JP2013176961A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate in which a fluoropolymer having a copolymerization unit derived from chlorotrifluoroethylene adheres strongly to acrylic rubber.SOLUTION: A laminate comprises 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 which includes: at least one compound (a2) selected from the group consisting of acrylic rubber (a1), 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 1,5-diazabicyclo(4.3.0)-nonene-5; and iron dithiocarbamate (a4). The fluororesin layer (B) is a layer formed from a fluoropolymer composition which includes a fluoropolymer (b1) having a copolymerization unit derived from chlorotrifluoroethylene.

Description

The present invention relates to a laminate.

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

In particular, in fuel 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, More 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 winding method is required, and the work process is complicated, resulting in a significant reduction in productivity and a substantial increase in cost.

In order to improve the adhesion between the fluororesin layer and the rubber layer, for example, as in Patent Document 1, a diene rubber such as NBR, a DBU salt, a sulfur vulcanizing agent, a carbamate metal salt, and a thiazole metal There is also known a fuel hose having a layer structure in which at least one of a salt and a diene rubber layer formed by adding magnesium oxide and a vinylidene fluoride copolymer (THV) layer are adjacent to each other.

As described in Patent Documents 2 and 3, a fluoropolymer in which at least one monomer containing a plurality of hydrogen atoms is present or a fluoropolymer essentially comprising vinylidene fluoride is used, and the dehydrofluorinated composition is mixed to obtain the fluoropolymer. It is also known to improve the adhesion of the curable elastomeric compound to the layer.

In patent document 4, it is a laminated body provided with the rubber layer and the fluororesin layer laminated | stacked on the rubber layer, Comprising: A rubber layer is a layer formed from the rubber composition for vulcanization | cure, The rubber | gum for vulcanization | cure The composition contains a compound such as unvulcanized rubber, DBU salt, magnesium oxide, and silica. The fluororesin layer is a layer formed from a fluoropolymer composition. A laminate comprising a fluoropolymer having a copolymer unit derived from fluoroethylene is known. However, Patent Document 4 does not specifically describe a laminate in which acrylic rubber and fluororesin are bonded.

JP 2007-261079 A Special table 2001-527104 gazette JP 2001-526972 A International Publication No. 2011/001756 Pamphlet

A fluoropolymer having a copolymerized unit derived from chlorotrifluoroethylene is known as a low-permeability fluororesin, but when this fluoropolymer is used as a fluororesin, conventional methods use acrylic rubber and fluororesin. It was not possible to bond directly.

The present invention provides a laminate in which a fluoropolymer having a copolymer unit derived from chlorotrifluoroethylene and an acrylic rubber are firmly bonded.

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 made of acrylic rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt, 1,5-diazabicyclo (4.3.0). ) -Nonene-5 salt, at least one selected from the group consisting of 1,8-diazabicyclo (5.4.0) undecene-7 and 1,5-diazabicyclo (4.3.0) -nonene-5. It contains seed compound (a2) and iron dithiocarbamate (a4), and the fluororesin layer (B) is a layer formed from a fluoropolymer composition. Fluoropolymer having copolymer units derived therefrom A laminate which is characterized by containing (b1).

It is one of the preferred embodiments that the vulcanizing rubber composition further contains magnesium oxide (a3).

It is also one of the preferable modes that the rubber composition for vulcanization further contains 0 to 20 parts by mass of magnesium oxide (a3) with respect to 100 parts by mass of the acrylic rubber (a1).

In the rubber composition for vulcanization, the compound (a2) is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the acrylic rubber (a1).

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, the rubber layer (A) is laminated on both sides of the fluororesin layer (B), and the polymer layer (C) other than the fluororesin layer (B) is further laminated on both sides or one side thereof. Is preferred.

In the laminate of the present invention, the rubber layer (A) is laminated on one side of the fluororesin layer (B), and the polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B) is laminated on the other side. It is preferable.

In the laminate of the present invention, the polymer layer (C) is preferably made of acrylonitrile-butadiene rubber or a hydride thereof.

In the laminate of the present invention, the fluororesin layer (B) is preferably laminated on both sides of the rubber layer (A).

The laminate of the present invention is obtained by vulcanizing the above laminate, and the rubber layer (A1) obtained by vulcanizing the rubber layer (A) and the fluororesin layer (B) are bonded by vulcanization. Is preferred.

The laminate of the present invention is preferably a tube or a hose.

The laminate of the present invention is preferably an automobile fuel piping tube or hose.

The laminate of the present invention has a chemically strong adhesion during rubber vulcanization without laminating particularly complicated processes when laminating a fluoropolymer having a copolymer unit derived from chlorotrifluoroethylene and acrylic rubber. As a result, no special process is required for bonding, molding at low cost is possible, and molding is easy. Moreover, since it can shape | mold by a normal method like extrusion molding, thin film formation is also possible and the softness | flexibility point is also improved.

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 made of acrylic rubber (a1), 1,8-diazabicyclo (5.4.0) undecene-7 salt, 1,5-diazabicyclo (4.3.0). ) -Nonene-5 salt, at least one selected from the group consisting of 1,8-diazabicyclo (5.4.0) undecene-7 and 1,5-diazabicyclo (4.3.0) -nonene-5. It contains seed compound (a2) and iron dithiocarbamate (a4), and the fluororesin layer (B) is a layer formed from a fluoropolymer composition. Fluoropolymer having copolymer units derived therefrom A laminate which is characterized by containing (b1).
In the laminate of the present invention, the rubber composition for vulcanization uses the above-mentioned specific structure, particularly iron dithiocarbamate (a4), whereby the acrylic rubber and the fluororesin are firmly and directly bonded.

