JPH10264314A - Laminate and hose made thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate and a hose wherein a lead compound is not used as a vulcanizing system, adhesion between fluororubber or fluroresin and epichlorohydrin is raised, and the laminate and the hose are made to have further effective monolithic structures. SOLUTION: In a laminate and a hose which are constituted by containing at least a first layer 2 composed of fluororubber or fluororesin, and a second layer 4 composed of epichlorohydrin rubber which is laminated in contact with the first layer, the second layer 4 is composed of a rubber composition wherein epichlorohydric rubber material is used as its base constituent, and 0.1-5 pts.wt. of a vulcanizing agent composed of 2,3-diemercapto quinoxaline derivative, 0.1-5 pts.wt. of 1.8-diazabicyclo (5, 4, 0) undecene-7 salt, and 1-20 pts.wt. pf hydrotalcite group are blended in its 100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate and a hose comprising the same, and more particularly, to a laminate having excellent adhesion between a first layer made of fluororubber or fluororesin and a second layer made of epichlorohydrin rubber, and a laminate thereof. The present invention relates to a hose composed of such a laminated body, particularly to a fuel hose.

[0002]

2. Description of the Related Art Hitherto, a laminate formed by laminating and integrating a plurality of layers has been used in various applications, and a first layer made of a fluororubber or a fluororesin and a first layer made of a layer in contact with the first layer are laminated. The same applies to a laminate including at least a second layer made of epichlorohydrin rubber. Such a laminate is characterized by utilizing the properties of the material constituting the layer to be laminated and integrated, particularly as a hose, especially the excellent fuel barrier properties of the fluororubber or fluororesin constituting the first layer ( Utilizing fuel impermeability), the fuel hose has been used as a fuel hose having the first layer as the innermost layer.

However, in order to obtain such a laminate, it is necessary to laminate and integrate the first layer made of fluororubber or fluororesin and the second layer made of epichlorohydrin-based rubber. Adhesive technology is required, but because these fluororubbers and fluororesins have poor adhesion to other materials, various studies are being continued today to improve them. However, this is the current situation. However, any of the bonding techniques proposed up to now have too much emphasis on the adhesiveness with fluororubber and fluororesin, and the compression set of epichlorohydrin rubber to be bonded, sour gasoline resistance,
Any property such as storage stability of the unvulcanized rubber was sacrificed.

Further, at present, when vulcanizing and bonding fluorocarbon rubber or fluorocarbon resin to epichlorohydrin rubber, vulcanizing systems of epichlorohydrin rubber generally include ethylenethiourea as a vulcanizing agent and an acid acceptor. A combination system with a lead compound such as leadtan is used, and calcium hydroxide, 1,8-diazabicyclo (5,4,
0) Undecene-7 salt, onium salt, etc. are added to achieve adhesion with fluoro rubber or fluoro resin.
It is thought that it is desirable to control the disposal of lead compounds used in the world in recent years with increasing global safety, and it is desirable not to use them. Immediate development is desired.

[0005] For this reason, the present inventors have conducted various studies on alternative vulcanization systems that do not use lead compounds in place of the vulcanization systems that have been conventionally used. By this, the fact that the adhesiveness between the fluororubber or fluororesin and epichlorohydrin-based rubber is remarkably enhanced, and that excellent results such as compression set and sour gasoline resistance are obtained is found, and the present invention is completed. It was reached.

[0006]

Accordingly, the object of the present invention is to improve the adhesiveness between a fluororubber or a fluororesin and epichlorohydrin rubber without using a lead compound in the vulcanization system, thereby achieving a more effective integration. It is another object of the present invention to provide a laminated body having a structure, and to provide a hose made of such a laminated body, particularly a fuel hose useful for fuel piping.

[0007]

According to the present invention, a first layer made of fluororubber or a fluororesin and a layer in contact with the first layer are laminated in order to solve the problem relating to the laminated body among those problems. Further, in a laminate comprising at least a second layer made of epichlorohydrin-based rubber, the second layer, using an epichlorohydrin-based rubber material as its base rubber component, based on 100 parts by weight thereof,
0.1 to 5 parts by weight of a vulcanizing agent comprising a 2,3-dimercaptoquinoxaline derivative, 0.1 to 5 parts by weight of 1,8-diazabicyclo (5,4,0) undecene-7 salt, It is characterized by being formed from a rubber composition containing 1 to 20 parts by weight of talcites.

