JP6357768B2 - Laminate - Google Patents

Description

The present invention relates to a laminate.

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

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

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

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

International Publication No. 2013/058130

An object of the present invention is to provide a laminate in which a rubber layer and a fluororesin layer are firmly bonded without using an adhesive and without subjecting the rubber layer and the fluororesin layer to surface treatment. And

The present invention is a laminate comprising a rubber layer (A) and a fluororesin layer (B) laminated on the rubber layer (A), wherein the rubber layer (A) is a rubber composition for vulcanization. The rubber composition for vulcanization is composed of acrylonitrile-butadiene rubber and its hydride, styrene-butadiene rubber, chloroprene rubber, butadiene rubber, natural rubber, isoprene rubber, ethylene-propylene-termonomer copolymer. Unvulcanized rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt, which is at least one selected from the group consisting of coalesced rubber, silicone rubber, butyl rubber, and acrylic rubber, 1,5-diazabicyclo (4.3.0) -nonene-5 salt, 1,8-diazabicyclo (5.4.0) undecene-7, and 1,5-diazabicyclo (4.3 0) -nonene-5 containing at least one compound (a2) selected from the group consisting of nonene-5, thiuram compound (a3), magnesium oxide (a4), and silica (a5), a fluororesin layer (B ) Is a layer formed from a fluoropolymer composition, and the fluoropolymer composition relates to a laminate comprising a fluoropolymer (b1) having copolymerized units derived from chlorotrifluoroethylene.

（式中、Ｒ^１及びＲ^２は、独立して、炭素数１〜１２の直鎖又は分岐のアルキル基、ベンジル基、若しくは、フェニル基であり、ｎ１は１〜４の整数である。）で示される化合物、及び、下記一般式（２）：

（式中、環Ａは、環中の水素原子が置換されていてもよい３員、４員、５員又は６員の含窒素複素環であり、ｎ２は１〜４の整数である。）で示される化合物、からなる群より選択される少なくとも１種であることが好ましい。 The thiuram compound (a3) has the following general formula (1):

(In the formula, R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a benzyl group, or a phenyl group, and n1 is an integer of 1 to 4.) And a compound represented by the following general formula (2):

(In the formula, ring A is a 3-membered, 4-membered, 5-membered or 6-membered nitrogen-containing heterocyclic ring in which a hydrogen atom in the ring may be substituted, and n2 is an integer of 1 to 4). It is preferable that it is at least 1 sort (s) selected from the group which consists of a compound shown by these.

The rubber composition for vulcanization preferably further contains at least one vulcanizing agent (a6) selected from the group consisting of a sulfur vulcanizing vulcanizing agent and a peroxide vulcanizing vulcanizing agent.

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

Compound (a2) contains 1,8-diazabicyclo (5.4.0) undecene-7, 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride, 1,8- Diazabicyclo (5.4.0) undecene-7 naphthoate, 1,8-diazabicyclo (5.4.0) undecene-7 phenol salt, 1,8-diazabicyclo (5.4.0) undecene-7 And at least one compound selected from the group consisting of 1,8-diazabicyclo (5.4.0) undecene-7 formate.

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

In the laminate of the present invention, the rubber layer (A) is preferably laminated on both sides of the fluororesin layer (B). In the laminate of the present invention, it is also preferred that the fluororesin layer (B) is laminated on both sides of the rubber layer (A). Furthermore, the laminate of the present invention preferably includes a polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B) on the rubber layer (A) or the fluororesin layer (B).

The laminate of the present invention is preferably obtained by vulcanization, and the rubber layer (A) and the fluororesin layer (B) are vulcanized and bonded.

In the laminate of the present invention, the rubber layer and the fluororesin layer are firmly bonded without using an adhesive and without subjecting the rubber layer and the fluororesin layer to surface treatment.

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

Hereinafter, each layer will be described.

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

The vulcanized rubber composition contains unvulcanized rubber (a1), compound (a2), thiuram compound (a3), magnesium oxide (a4), and silica (a5) as essential components.