Hereinafter, each component which comprises the laminated body of this invention is demonstrated.

The laminate of the present invention comprises a rubber layer (A) and a fluororesin layer (B) laminated on the rubber layer (A).

Hereinafter, each layer will be described.

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

The rubber composition for vulcanization contains acrylic rubber (a1), compound (a2), and iron dithiocarbamate (a4) as essential components.

(A1) Acrylic rubber The acrylic rubber (a1) is a polymer composed of polymerized units based on an acrylate ester. The acrylic rubber (a1) may be a homopolymer composed of polymer units based on one kind of acrylate ester, or a copolymer composed of polymer units based on two or more kinds of acrylate esters, The copolymer which consists of a polymer unit based on the seed | species or 2 or more types of acrylic ester, and a polymer unit based on the monomer copolymerizable with an acrylic ester may be sufficient.
The acrylic rubber (a1) can adjust the normal physical properties, cold resistance, oil resistance, etc. of the acrylic rubber composition by selecting the type of acrylic ester and the amount of polymerized units.

The acrylic acid ester is preferably an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms or an acrylic acid alkoxyalkyl ester having an alkoxyalkyl group having 1 to 12 carbon atoms.
Examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, and n-octyl. Examples include acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, and n-octadecyl acrylate.
Examples of the alkoxyalkyl acrylate include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl Examples thereof include acrylate, 2- (n-propoxy) propyl acrylate, 2- (n-butoxy) propyl acrylate and the like.

By adjusting the amount of polymerized units based on these acrylates, it is possible to adjust the cold resistance and oil resistance of the resulting vulcanized rubber composition and the laminate obtained from the vulcanized rubber composition. .
For example, increasing the copolymerization ratio of n-butyl acrylate can improve cold resistance. Moreover, oil resistance can be improved by increasing the copolymerization ratio of ethyl acrylate.

The acrylic rubber (a1) is also preferably a copolymer comprising polymerized units based on an acrylate ester and polymerized units based on a monomer copolymerizable with the acrylate ester.

The monomer copolymerizable with the acrylate ester is at least one monomer selected from the group consisting of methacrylate ester, vinyl acetate, cross-linking site-containing monomer (excluding vinyl acetate), and ethylene. The body is preferred.

Examples of methacrylic acid esters include methacrylic acid alkyl esters and methacrylic acid alkoxyalkyl esters. The methacrylic acid ester is preferably, for example, a methacrylic acid alkyl ester having an alkyl group having 2 to 14 carbon atoms or a methacrylic acid alkyl ester having an alkoxyalkyl group having 2 to 14 carbon atoms.

Vinyl acetate is used to maintain mechanical properties such as elongation of the vulcanized rubber composition by crosslinking the molecules when the vulcanized rubber composition is heat-aged. By adjusting the compounding amount of vinyl acetate, the intermolecular crosslinking of the resulting rubber composition for vulcanization can be adjusted.
In the acrylic rubber composition, the main chain may be cut by the influence of heat, ultraviolet rays, etc., and mechanical properties such as tensile strength and elongation at break may be deteriorated. Therefore, if vinyl acetate having a carboxyl group that easily causes a crosslinking reaction is copolymerized with the main chain of the acrylic rubber (a1), the vinyl acetate is converted into vinyl acetate when the main chain of the acrylic rubber (a1) is cut. The carboxyl group in the polymerized unit based becomes a cross-linking site, and the broken molecules can be cross-linked again.

The polymerized units based on vinyl acetate are preferably 15% by mass or less based on all polymerized units constituting the acrylic rubber (a1). When the content of the polymerized units based on vinyl acetate is within this range, it is possible to suppress the deterioration of the mechanical properties while maintaining the heat aging resistance of the acrylic rubber composition.

The crosslinking site-containing monomer is copolymerized with acrylic rubber as necessary, and is for adjusting the hardness and elongation characteristics of the resulting acrylic rubber by promoting intermolecular crosslinking.

The crosslinking site-containing monomer is preferably a monomer having at least one selected from the group consisting of an active chlorine group, an epoxy group, a carboxyl group, and a hydroxyl group (excluding the hydroxyl group contained in the carboxyl group).

Although it does not specifically limit as a crosslinking site containing monomer, For example, the monomer which has active chlorine groups, such as 2-chloroethyl vinyl ether, 2-chloroethyl acrylate, vinyl benzyl chloride, vinyl chloroacetate, allyl chloroacetate Monomers containing carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and cinnamic acid; glycidyl Examples include monomers containing an epoxy group such as acrylate, glycidyl methacrylate, allyl glycidyl ether, and methallyl glycidyl ether.

The hydroxyl group is preferably a phenolic hydroxyl group. Examples of the crosslinking site-containing monomer having a phenolic hydroxyl group include α-methyl-o-hydroxystyrene, o-cabycol, p, m-hydroxyvinyl benzoate, vinyl salicylate, eugenol, Examples include eugenol, p-isopropenylphenol, o, m, p-allylphenol, 2,2- (o, m, p-hydroxyphenyl-4-vinylacetyl) propane.

Examples of the crosslinking site-containing monomer having an active chlorine group include o, m, p-hydroxystyrene, 2-chloroethyl vinyl ether, vinyl monochloroacetate, chloromethyl styrene, and allyl chloride.

The polymer unit based on the crosslinking site-containing monomer is preferably 10% by mass or less, more preferably 5% by mass or less, based on all polymer units constituting the acrylic rubber (a1). When the polymerization unit based on the crosslinking site-containing monomer is used in this range, it can be efficiently crosslinked, the rubber elasticity is not lost, and the strength of the obtained laminate is excellent. When the polymerization unit based on the crosslinking site-containing monomer exceeds 10% by mass, the obtained vulcanizate may be cured and lose rubber elasticity.