As described above, according to the present invention, as a new vulcanization system of epichlorohydrin rubber material, 2,3-
A dimercaptoquinoxaline derivative, 1,8-diazabicyclo (5,4,0) undecene-7 salt, and a combination of hydrotalcites are used, whereby a conventional lead compound such as leadtan is obtained. Needless to say, the adhesiveness between the fluororubber or the fluorocarbon resin and the epichlorohydrin-based rubber is remarkably improved, and the lamination and integration of the first layer and the second layer are more advantageously performed. The second layer made of epichlorohydrin rubber formed by using such a vulcanization system is excellent in compression set,
In addition to being excellent in elongation set, it is also excellent in sour gasoline resistance.

The present invention also provides a hose made of the above-mentioned laminated body, which is characterized by a first layer made of fluororubber or fluororesin, In a hose having a laminated structure including at least a second layer made of epichlorohydrin rubber laminated in contact with one layer, the second layer is made of an epichlorohydrin rubber material as a base rubber component, and 100 parts by weight thereof is used. On the other hand, 0.1 to 5 parts by weight of a vulcanizing agent comprising a 2,3-dimercaptoquinoxaline derivative,
1,8-diazabicyclo (5,4,0) undecene-7
0.1 to 5 parts by weight of salt and 1 to 1 of hydrotalcites
And 20 parts by weight.

In the hose having such a configuration, the second layer made of epichlorohydrin-based rubber is excellent in compression set and extension set. This has the advantage that the sealing property can be effectively secured.

Further, the present invention provides, among the above hoses, a first layer made of fluororubber or fluororesin and a second layer made of epichlorohydrin rubber laminated in contact with the first layer. A fuel layer including at least the first layer, wherein the first layer is located inside the hose with respect to the second layer and is the innermost layer in contact with the fuel flowing through the hose.
The second layer is made of an epichlorohydrin rubber material as a base rubber component.
0.1 to 5 parts by weight of a vulcanizing agent comprising a 2,3-dimercaptoquinoxaline derivative and 0.1 to 1 part by weight of 1,8-diazabicyclo (5,4,0) undecene-7 salt
The gist of the present invention is also a fuel hose formed of a rubber composition obtained by blending 1 to 20 parts by weight of hydrotalcites with 1 to 20 parts by weight of a hydrotalcite.

In such a fuel hose, the second layer made of epichlorohydrin rubber is formed from the rubber composition using the vulcanization system according to the present invention described above, so that its sour gasoline resistance is improved. As a result, it has an effective fuel barrier property (fuel impermeability) together with the first layer (fluororubber or fluororesin) that constitutes the innermost layer, and thus has excellent functions for fuel piping. Is played.

According to one of the advantageous embodiments of the laminate, the hose and the fuel hose according to the present invention as described above, the rubber composition comprises at least one of a metal oxide and a metal hydroxide. Is contained in a proportion of 0.1 to 3 parts by weight, preferably 0.3 to 1.5 parts by weight per 100 parts by weight of the epichlorohydrin rubber material. By including such a metal oxide or metal hydroxide, the heat resistance of the epichlorohydrin-based rubber can be advantageously improved.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A laminate, a hose or a fuel hose according to the present invention comprises a first layer made of a fluororubber or a fluororesin and an epichlorohydrin rubber laminated in contact with the first layer. And a second layer comprising at least not only the two layers, but also a third layer and a fourth layer made of a suitable rubber or resin. It is also possible to adopt a configuration in which a plurality of layers are laminated and integrated on one or both sides of a laminated structure composed of the first layer and the second layer.

However, in the case of a fuel hose, as shown in FIGS. 1 and 2, the innermost layer 2 of the hose is made of fluoro rubber or fluoro resin and is used as the first layer. Outside the innermost layer 2, the outer layer 4 is made of epichlorohydrin-based rubber and serves as a second layer. In the example shown in FIG. 2, an outer tube layer 6 made of epichlorohydrin rubber or the like is further integrally formed on the outer side of the outer layer 4, and a gap between the outer layer 4 and the outer tube layer 6 is formed. In addition, a fiber reinforcing layer 8 similar to the conventional one is integrally formed.