As the unvulcanized rubber (a1), non-fluororubber is used because of its good cold resistance and excellent cost.

The non-fluorine rubber includes acrylonitrile-butadiene rubber (NBR) and its hydride (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), isoprene rubber ( IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, and at least one unvulcanized rubber selected from the group consisting of acrylic rubber.
As the termonomer of the ethylene-propylene-teromer copolymer rubber, a monomer constituting a diene rubber such as natural rubber, butadiene rubber (BR), isoprene rubber, butyl rubber, chloroprene rubber is preferable.

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

The rubber composition for vulcanization may contain a resin in order to give the rubber layer (A) properties different from those of the unvulcanized rubber (a1). Examples of the resin include PVC, chlorinated polystyrene, chlorosulfonated polystyrene ethylene, 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.

The compound (a2) includes 1,8-diazabicyclo (5.4.0) undecene-7 salt (DBU salt), 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt), At least one selected from the group consisting of 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) and 1,5-diazabicyclo (4.3.0) -nonene-5 (DBN) It is a compound of this. By containing the compound (a2), the vulcanization characteristics of the rubber composition for vulcanization can be improved and the adhesion between the rubber layer (A) and the fluororesin layer (B) can be strengthened.

Examples of the DBU salt and DBN salt include DBU or DBN carbonate, long chain aliphatic carboxylate, aromatic carboxylate, orthophthalate, p-toluenesulfonate, phenol salt, phenol resin salt, naphthoic acid. Salt, octylate, oleate, formate, phenol novolac resin salt, etc., and 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride (DBU-B). DBU or DBN naphthoate, DBU or DBN orthophthalate, DBU or DBN phenol salt, and DBU or DBN formate are preferred.

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

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

It is preferable that a compound (a2) is 0.1 mass part or more with respect to 100 mass parts of unvulcanized rubber (a1). The compound (a2) is more preferably 0.2 parts by mass or more with respect to 100 parts by mass of the unvulcanized rubber (a1). When there is too little compound (a2), there exists a possibility that adhesive force may not be enough.
Further, from the viewpoint of reducing the compression set and rubber hardness after vulcanization and reducing the cost of the rubber, the compound (a2) is 5.0% relative to 100 parts by mass of the unvulcanized rubber (a1). The amount is preferably at most 3 parts by mass, more preferably at most 3.0 parts by mass.
By including the compound (a3) in the rubber composition for vulcanization, the adhesive strength between the layer (A) and the layer (B) is excellent even when the content of the compound (a2) is small. be able to.

（式中、Ｒ^１及びＲ^２は、独立して、炭素数１〜１２の直鎖又は分岐のアルキル基、ベンジル基、若しくは、フェニル基であり、ｎ１は１〜４の整数である。）で示される化合物、及び、下記一般式（２）：

（式中、環Ａは、環中の水素原子が置換されていてもよい３員、４員、５員又は６員の含窒素複素環であり、ｎ２は１〜４の整数である。）で示される化合物、からなる群より選択される少なくとも１種であることが好ましい。上記含窒素複素環は、環式炭化水素基の環骨格の炭素の一つが窒素で置換されたものであることが好ましい。 In the laminate of the present invention, when the rubber composition for vulcanization contains the thiuram compound (a3), the adhesion between the rubber layer (A) and the fluororesin layer (B) can be strengthened.
A conventionally known thiuram compound can be used as the thiuram compound (a3). Among them, since the adhesive strength between the layer (A) and the layer (B) can be excellent, the following general formula (1):

(In the formula, R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a benzyl group, or a phenyl group, and n1 is an integer of 1 to 4.) And a compound represented by the following general formula (2):

(In the formula, ring A is a 3-membered, 4-membered, 5-membered or 6-membered nitrogen-containing heterocyclic ring in which a hydrogen atom in the ring may be substituted, and n2 is an integer of 1 to 4). It is preferable that it is at least 1 sort (s) selected from the group which consists of a compound shown by these. The nitrogen-containing heterocycle is preferably one in which one of the carbons in the ring skeleton of the cyclic hydrocarbon group is substituted with nitrogen.