The acrylic rubber (a1) has 40 to 95% by mass of polymerized units based on acrylic acid ester with respect to all polymerized units, and consists of active chlorine groups and hydroxyl groups (excluding hydroxyl groups contained in carboxyl groups). The polymerization unit based on a monomer having at least one group selected from the group is preferably 1 to 20% by mass. More preferably, the polymerized unit based on an acrylate ester is 50 to 90% by mass, and is at least one group selected from the group consisting of an active chlorine group and a hydroxyl group (excluding the hydroxyl group contained in the carboxyl group). The polymerized units based on the monomer having a content of 2 to 10% by mass.

When the acrylic rubber (a1) has a polymerized unit based on ethylene, the polymerized unit based on ethylene is preferably 50% by mass or less based on all polymerized units constituting the acrylic rubber (a1). By copolymerizing ethylene, an acrylic rubber with significantly improved strength can be obtained.

The acrylic rubber (a1) can be copolymerized with other monomers copolymerizable with these monomers within a range not impairing the object of the present invention. Examples of other copolymerizable monomers include, but are not limited to, alkyl vinyl ketones such as methyl vinyl ketone; vinyl ethers or allyl ethers such as vinyl ethyl ether and allyl methyl ether; styrene, α-methyl styrene. Vinyl aromatic compounds such as chlorostyrene, vinyl toluene and vinyl naphthalene; vinyl nitriles such as acrylonitrile and methacrylonitrile; acrylamide, propylene, butadiene, isoprene, pentadiene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, Examples thereof include ethylenically unsaturated compounds such as ethylene and vinyl propionate.

The acrylic rubber (a1) can be obtained by copolymerizing the above monomers by a known method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like.

The acrylic rubber (a1) is produced, for example, by coagulating a polymer obtained by the following polymerization method by a normal salting out operation, washing with water and drying. As a salting-out agent, salt etc. can be used.

In a 2 liter beaker, 5.0 g of anionic emulsifier, dioctylsulfosuccinate sodium salt is dissolved in 1250 g of deionized water, and 300 g of the monomer mixture constituting acrylic rubber (a1) is added to the beaker. Emulsify. Next, the monomer emulsion is introduced into a polymerization vessel with a 2-liter reflux condenser, and the temperature is raised to 70 ° C. under a nitrogen stream. To this, 10 g of a 10% aqueous solution of ammonium persulfate is added to initiate polymerization. After the start of polymerization, the temperature in the polymerization vessel is increased from the initial 70 ° C. to 80 ° C., and maintained in the range of 80 to 82 ° C. for 2 hours to complete the polymerization reaction.

The rubber composition for vulcanization may further contain a vulcanizing agent (a9). The vulcanizing agent (a9) may be appropriately selected depending on the type of acrylic rubber (a1) and the like, and a vulcanizing agent generally used for vulcanizing acrylic rubber can be used. The vulcanizing agent (a9) may not be used depending on the type of acrylic rubber (a1).

Although the addition amount of a vulcanizing agent (a9) is not specifically limited, 0.5-5.0 mass parts is preferable with respect to 100 mass parts of acrylic rubber (a1). When the amount is within the above range, sufficient vulcanization treatment can be performed. When the amount of the vulcanizing agent (a9) is 0.5 parts by mass or less, the rubber composition for vulcanization becomes insufficiently vulcanized, and mechanical properties such as tensile strength and elongation at break of the resulting rubber layer (A) are lowered. There is a fear. Moreover, when it exceeds 5.0 mass parts, there exists a possibility that the vulcanizate obtained may be hardened and lose elasticity.

As the vulcanizing agent (a9), sulfur vulcanizing vulcanizing agent, polyamine vulcanizing vulcanizing agent, polyol vulcanizing vulcanizing agent, peroxide vulcanizing vulcanizing agent, imidazole vulcanizing vulcanizing agent, At least one selected from the group consisting of a triazine vulcanizing agent, an oxazole vulcanizing agent, a thiazole vulcanizing agent, and a peroxide vulcanizing agent is preferable. When the acrylic rubber (a1) contains a polymer unit based on a crosslinking site-containing monomer, an appropriate vulcanizing agent may be selected depending on the crosslinking site-containing monomer.

Examples of the polyamine compound include 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenyl sulfide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,3. -Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) pentane, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-diaminodiphenylsulfone, bis (4-3-aminophenoxy) phenyl sulfone, 2,2-bis [ 4- (4-Aminophenoxy) phenyl] hexafluoropropane, 3,4'-diaminodiphenyl ether, 4,4'-diamy Aromatic polyamine compounds such as diphenyl ether, 4,4′-diaminobenzanilide, bis [4- (4-aminophenoxy) phenyl] sulfone, hexamethylene diamine, hexamethylene diamine carbamate, N, N′-dicinenamilidene-1,6 -Aliphatic polyamine compounds such as hexanediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

Examples of the guanidine-based compound include guanidine, tetramethylguanidine, dibutylguanidine, diphenylguanidine, di-o-tolylguanidine and the like.

