strength is 5 N / cm or more ×: Interlayer initial adhesive strength is less than 5 N / cm

The hose flexibility was evaluated by the degree of difficulty when inserting the hose into the iron pipe.
○: Can be easily inserted ×: Could not be inserted

An isooctane / toluene / ethanol mixed solvent in which isooctane, toluene and ethanol were mixed at a volume ratio of 45:45:10 was put into a hose inserted into a sealing iron pipe, and leakage from between the hose and the iron pipe was evaluated.
○: No leakage ×: Leakage occurred

The thickness hose cross section of each layer was measured using a microscope, the thickness of each layer was measured, and the average value of the obtained four points of data was calculated.

The materials used in Examples and Comparative Examples are shown below.
[Fluorine material (1)]
Fluoro rubber X (binary rubber consisting of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) (VdF: HFP = 78: 22 mol%, Mooney viscosity at 121 ° C. = 41)) is cross-linked to 100 parts by mass. 2 parts by weight of an agent (2,2-bis (4-hydroxyphenyl) perfluoropropane) and 0.5 parts by weight of a crosslinking accelerator (benzyltriphenylphosphonium chloride), an acid acceptor (magnesium oxide “Kyowa Chemical Industry” MA150 ") 3 parts by mass were kneaded with an open roll to prepare a fluororubber composition.

Subsequently, a fluorine-containing ethylenic polymer Y (ethylene-tetrafluoroethylene copolymer (ETFE) composed of tetrafluoroethylene and ethylene, MFR at 297 ° C./5000 g load = 30 g / 10 min, melting point 220 ° C.) was prepared as described above. After the fluororubber composition is mixed at fluororubber X / fluororesin Y = 20/80 (mass ratio), it is supplied to a twin screw extruder and melt kneaded under conditions of a cylinder temperature of 250 ° C. and a screw rotation speed of 300 rpm. And pellets of the thermoplastic polymer composition were produced.
Fuel permeability coefficient 5.3 g · mm / m ² / day, flexural modulus 340 MPa, crosslinked fluororubber X / fluororesin Y = 20/80 (mass ratio)
[Fluorine material (2)]
Composition in which carbon is added to the fluorine material (1) so as to be 10% by mass [fluorine resin (3)]
TFE / CTFE / PPVE copolymer, MFR = 30 g / 10 min (temperature 297 ° C., weight 5.0 kg), melting point 247 ° C., fuel permeability coefficient 0.4 g · mm / m ² / day, flexural modulus 600 MPa
[Fluororesin (4)]
Product name: THV815, VdF / TFE / HFP copolymer, melting point 222 ° C., fuel permeability coefficient 2.5 g · mm / m ² / day
[Fluororesin (5)]
VdF / TFE / HFP / PPVE copolymer, VdF / TFE / HFP / PPVE = 8.1 / 84.5 / 7.0 / 0.4 (molar ratio), melting point 248 ° C., fuel permeability coefficient 0.8 g · mm / m ² / day
[Fluororesin (6)]
Product name: THV500, melting point 168 ° C., fuel permeation coefficient 10 g · mm / m ² / day, VdF / TFE / HFP copolymer

Other ECO: Epichlorohydrin rubber, trade name: Epichromer CG, Daiso Co., Ltd. NBR: acrylonitrile-butadiene rubber, trade name: Nipol DN101, Nippon Zeon Co., Ltd. fluoro rubber: fluoro rubber X (vinylidene fluoride (VdF) and hexafluoro) Binary rubber (VdF: HFP = 78: 22 mol%, Mooney viscosity at 121 ° C. = 41) 100 parts by mass of propylene (HFP) is used as a crosslinking agent (2,2-bis (4-hydroxyphenyl) 2 parts by mass of perfluoropropane), 0.5 parts by mass of a crosslinking accelerator (benzyltriphenylphosphonium chloride) and 3 parts by mass of an acid acceptor (magnesium oxide “MA150” manufactured by Kyowa Chemical Industry) are kneaded with an open roll. Fluororubber composition obtained by

Example 1
The rubber material and fluororesin described above were continuously extruded using an extruder. Rubber material (1) was used as the innermost layer rubber material, NBR was used as the inner layer rubber material, fluororesin (3) was used as the intermediate layer resin material, and ECO was used as the outer layer rubber material. The obtained molded product was steam vulcanized using a vulcanizing can to obtain a multilayer hose having the above-mentioned four-layer structure.

Examples 2-4 and Comparative Examples 1-5
A multilayer hose was obtained in the same manner as in Example 1 except that the innermost rubber layer, inner rubber layer, intermediate resin layer, and outer rubber layer were changed as shown in Table 1 or 2.

11 Laminated body 11a Fluoro rubber layer 11b, 11d Rubber layer 11c Fluoro resin layer 12 Sleeve member 13 Iron pipe 13a Stopper

Claims (9)

A layer (A) comprising a cross-linked fluororubber (a) and a fluororesin (a),
A layer (B) comprising rubber (b),
A layer (C) made of a fluororesin (c) having a fuel permeability coefficient of 5.0 g · mm / m ² / day or less, and
Layer (D) made of rubber (d) (excluding fluoro rubber)
The laminated body characterized by including. In the layer (A), the crosslinked fluororubber (a) dynamically crosslinks the uncrosslinked fluororubber (a) in the presence of the fluororesin (a) under the melting condition of the fluororesin (a). The laminate according to claim 1, which is obtained by the following. The laminate according to claim 1 or 2, wherein in the layer (A), the fluororesin (a) forms a continuous layer, and the crosslinked fluororubber (a) forms a dispersed phase. The layer (A) is a step of obtaining a composition (a1) containing an uncrosslinked fluororubber (a) and a crosslinking agent (a), and the composition (a1) and the fluororesin (a) are mixed with the melting point of the fluororesin (a). It is manufactured by a manufacturing method including a step of obtaining a composition (a2) by kneading at the above temperature, and a step of forming the composition (a2),
The laminate according to claim 1, 2, or 3, wherein the composition (a2) has a fuel permeability coefficient of 10.0 g · mm / m ² / day or less. The layer (A) is a step of obtaining a composition (a1) containing an uncrosslinked fluororubber (a) and a crosslinking agent (a), and the composition (a1) and the fluororesin (a) are mixed with the melting point of the fluororesin (a). It is manufactured by a manufacturing method including a step of obtaining a composition (a2) by kneading at the above temperature, and a step of forming the composition (a2),
The laminate according to claim 1, 2, 3 or 4, wherein the composition (a2) has a flexural modulus of 1000 MPa or less. The laminate according to claim 1, 2, 3, 4 or 5, wherein the flexural modulus of the fluororesin (c) is 1000 MPa or less. The laminate according to claim 1, 2, 3, 4, 5, or 6 having an interlayer initial adhesive strength of 5 N / cm or more among all the layers. The laminate according to claim 1, which is a hose. It is a fuel piping hose, The laminated body of Claim 1, 2, 3, 4, 5, 6, 7 or 8.

Images