In the general formula (1), R ¹ and R ² are independently preferably a linear or branched alkyl group having 1 to 8 carbon atoms, a benzyl group, or a phenyl group, and the above R ¹ and R ² Is preferably a linear or branched alkyl group having 1 to 8 carbon atoms or a benzyl group.

In the general formula (2), ring A is preferably a 5- or 6-membered nitrogen-containing heterocyclic ring in which a hydrogen atom in the ring may be substituted, and the hydrogen atom in the ring is substituted. More preferably, it is a 6-membered nitrogen-containing heterocyclic ring.
A hydrogen atom in ring A may be substituted with an OH group, a halogen atom, or the like, or may not be substituted. Ring A preferably does not contain a double bond.

で示されるテトラメチルチウラムジスルフィド（ＴＭＴＤ）、下記式：

で示されるテトラエチルチウラムジスルフィド（ＴＥＴＤ）、下記式：

で示されるテトラブチルチウラムジスルフィド（ＴＢＴＤ）、下記式：

で示されるテトラキス（２−エチルヘキシル）チウラムジスルフィド、下記式：

で示されるテトラベンジルチウラムジスルフィド、下記式：

で示されるテトラメチルチウラムモノスルフィド（ＴＭＴＭ）等が挙げられる。 Examples of the compound represented by the general formula (1) include the following formula:

Tetramethylthiuram disulfide (TMTD) represented by the following formula:

Tetraethylthiuram disulfide (TETD) represented by the following formula:

Tetrabutylthiuram disulfide (TBTD) represented by the following formula:

Tetrakis (2-ethylhexyl) thiuram disulfide represented by the following formula:

Tetrabenzylthiuram disulfide represented by the following formula:

And tetramethylthiuram monosulfide (TMTM).

As the thiuram compound represented by the general formula (1), commercially available products can be used. For example, Noxeller TT-P (TMTD), Noxeller TET-G (TETD) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. Noxeller TBT (TBTD), Noxeller TOT-N, Noxeller TBZTD, Noxeller TS (TMTM), etc. can be used.

（式中、ｎ２は１〜４の整数である。）で示される化合物が好ましい。具体例としては、下記式：

で示されるジペンタメチレンチウラムテトラスルフィド（ＤＰＴＴ）等が挙げられる。上記ＤＰＴＴとしては、例えば、大内新興化学工業（株）製のノクセラーＴＲＡを用いることができる。 Examples of the compound represented by the general formula (2) include the following general formula:

(Wherein n2 is an integer of 1 to 4) is preferred. As a specific example, the following formula:

And dipentamethylene thiuram tetrasulfide (DPTT). As the DPTT, for example, Noxeller TRA manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. can be used.

Since the compound (a3) can strengthen the adhesion between the rubber layer (A) and the fluororesin layer (B), it is 0.1 part by mass or more with respect to 100 parts by mass of the unvulcanized rubber (a1). Is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, and particularly preferably 1.0 parts by mass or more.
Moreover, from an economical viewpoint, the compound (a3) is preferably 5.0 parts by mass or less and 100 parts by mass or less with respect to 100 parts by mass of the unvulcanized rubber (a1). More preferred.

The blending amount of the magnesium oxide (a4) 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 (a1) from the viewpoint of adhesiveness and rubber physical properties. is there. The laminate having a specific structure of the present invention has excellent adhesiveness by requiring magnesium oxide (a4) as an essential component.

As silica (a5), basic silica and acidic silica can be used, and it is preferable to use basic silica from the viewpoint of adhesiveness. Examples of basic silica include Carplex 1120 (manufactured by DSL Japan Co., Ltd.). Further, the blending amount of silica (a5) is preferably 10 to 40 parts by weight, particularly preferably 15 to 25 parts by weight, based on 100 parts by weight of the unvulcanized rubber (a1), from the viewpoint of adhesiveness and rubber physical properties. is there. The laminate having a specific structure of the present invention has excellent adhesiveness by making silica (a5) essential.