When the crosslinking site-containing monomer is a monomer having an epoxy group, the crosslinking agent is preferably an imidazole compound. Examples of imidazole compounds include 1-methylimidazole, 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2- Ethyl-5-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitic acid salt, 1-aminoethylimidazole, 1-aminoethyl-2-methylimidazole, 1-aminoethyl 2-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1 -Cyanoethyl-2-me Ruimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 2,4 -Diamino-6- [2'-methylimidazolyl- (1) '] ethyl-s-triazine isocyanuric acid adduct, 1-cyanoethyl-2-phenyl-4,5-di- (cyanoethoxymethyl) imidazole, N- (2-methylimidazolyl-1-ethyl) urea, N, N′-bis- (2-methylimidazolyl-1-ethyl) urea, 1- (cyanoethylaminoethyl) -2-methylimidazole, N, N ′ -[2-Methylimidazolyl- (1) -ethyl] -aziboyldiamide, N, N '-[2- Tylimidazolyl- (1) -ethyl] -dodecandioyldiamide, N, N ′-[2-methylimidazolyl- (1) -ethyl] -eicosanedioyldiamide, 2,4-diamino-6- [2′- Methylimidazolyl- (1) ′)-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1) ′]-ethyl-s-triazine, 1-dodecyl-2-methyl Examples include -3-benzylimidazolium chloride and 1,3-dibenzyl-2-methylimidazolium chloride.

When the crosslinking site-containing monomer is a monomer having an epoxy group, the vulcanization accelerator includes a curing agent for epoxy resin, such as pyrolysis ammonium salt, organic acid, acid anhydride, amines, sulfur and sulfur compounds. Etc. can be used.

The rubber composition for vulcanization can be vulcanized using a vulcanization accelerator without using a vulcanizing agent. As the vulcanization accelerator, a quaternary ammonium salt or a quaternary phosphonium salt can also be used. Examples of the quaternary ammonium salt include tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, n-dodecyltrimethylammonium chloride, n-dodecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, cetyldimethylammonium. Examples include chloride, 1,6-diaza-bicyclo (5.4.0) undecene-7-cetylpyridium sulfate, trimethylbenzylammonium benzoate, and the like. Examples of the quaternary ammonium salt include triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, tricyclohexylbenzylphosphonium chloride, tricyclohexylbenzylphosphonium bromide and the like.

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), 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. By including the compound (a2), the vulcanization characteristics of the rubber composition for vulcanization can be improved.

DBU salt and DBN salt include DBU or DBN carbonate, long chain aliphatic carboxylate, aromatic carboxylate, orthophthalate, p-toluenesulfonate, phenol salt, phenol resin salt, naphthoate Octylate, oleate, formate, phenol novolak 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 (a2) is a 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.

More preferably, the compound (a2) is 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride and 1,8-diazabicyclo (5.4.0) undecene. It is at least one compound selected from the group consisting of -7 formate. Particularly preferred is 8-benzyl-1,8-diazabicyclo (5.4.0) -7-undecenium chloride.

As the compound (a2), two or more of the above compounds may be used in combination.

It is preferable that a compound (a2) is 0.5 mass part or more with respect to 100 mass parts of acrylic rubber (a1). More preferably, it is 1.0 part by mass or more. When there is too little compound (a2), there exists a possibility that adhesive force may not be enough.
The compound (a2) is preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, and 3.5 parts by mass or less with respect to 100 parts by mass of the acrylic rubber (a1). More preferably, it is particularly preferably 2.0 parts by mass or less.

The rubber composition for vulcanization is one of the preferred forms containing magnesium oxide (a3). The laminated body which has a specific structure of this invention has more excellent adhesiveness by including magnesium oxide (a3).
The blending amount of magnesium oxide (a3) is preferably 3 to 20 parts by mass, more preferably 3 to 15 parts by mass, particularly 100 parts by mass of acrylic rubber (a1) from the viewpoint of adhesiveness and rubber physical properties. Preferably it is 5-10 mass parts.

It is also one of preferable forms that the rubber composition for vulcanization also contains 0 to 20 parts by mass of magnesium oxide (a3) with respect to 100 parts by mass of the acrylic rubber (a1).
Conventionally, in order to bond fluororubber and acrylic rubber, it has been considered necessary to add magnesium oxide to a vulcanizing rubber composition for forming a rubber layer.
However, in the laminate of the present invention, the vulcanized rubber composition contains the compound (a2) and the iron dithiocarbamate (a4), so that the content of magnesium oxide in the vulcanized rubber composition is small or added. Even when the rubber composition for vulcanization does not contain magnesium oxide, a firmly bonded vulcanized laminate can be obtained.
When content of magnesium oxide (a3) exceeds 20 mass parts, there exists a possibility that fluidity | liquidity, a dispersibility, and acid resistance may fall. As for content of magnesium oxide (a3), 0-15 mass parts is more preferable, Most preferably, it is 0-10 mass parts.

The rubber composition for vulcanization preferably further contains 0 to 5 parts by mass of magnesium oxide (a3) with respect to 100 parts by mass of the acrylic rubber (a1). As a result of intensive studies by the present inventors, the content of magnesium oxide (a3) is 5 parts by mass or less with respect to 100 parts by mass of the unvulcanized acrylic rubber (a1), thereby having particularly excellent acid resistance. It has been found that a vulcanized laminate can be obtained.
From the viewpoint of more excellent acid resistance, the content of magnesium oxide (a3) is more preferably less than 5 parts by mass, further preferably 3 parts by mass or less, and particularly preferably less than 3 parts by mass. Most preferably, it does not contain magnesium oxide (a3).

The rubber composition for vulcanization contains iron dithiocarbamate (a4). In addition to the compound (a2), the rubber composition for vulcanization further contains iron dithiocarbamate (a4), whereby the laminate having strong adhesion between the fluororesin layer (B) and the rubber layer (A). Is obtained.

As iron dithiocarbamate (a4), iron salt of dimethyldithiocarbamate (FeMDC), iron salt of diethyldithiocarbamate, iron salt of diisopropyldithiocarbamate, iron salt of dibutyldithiocarbamate, iron salt of dibenzyldithiocarbamate, piperazine dithio Examples include carbamate iron salts.

The compounding amount of iron dithiocarbamate (a4) is preferably 0.1 to 7.0 parts by weight, more preferably 0.3 to 5.0 parts by weight, particularly preferably 100 parts by weight of acrylic rubber (a1). 0.5 to 3.0 parts by mass.
If the amount of iron dithiocarbamate (a4) is too small, the fluororesin layer (B) and the rubber layer (A) may not be sufficiently bonded. In addition, physical properties of vulcanized rubber tend to deteriorate. When there is too much iron dithiocarbamate (a4), the tendency for unvulcanized physical properties to worsen is seen.

The rubber composition for vulcanization may contain a metal salt of carbamic acid other than iron dithiocarbamate (a4). Examples of carbamic acid metal salts other than iron dithiocarbamate (a4) include dimethyldithiocarbamate zinc salt (ZnMDC), diethyldithiocarbamate zinc salt (ZnEDC), dibutyldithiocarbamate zinc salt (ZnBDC), and ethylphenyldithiocarbamate. Zinc salt (ZnEPDC), zinc salt of N-pentamethylenedithiocarbamate, zinc dithiocarbamate such as zinc salt of dibenzyldithiocarbamate, copper dithiocarbamate such as copper salt of dimethyldithiocarbamate (CuMDC), sodium salt of dimethyldithiocarbamate (NaMDC), sodium salt of diethyldithiocarbamate (NaEDC), sodium salt of dibutyldithiocarbamate (NaBDC), tellurium salt of diethyldithiocarbamate (Te DC), and the like. These may be used alone or in combination of two or more.

Although the compounding quantity of carbamic acid metal salt other than iron dithiocarbamate (a4) is not specifically limited, For example, 0.5-3.0 mass parts is preferable with respect to 100 mass parts of acrylic rubber (a1).

The rubber composition for vulcanization preferably further contains at least one dithiocarbamate (a5) selected from the group consisting of zinc dithiocarbamate and copper dithiocarbamate. In addition to the iron dithiocarbamate (a4), by using the dithiocarbamate (a5) in combination, the fluororesin layer (B) and the rubber can be used even when the content of iron dithiocarbamate (a4) is small. A laminate with strong adhesion to the layer (A) is obtained.
Although the compounding quantity of the at least 1 sort (s) of dithiocarbamate (a5) selected from the group which consists of zinc dithiocarbamate and copper dithiocarbamate is not specifically limited, For example, it is 0.00 with respect to 100 mass parts of acrylic rubber (a1). 5-3.0 mass parts is preferable.

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 (1):
_{Mg x Zn y Al z (OH} ) 2 (x + y) +3 z-2 CO 3 · wH 2 O (1)
(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 a general formula ( 2):
[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (2)
(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 (1) include Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ .wH ₂ O. Further, the following general formula (3) included in the general formula (1):
_{Mg x Al y (OH) 2x} + 3y-2 CO 3 · wH 2 O (3)
(Where x is 1 to 10, y is 1 to 10, and w is a positive integer). In more specific _{examples, 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 (2) 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.

The rubber composition for vulcanization may further contain another resin in order to give the rubber layer (A) different properties from the acrylic rubber (a1). 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 the acrylic rubber (a1).

In the present invention, the usual additives to be blended with a general vulcanizing rubber composition, for example, fillers, processing aids, plasticizers, softeners, anti-aging agents, coloring agents, 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 fluororesin layer (B) which is the object of the present invention.

Fillers include basic silica, acidic silica, zinc oxide, calcium oxide, titanium oxide, aluminum oxide and other metal oxides; magnesium hydroxide, aluminum hydroxide, calcium hydroxide and other metal hydroxides; magnesium carbonate, Carbonates such as aluminum carbonate, calcium carbonate and barium carbonate; silicates such as magnesium silicate, calcium silicate, sodium silicate and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; synthetic hydrotals Sites, metal sulfides such as molybdenum disulfide, iron sulfide, copper sulfide; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, quartz fine powder , Zinc white, talc, mica powder, wollastonite 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; Examples thereof include silicone oils, silicone polymers, low molecular weight polyethylene, phthalates, phosphates, rosin, (halogenated) dialkylamine, (halogenated) dialkyl sulfone, and surfactants.

Examples of plasticizers include epoxy resins, phthalic acid derivatives and sebacic acid derivatives, softeners such as lubricating oils, process oils, coal tar, castor oil, calcium stearate, and anti-aging agents such as phenylenediamines and phosphines. Fate, quinoline, cresol, phenol, dithiocarbamate metal salt and the like.

The rubber composition for vulcanization is prepared by kneading acrylic rubber (a1), compound (a2), and other additives such as iron dithiocarbamate (a4) and, if necessary, magnesium oxide (a3). The

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.

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 from the viewpoint of fuel barrier properties, and is at least one selected from the group consisting of polychlorotrifluoroethylene (PCTFE) and a CTFE copolymer. More preferred.

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)
A copolymer unit derived from at least one monomer selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, vinyl chloride, and vinylidene chloride It is preferable. Further, the CTFE copolymer is more preferably a perhalopolymer.

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 copolymerized 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. Perhalopolymers are usually difficult to adhere to acrylic rubber, but according to the configuration of the present invention, even if the fluororesin layer is a layer made of perhalopolymer, the adhesion between the fluororesin layer and the rubber layer is 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.