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

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

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

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

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

The compounding amount of the sulfur vulcanizing vulcanizing agent is preferably 1.0 to 10.0 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). 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 0.1-15.0 mass parts normally with respect to 100 mass parts of unvulcanized rubbers, Preferably it is 0.3-5.0 mass parts.

The vulcanizing agent (a6) is preferably at least one selected from the group consisting of a sulfur vulcanizing vulcanizing agent and a peroxide vulcanizing vulcanizing agent. It is also preferable to use a sulfur vulcanizing agent and a peroxide vulcanizing agent in combination.
The addition amount of the vulcanizing agent (a6) is preferably 0.5 to 5.0 parts by mass, more preferably 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). Part.

The rubber composition for vulcanization preferably contains a thiazole vulcanization accelerator from the viewpoint of vulcanization speed control.
Examples of the thiazole vulcanization accelerator include N-oxydiethylene-2-benzothiazolylsulfenamide.
The addition amount of the thiazole vulcanization accelerator is preferably 0.5 to 5.0 parts by mass, more preferably 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1). Part.

The rubber composition for vulcanization may contain a thiazole metal salt from the viewpoint of vulcanization speed control. As the thiazole metal salt, a zinc salt of mercaptobenzothiazole (ZnMBT) is preferably used.
The amount of the thiazole-based metal salt is preferably 0.01 to 3.0 parts by mass, more preferably 0.01 to 0.5 parts by mass, and still more preferably 100 parts by mass of the unvulcanized rubber (a1). It is 0.05-0.3 mass part.

The rubber composition for vulcanization may further contain at least one compound selected from the group consisting of dithiocarbamic acid metal salts, aldehyde-amine compounds, and metal hydrates.

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

The metal hydrate is preferably a hydrate of at least one metal selected from copper, zinc, aluminum, cobalt, calcium, zirconium, nickel and magnesium. Specifically, CuSO ₄ .5H ₂ O, ZnSO ₄ .H ₂ O, ZnSO ₄ .7H ₂ O, AlCl ₃ . 6H ₂ O, aluminum silicate _{n-hydrate, (Al (NO 3) 3} · 9H 2 O), 1.5 hydrate of CoCl _2, 2 hydrate, tetrahydrate or hexahydrate, CaCl ₂ dihydrate, tetrahydrate or hexahydrate, calcium silicate hydrate, calcium sulfate hydrate, zirconium oxychloride octahydrate, zirconium oxynitrate dihydrate, zirconium dioxide water hydrate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, nickel chloride hexahydrate, magnesium sulfate hydrate, magnesium fluoride hydrate, magnesium chloride _hexahydrate, CaSO 4 · 0.5H ₂ O, CaSO ₄ .2H ₂ O, calcium acetate monohydrate and the like. The metal hydrate is preferably at least one hydrate selected from the group consisting of CaSO ₄ .2H ₂ O and calcium acetate monohydrate, more preferably calcium acetate monohydrate. is there.

The aldehyde-amine compound is at least selected from the group consisting of n-butyraldehyde aniline, acetaldehyde aniline, butyraldehyde acetaldehyde aniline, butyraldehyde monobutylamine, butyraldehyde butylidene aniline, formaldehyde acetaldehyde aniline, and aldehyde amine. One is preferred. More preferred as an aldehyde-amine compound is n-butyraldehyde aniline.

The content of at least one compound selected from the group consisting of the dithiocarbamic acid metal salt, aldehyde-amine compound, and metal hydrate is 0 with respect to 100 parts by mass of the unvulcanized rubber (a1). It is preferably 1 part by mass or more, more preferably 0.3 part by mass or more, and further preferably 1.0 part by mass or more.
From the viewpoint of cost, it is preferably 35.0 parts by mass or less, more preferably 25.0 parts by mass or less, with respect to 100 parts by mass of the unvulcanized rubber (a1), and 23.0 parts by mass or less. More preferably.

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 said thing. However, these additives are blended in such an amount that does not impair the adhesive force with the fluororesin layer (B) which is the object of the present invention.

Fillers include metal oxides such as calcium oxide, titanium oxide, and aluminum oxide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; magnesium carbonate, aluminum carbonate, calcium carbonate, barium carbonate, etc. Carbonates; silicates such as magnesium silicate, calcium silicate, sodium silicate, and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate, and barium sulfate; synthetic hydrotalcite, molybdenum disulfide, iron sulfide, sulfide Metal sulfides such as copper; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, quartz fine powder, zinc white, talc, mica powder, wax Lastite, carbon fiber, aramid fiber Various whiskers, glass fiber, organic reinforcing agents, organic fillers and the like.
The content of the filler is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, with respect to 100 parts by mass of the unvulcanized rubber (a1), and 3.0 masses. More preferably, it is part or more.
From the viewpoint of cost, it is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 50 parts by mass or less with respect to 100 parts by mass of the unvulcanized rubber (a1). .

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

Examples of the plasticizer include phthalic acid derivatives, sebacic acid derivatives, adipic acid derivatives, and the like.
The content of the plasticizer is preferably 1.0 parts by mass or more, more preferably 3.0 parts by mass or more, with respect to 100 parts by mass of the unvulcanized rubber (a1), and 5.0 masses. More preferably, it is part or more.
From the viewpoint of cost, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less with respect to 100 parts by mass of the unvulcanized rubber (a1). .

Examples of softeners include lubricating oil, process oil, coal tar, castor oil, calcium stearate, and anti-aging agents such as phenylenediamines, phosphates, quinolines, cresols, phenols, and dithiocarbamate metal salts. Can be given.

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

An epoxy resin represented by the formula is particularly preferred. Here, in Formula (3), n is an average value, 0.1-3 are preferable, 0.1-0.5 are more preferable, 0.1-0.3 are further more preferable. When n is less than 0.1, the adhesive strength with the fluororesin (b) tends to decrease. On the other hand, when n exceeds 3, the viscosity of the epoxy resin itself 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, 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 force with the fluororesin (b). More preferred is 3 parts by mass or more. 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 (a1), compound (a2), compound (a3), magnesium oxide (a4), and silica (a5), and if necessary, vulcanizing agent (a6), It is prepared by kneading a thiazole vulcanization accelerator and 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 (T90) of 18 minutes or less. More preferably, it is 15 minutes or less. Although the minimum of T90 is not specifically limited, For example, it is 1 minute or more.
Since the rubber composition for vulcanization has the above configuration, the vulcanization time can be shortened and the productivity can be improved. T90 is a value obtained by measuring the maximum torque value (MH) and the minimum torque value (ML) at 160 ° C., and is a value obtained by {(MH) − (ML)} × 0.9 + ML. MH and ML are values measured according to JIS K 6300-2.

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

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

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

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

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

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

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

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

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

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

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

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

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

The fluoropolymer (b1) is particularly preferably PCTFE or CTFE-TFE-PAVE copolymer. The CTFE-TFE-PAVE copolymer is a copolymer consisting essentially of CTFE, TFE and PAVE. Even more preferred is a CTFE-TFE-PAVE copolymer.
In the present invention, since the rubber layer (A) is a layer formed from a vulcanizing fluororubber composition having a limited composition, the fluororesin layer (B) is a PCTFE or CTFE-TFE-PAVE copolymer. Even if it exists, the adhesion | attachment of a rubber layer (A) and a fluororesin layer (B) is strong.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In order to impart conductivity, a conductive filler may be added. The conductive filler is not particularly limited, and examples thereof include conductive simple powder such as metal and carbon or conductive simple fiber; powder of conductive compound such as zinc oxide; surface conductive powder. When blending the conductive filler, it is preferable to prepare a pellet in advance by melt-kneading.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Valve stem seals for engine valves, etc.