“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 addition of the monomer (α) in 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 (in the formula, , Rf ¹ is a perfluoro (alkyl vinyl ether) (PAVE) 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), ₂ = CF—OCH ₂ —Rf ² (wherein Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) and the like. Nyl monomer and at least one selected from the group consisting of alkyl perfluorovinyl ether derivatives are preferable, and at least one selected from the group consisting of PAVE and HFP is more preferable.

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

The ratio of CTFE units to TFE units in the CTFE copolymer is 85 to 10 mol% of TFE units relative to 15 to 90 mol% of CTFE units, and more preferably 20 to 90 mol% of CTFE units. And the TFE unit is 80 to 10 mol%. Moreover, what is comprised from 15-25 mol% of CTFE units and 85-75 mol% of TFE units is also 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%, it tends to be inferior in moldability, environmental stress crack resistance and fuel crack resistance, and if it exceeds 10 mol%, low fuel permeability, heat resistance, It tends to be inferior in mechanical properties.

Most preferably, the fluoropolymer (b1) is PCTFE or CTFE-TFE-PAVE copolymer. The CTFE-TFE-PAVE copolymer is a copolymer consisting essentially of CTFE, TFE and PAVE. In the PCTFE and CTFE-TFE-PAVE copolymers, there are no hydrogen atoms directly bonded to the carbon atoms constituting the main chain, and the dehydrofluorination reaction does not proceed. Therefore, the conventional adhesion improving method using the unsaturated bond formed in the fluoropolymer by the dehydrofluorination reaction cannot be applied.

Examples of PAVE include perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (butyl vinyl ether), among others, PMVE, PEVE. And at least one selected from the group consisting of 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) -) and the like, include 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, carbamoyl group, hydroxyl group, carboxyl group , A carbonate group, a carboxylic acid halide group, and an acid anhydride bond are preferable, and an amide group, a carbamoyl group, a hydroxyl group, a carbonate group, a carboxylic acid halide group, and an acid anhydride bond are more preferable.

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, the conditions such as temperature and pressure, the polymerization initiator and other additives can be appropriately set according to the composition and amount of the fluoropolymer (b1).

Although melting | fusing point of a fluoropolymer (b1) is not specifically limited, It is preferable that it is 160-270 degreeC.

The molecular weight of the fluoropolymer (b1) is preferably in a range where the resulting laminate can exhibit good mechanical properties, low fuel permeability, and the like. For example, when melt flow rate (MFR) is used as an index of molecular weight, MFR at an arbitrary temperature in the range of about 230 to 350 ° C., which is a general molding temperature range of fluoropolymers, is 0.5 to 100 g / 10 min. It is preferable. More preferably, it is 2-50 g / 10min, More preferably, it is 5-35g / 10min.

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). The MFR uses a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), for example, the weight of the polymer flowing out per unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 297 ° C. and 5 kg (g) ) Can be measured.

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

The fluororesin layer (B) in the laminate of the present invention preferably has a fuel permeability coefficient of 1.0 g · mm / m ² / day or less when the laminate is used as a material around the fuel, and 0.6 g -It is more preferable that it is below mm / m < ² > / day, and it is still more preferable that it is below 0.4g * mm / m < ² > / day.

The fuel permeation coefficient is obtained by incorporating a sheet obtained from the resin to be measured into a fuel permeation coefficient measuring cup charged with a mixed solvent of isooctane / toluene / ethanol 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 ° 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, a laminate excellent in impact resistance and strength can be provided.

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 a blend of various fillers such as inorganic powder, glass fiber, carbon powder, carbon fiber, and metal oxide, as long as the performance is not impaired depending on the purpose and application. There may be.

For example, in order to further reduce fuel permeability, smectite-based lamellar 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 single 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 is described in, for example, metal powder such as copper and nickel; metal fiber such as iron and stainless steel; carbon black, carbon fiber, and Japanese Patent Laid-Open No. 3-174018 Carbon fibrils and the like.

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. Further, the rubber layer (A) may be laminated on one side of the fluororesin layer (B).

The rubber layer (A) and the fluororesin layer (B) can be 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 in which the rubber layer (A) and the fluororesin layer (B) are separately molded and then laminated by means such as pressure bonding, a molding method of a fluoropolymer and a molding method of a rubber composition for vulcanization can be employed. .

The rubber layer (A) can be molded by various methods such as sheet-like, tube-like, etc. by subjecting the rubber composition for vulcanization to 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, various coating devices, etc., 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.

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, the rubber layer (A) and the fluororesin layer (B), which are unvulcanized molded bodies, can be laminated at the same time, and therefore a step of closely adhering the rubber layer (A) and the fluororesin layer (B) is particularly necessary. In addition, it is suitable for obtaining strong adhesion in the subsequent vulcanization step.

The laminate of the present invention may be a laminate of an unvulcanized rubber layer (A) and a fluororesin layer (B), but by further vulcanizing the unvulcanized laminate, Interlayer adhesion can be obtained.

That is, the present invention is obtained by vulcanizing the unvulcanized laminate of the present invention, and the rubber layer (A1) obtained by vulcanizing the rubber layer (A) and the fluororesin layer (B) are vulcanized and bonded. The present invention also relates to a laminate (hereinafter also referred to as “vulcanized laminate”).

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 the unvulcanized laminate in a relatively short time (vulcanization is also occurring), and then vulcanizing over a long time There is a way to do it. 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 period of time is a rubber layer (A) and a fluororesin layer (B) in the pretreatment. Since the rubber layer (A) has already been vulcanized in the pretreatment and the shape is stabilized, various methods for holding the laminate in the subsequent vulcanization are selected. This is preferable.

The conditions for the vulcanization treatment are not particularly limited and can be performed under normal conditions, but at 160 to 170 ° C. for 10 to 80 minutes, 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 ° C. over 20 to 45 minutes.

In the obtained vulcanized laminate, the vulcanized rubber layer (A1) and the fluororesin layer (B) are vulcanized and bonded, and a strong interlayer adhesion is generated.

The laminate of the present invention (unvulcanized laminate and vulcanized laminate) may have a two-layer structure including a rubber layer (A, A1, hereinafter, the rubber layer (A) is representative) and a fluororesin layer (B). Alternatively, a three-layer structure such as (A)-(B)-(A) or (B)-(A)-(B) may be used. Furthermore, it may be a multilayer structure of three or more layers in which a polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B) is bonded, and (A)-(B)-(C) 3 A layered structure is also a preferred form. In the laminate of the present invention, the rubber layer (A) is laminated on one side of the fluororesin layer (B), and the polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B) is laminated on the other side. The rubber layer (A) may be laminated on both sides of the fluororesin layer (B), and the polymer layer (C) other than the fluororesin layer (B) may be further laminated on both sides or one side thereof. .

The polymer layer (C) may be a rubber layer (C1) other than the rubber layer (A). Moreover, you may have a (C) layer in the one side or both sides of the outer side of the (A) layer of (A)-(B)-(A).

Examples of the material for the rubber layer (C1) include rubbers other than acrylic rubber, and may be fluororubber or non-fluororubber. From the viewpoint of fuel resistance and fuel barrier properties, fluororubber is preferable, and from the viewpoint of good cold resistance and cost, non-fluorine rubber is preferable.

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

The non-fluorine rubber is preferably a diene rubber from the viewpoint of good heat resistance, oil resistance, weather resistance and extrusion moldability. More preferred is NBR or HNBR. The polymer layer (C) is preferably made of acrylonitrile-butadiene rubber or a hydride thereof.

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

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 an 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.

The three-layer structure (A)-(B)-(C1) is preferably a layer made of NBR or HNBR as the rubber layer (C1).

Further, the fuel pipe has a (A)-(B)-(C1) type structure, a fluororubber layer is provided as the rubber layer (C1), and the rubber layer (C1) is used as an inner layer of the pipe. Improved low fuel permeability.

(3) Three-layer structure of resin layer-rubber layer (A) -resin layer (B)-(A)-(B) The inner and outer resin layers are the same type, but different types It may be.

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

(5) Four-layer structure or more In addition to the three-layer structure of (2) to (4), any rubber layer (A) or (C1) or resin layer (B) may be further laminated depending on the purpose. . Moreover, a layer such as a metal foil may be provided, or an adhesive layer may be interposed other than the interlayer between the rubber layer (C) 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.
In addition, for the purpose of improving pressure resistance, a reinforcing layer such as a reinforcing yarn may be provided as appropriate.

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, weather resistance, and ozone resistance. Further, it can sufficiently withstand use under severe conditions and can be used in various applications.

For example, automotive engine main body, main motion system, valve 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, steam resistance, non-contact type and contact type packings (self-sealing) such as basic electric parts, control system electric parts, equipment electric parts, etc. (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 the main motion system.

Valve stem seals for valve valves and engine valves.

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

Fuel seals, fuel pump oil seals, diaphragms, valves, etc. Filler (neck) hoses, fuel supply hoses, fuel return hoses, vapor (evaporation) hose fuel hoses, fuel tank in-tank hoses, filler seals, tanks Packing, in-tank fuel pump mount, fuel pipe tube body and connector O-ring, etc. 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. Especially, it is suitable as an in-tank hose of a fuel hose and a fuel tank.

Intake / exhaust manifold manifold manifold packing, exhaust manifold packing, EGR diaphragm, control hose, emission control hose, BPT diaphragm, AB valve after-burn prevention valve seat, throttle, 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, etc. AT transmission oil hoses, ATF hoses, O-rings, packings, etc.

Steering power steering oil hose, etc.

Brake system oil seal, O-ring, packing, brake oil hose, etc., master back atmospheric valve, vacuum valve, diaphragm, etc., master cylinder piston cup (rubber cup), caliper seal, boots, etc.

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

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

Car equipment air conditioner O-ring, packing, cooler hose, exterior wiper blade, etc.

In addition to automobiles, for example, in 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, OA equipments, general industrial parts Packing, O-ring, hose, sealing material, die Fram is suitable valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, the use of the roll blade or the like of the 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 flavor and 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 is particularly preferably used as a tube or a hose. That is, the laminate is preferably a tube or a hose. Among tubes, it can be suitably used as a fuel piping tube or hose for automobiles in terms of heat resistance and low fuel permeability.

The fuel pipe made of the laminate in the present invention can be produced by a usual method and is not particularly limited.

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

Hereinafter, it describes about the fluororesin used in an Example and a comparative example, and its measuring method.

(1) 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.

(2) 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 a load of 297 ° C. and 5 kg was measured.

(3) Measurement of single layer fuel permeability coefficient Each resin pellet of fluororesin (1) is placed in a 120 mm diameter mold and set in a press machine heated to 300 ° C., and melted at a pressure of about 2.9 MPa. A sheet having a thickness of 0.15 mm was obtained by pressing. 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 permeation coefficient (g · mm / m ² / day) was calculated from the change in mass per hour, the surface area of the sheet in the wetted part, and the thickness of the sheet.

Hereinafter, the fluororesins in Examples and Comparative Examples are shown in Table 1 below.