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

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

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

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

Steering power steering oil hose, etc.

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

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

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

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

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

In addition, in food rubber seal material applications, there is a problem that flavoring or rubber fragments are mixed into food in conventional rubber seal materials, but by using the laminate of the present invention, this problem can be improved and preferably Can be used. Rubber seal materials for pipes that use solvents for pharmaceutical and chemical applications have a problem that rubber materials swell in the solvent. However, the use of the laminate of the present invention improves the rubber materials. 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.

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

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

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

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

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

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

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

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

Synthesis Example 1 (Synthesis of fluororesin (1))
51.5 kg of demineralized pure water was charged in a jacketed stirring polymerization tank capable of containing 174 kg of water, the interior space was sufficiently replaced with pure nitrogen gas, and then the nitrogen gas was removed in vacuum. Next, 40.6 kg of octafluorocyclobutane, 1.3 kg of chlorotrifluoroethylene (CTFE), 4.5 kg of tetrafluoroethylene (TFE), and 2.8 kg of perfluoro (propyl vinyl ether) (PPVE) were injected. 0.075 kg of n-propyl alcohol (PrOH) was added as a chain transfer agent, the temperature was adjusted to 35 ° C., and stirring was started. Here, 0.44 kg of a 50 mass% methanol solution of di-n-propyl peroxydicarbonate (NPP) was added as a polymerization initiator to initiate polymerization. During the polymerization, the mixed monomer prepared to the same composition (monomer ratio) as the copolymer composition to be obtained was polymerized while being additionally charged so that the pressure inside the tank was maintained at 0.66 MPa, The polymer produced by exhausting the residual gas was taken out, washed with demineralized pure water, and dried to obtain 30.5 kg of a granular powder CTFE copolymer (fluororesin (1)). Next, melt kneading was performed at a cylinder temperature of 290 ° C. using a φ50 mm short axis extruder to obtain pellets. Next, the obtained pellet-like CTFE copolymer was heated at 205 ° C. for 8 hours. The obtained polymer was a CTFE / TFE / PPVE copolymer having CTFE / TFE / PPVE = 21.3 / 76.3 / 2.4 (mol%), and the melting point was MFR measured at 246 ° C. and 297 ° C. Was 29.2 g / 10 min, and the fuel permeability coefficient was 0.4 g · mm / m ² / day. The number of functional groups to the main chain carbon ¹⁰⁶ was 180.

Production Example 1 (Production of fluororesin sheet)
Using the fluororesin (1) obtained in Synthesis Example 1, a fluororesin sheet was obtained using a φ30 mm single layer extruder. Extrusion is a 120 μm sheet by setting the cylinder temperature to 275 to 285 ° C., the head temperature to 285 ° C., the die temperature to 290 to 295 ° C., the screw speed to 33 rpm, the sheet take-up speed to 3 m / min, and the lip width to 1150 μm It was.

Production Examples 2 to 8 (Production of vulcanized rubber composition sheet)
The material shown in Table 2 below was kneaded using an 8-inch open roll to obtain a sheet of a rubber composition for vulcanization having a thickness of about 3 mm. In addition, each numerical value of Table 2 represents a mass part.
In addition, with respect to the obtained rubber composition for vulcanization, a maximum torque value (MH) and a minimum torque value at 160 ° C. using a curast meter type II (model number: JSR curast meter, manufactured by JSR). (ML) was measured, and induction time T10 and optimum vulcanization time T90 were determined. MH and ML are values measured according to JIS K 6300-2. The measurement results are shown in Table 2.