(Rubber compositions 1 to 13 for vulcanization)
The materials shown in Table 2 below were kneaded using an 8-inch open roll whose temperature was adjusted to 40 ° C. to obtain sheet-like rubber compositions for vulcanization 1 to 13 having a thickness of about 3 mm. In addition, each numerical value which shows the compounding quantity of Table 2 represents a mass part.
Further, for the rubber compositions 1 to 13 for vulcanization, the maximum torque value (M _H ) and the minimum torque at 160 ° C. using a curast meter type II (model number: JSR curast meter, manufactured by JSR). The value (M _L ) was measured to determine the induction time (T ₁₀ ) and the optimum vulcanization time (T ₉₀ ). The measurement results are shown in Table 2. T ₉₀ is {(M _H ) − (M _L )} × 0.9 + M _L , T ₁₀ is the time for {(M _H ) − (M _L )} × 0.1 + M _L , M _H and _{M L} is the value measured according to JIS K 6300-2.

(Examples 1-11, Comparative Examples 1-2)
A sheet of the rubber composition for vulcanization shown in Table 2 having a thickness of about 3 mm and a fluororesin sheet having a thickness shown in Table 1 are overlapped, and a resin film having a width of about 10 to 15 mm (with a thickness of 10 μm) at one end. A release film) is sandwiched between both sheets, inserted into a mold with a metal spacer so that the resulting sheet has a thickness of 2 mm, and pressed at 170 ° C. for 15 minutes to form a sheet-like laminate. Got. The obtained laminate was cut into strips each having a width of 10 mm, a length of 40 mm, and a set of 3 pieces, and a release film was peeled off to prepare a test piece that was grasped. About this test piece, according to the method as described in JIS-K-6256 (adhesion test method of crosslinked rubber) using an autograph (manufactured by Shimadzu Corporation, AGS-J 5 kN), and 50 mm / 25 ° C. A peeling test was conducted at a tensile rate of min, and the peeling mode was observed and evaluated according to the following criteria. The obtained results are shown in Table 2.

(Adhesion evaluation)
A: The rubber layer or the fluororesin layer was destroyed at the interface of the laminate and could not be peeled off at the interface.
X: Peeled relatively easily at the interface of the laminate.

The materials shown in Table 2 are as follows.
Nipol AR31: Acrylic rubber (ACM), Nippon Zeon's stearic acid 50S: Stearic acid, Shin Nippon Rika's seast SO: Carbon black (FEF black), Tokai Carbon's Noxeller PZ: Zinc dimethyldithiocarbamate, emerging in Ouchi Noxeller TTFE made by Kagaku Kogyo Co., Ltd .: Ferric dimethyldithiocarbamate, Noxeller BZ made by Ouchi Shinsei Kagaku Kogyo Co., Ltd. Zinc dibutyldithiocarbamate, Noxeller TTCU made by Ouchi Shin Kagaku Kogyo Co., Ltd. Noxeller TTTE: Tellurium diethyldithiocarbamate, Noxeller PX: N-ethyl-N-phenyldithiocarbamate zinc, Ouchi Shinsei Chemical Co., Ltd. Kyowamag # 150: MgO, Kyowa Chemical Co., Carplex 1 20: basic silica, DSL Japan Co. DBU-B: DBU benzyl chloride salt, manufactured by Wako Pure Chemical Industries, Ltd. Sukonokku 7: phthalic anhydride, manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.

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, and steam resistance. Main motor system, valve system, lubrication / cooling system, fuel system, intake / exhaust system, drive transmission system, chassis steering system, brake system, etc. Gaskets that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance, and non-contact type and contact type packings (self-seal packing, piston ring, split ring type packing) , Mechanical seals, oil seals, etc.), bellows, diaphragms, hoses, tubes, electric wires, etc.

Claims (13)

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 acrylic rubber (a1),
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, and iron dithiocarbamate (a4),
The fluororesin layer (B) is a layer formed from a fluoropolymer composition,
The fluoropolymer composition comprises a fluoropolymer (b1) having a copolymer unit derived from chlorotrifluoroethylene. The laminated body according to claim 1, wherein the rubber composition for vulcanization further contains magnesium oxide (a3). The laminated body according to claim 1, wherein the rubber composition for vulcanization further contains 0 to 20 parts by mass of magnesium oxide (a3) with respect to 100 parts by mass of the acrylic rubber (a1). The laminated composition according to claim 1, 2 or 3, wherein the rubber composition for vulcanization is such that the compound (a2) is 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the acrylic rubber (a1). body. The laminate according to claim 1, 2, 3, or 4, wherein the fluoropolymer (b1) is a chlorotrifluoroethylene-tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer. The laminate according to claim 1, 2, 3, 4 or 5, wherein the rubber layer (A) is laminated on both sides of the fluororesin layer (B). The rubber layer (A) is laminated on both sides of the fluororesin layer (B), and the polymer layer (C) other than the fluororesin layer (B) is further laminated on both sides or one side thereof. The laminate according to 4 or 5. The rubber layer (A) is laminated on one side of the fluororesin layer (B), and the polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B) is laminated on the other side. The laminate according to 3, 4, 4 or 5. The laminate according to claim 7 or 8, wherein the polymer layer (C) comprises acrylonitrile-butadiene rubber or a hydride thereof. The laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the fluororesin layer (B) is laminated on both sides of the rubber layer (A). Obtained by vulcanizing the laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
A laminate in which a rubber layer (A1) obtained by vulcanizing a rubber layer (A) and a fluororesin layer (B) are bonded by vulcanization. It is a tube or a hose, The laminated body of Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. It is a fuel piping tube or hose for motor vehicles, The laminated body of Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.