(Examples 1-2 and Comparative Examples 1-5)
The sheet of the rubber composition for vulcanization shown in Table 2 having a thickness of about 3 mm obtained in Production Examples 2 to 8 and the fluororesin sheet having a thickness of 120 μm obtained in Production Example 1 are overlapped, and one end portion After sandwiching a fluororesin film having a width of about 10 to 15 mm (thickness 10 μm, manufactured by Daikin Industries, Ltd., trade name: Polyflon PTFE M731 skive film) between the two sheets, the resulting sheet is 2 mm thick The sheet-like laminate was obtained by inserting into a metal mold containing a metal spacer and pressing at 160 ° C. for 45 minutes.
The obtained laminate was cut into strips each having a width of 10 mm, a length of 40 mm, and 3 sets, and a fluororesin sheet was peeled off to prepare a test piece for gripping. About this test piece, using an autograph (manufactured by Shimadzu Corp., AGS-J 5 kN), conforming to the method described in JIS K 6256 (crosslinking rubber adhesion test method), 50 mm / min at 25 ° C. A peel test was conducted at a tensile speed of, and the peel mode was observed and evaluated according to the following criteria. The obtained results are shown in Table 2.
(Adhesion evaluation criteria)
○: The rubber composition for vulcanization or the fluororesin was destroyed at the interface of the laminate, and it was impossible to peel off at the interface.
X: Peeled relatively easily at the interface of the laminate.

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

Claims (8)

A laminate comprising a rubber layer (A) and a fluororesin layer (B) laminated on the rubber layer (A),
The rubber layer (A) is a layer formed from a rubber composition for vulcanization,
The rubber composition for vulcanization is
Unvulcanized rubber (a1) which is acrylonitrile-butadiene rubber or a hydride thereof,
1,8-diazabicyclo (5.4.0) undecene-7 salt, 1,5-diazabicyclo (4.3.0) -nonene-5 salt, 1,8-diazabicyclo (5.4.0) undecene-7 And at least one compound (a2) selected from the group consisting of 1,5-diazabicyclo (4.3.0) -nonene-5,
Thiuram compound (a3),
Magnesium oxide (a4), and
Containing silica (a5),
The thiuram compound (a3) is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the unvulcanized rubber (a1).
The fluororesin layer (B) is a layer formed from a fluoropolymer composition,
The fluoropolymer composition contains a fluoropolymer (b1) which is a chlorotrifluoroethylene-tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer. The thiuram compound (a3) has the following general formula (1):

(In the formula, R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a benzyl group, or a phenyl group, and n1 is an integer of 1 to 4.) And a compound represented by the following general formula (2):

(In the formula, ring A is a 3-membered, 4-membered, 5-membered or 6-membered nitrogen-containing heterocyclic ring in which a hydrogen atom in the ring may be substituted, and n2 is an integer of 1 to 4). A compound represented by
The laminate according to claim 1, which is at least one selected from the group consisting of: The rubber composition for vulcanization is further
The laminate according to claim 1 or 2, comprising at least one vulcanizing agent (a6) selected from the group consisting of a sulfur vulcanizing agent and a peroxide vulcanizing agent. Compound (a2) is
1,8-diazabicyclo (5.4.0) undecene-7,8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride, 1,8-diazabicyclo (5.4. 0) naphthoate salt of undecene-7, phenol salt of 1,8-diazabicyclo (5.4.0) undecene-7, orthophthalate salt of 1,8-diazabicyclo (5.4.0) undecene-7, and The laminate according to claim 1, which is at least one compound selected from the group consisting of 1,8-diazabicyclo (5.4.0) undecene-7 formate. The laminate according to claim 1, 2, 3, or 4, wherein the rubber layer (A) is laminated on both sides of the fluororesin layer (B). The laminate according to claim 1, 2, 3 or 4, wherein the fluororesin layer (B) is laminated on both sides of the rubber layer (A). The rubber layer (A) or the fluororesin layer (B) further includes a polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B). Or the laminated body of 6. The rubber layer (A) and the fluororesin layer (B) obtained by vulcanization treatment are vulcanized and bonded to each other. Laminated body.