The fluororubber or fluororesin that provides the first layer (2) constituting such a laminate or hose or fuel hose is not particularly limited, and any known one can be used. Can be used, but as the fluororubber, copolymers of vinylidene fluoride and propylene hexafluoride, terpolymers of vinylidene fluoride, propylene hexafluoride and ethylene tetrafluoride, vinylidene fluoride Copolymer of vinylidene trifluoride, terpolymer of vinylidene fluoride, perfluoromethyl ether and ethylene tetrafluoride, copolymer of ethylene tetrafluoride and propylene, vinylidene fluoride and tetrafluoroethylene A terpolymer of fluorinated ethylene and propylene, a blend of polyvinylidene fluoride and acrylic rubber, and the like are preferably used. Examples of the fluororesin include a terpolymer (THV) of vinylidene fluoride, propylene hexafluoride and ethylene tetrafluoride, a copolymer of ethylene and ethylene tetrafluoride, and a copolymer of propylene hexafluoride and tetrafluoroethylene. Copolymers with ethylene fluoride, polyvinylidene fluoride, polytetrafluoroethylene, etc., are preferred, and terpolymers (THV) of vinylidene fluoride, propylene hexafluoride and ethylene tetrafluoride are preferred. Used for

In the present invention, the epichlorohydrin-based rubber material as the base rubber component for providing the second layer (4) laminated and integrated with the first layer (2) is not only a homopolymer of epichlorohydrin but also epichlorohydrin. , Ethylene oxide, propylene oxide, copolymers with other epoxides such as allyl glycidyl ether, for example, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer And a terpolymer of epichlorohydrin-propylene oxide-allyl glycidyl ether and a terpolymer of epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether. It would be used.

The present invention relates to a vulcanizing system for such an epichlorohydrin rubber material, which comprises a 2,3-dimercaptoquinoxaline derivative, 1,8-diazabicyclo (5,4,0) undecene-7 salt, A combination with hydrotalcites is used.
The vulcanizing agent 2,3-dimercaptoquinoxaline derivative is represented by the following chemical formula 1:

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and specifically, quinoxaline-2, 3-dithiocarbonate, 6-methylquinoxaline-2,3-
Dithiocarbonate, 6-isopropylquinoxaline-
Examples thereof include 2,3-dithiocarbonate and 5,8-dimethylquinoxaline-2,3-dithiocarbonate. Among them, 6-methylquinoxaline-2,3-
Dithiocarbonate will be used advantageously. The 2,3-dimercaptoquinoxaline derivative is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the above-mentioned epichlorohydrin rubber material (base rubber component). Parts will be used. If the amount used is less than 0.1 part by weight, vulcanization becomes difficult, and if it exceeds 5 parts by weight, problems such as scorch may occur. It is.

Further, 1,8-
Diazabicyclo (5,4,0) undecene-7 (DB
The salts of U) are generally of the following formula 2:

Embedded image (Where X ⁻ is an acid radical of a carboxylic acid or a phenol resin), specifically, naphthoic acid,
Carboxylic acids such as 2-hydroxynaphthoic acid, sorbic acid, 2-ethylhexylic acid, gallic acid, p-hydroxybenzoic acid, and cinnamic acid, and DBU salts of phenolic resins, and in particular, in the present invention, Naphthoic acid or a DBU salt of a phenolic resin is preferably used. The amount of the DBU salt used is 0.1 to 5 parts by weight based on 100 parts by weight of the epichlorohydrin-based rubber material. If the amount is too small, vulcanization becomes difficult. If the amount is too large, problems such as scorching may be caused.

Further, the hydrotalcites constituting the vulcanization system employed in the present invention are generally represented by the following formula 3:

Embedded image(However, M₁Is a group consisting of Mg, Ca, Sr and Ba
At least one selected divalent metal;_TwoIs Z
bivalent gold selected from the group consisting of n, Cd, Pb and Sn
M represents Al, Fe, Cr, C
o represents a trivalent metal such as In or In, and A represents halogen, nitrate,
Carbonate, sulfate, ferrocyanate, acetate, oxalate,
It represents an n-valent anion such as salicylate, and a and b are
0 + 10, a + b = x, and
Where x is 1 to 10, y is 1 to 5, and w is a real number.
Shown, for example, Mg_4.5 Al_Two (O
H)₁₃CO_Three ・ 3.5H_Two O, Mg_4.5 Al_Two (OH)
₁₃CO_Three , Mg_Four Al_Two (OH)₁₂CO_Three ・ 3.5H_Two 
O, Mg₆ Al_Two (OH)₁₆CO_Three ・ 4H_Two O, Mg_Five 
Al_Two (OH) ₁₄CO_Three ・ 4H_Two O, Mg_Three Al_Two (O
H)_TenCO_Three ・ 1.7H_Two O, Mg_ThreeZnAl_Two(O
H)₁₂CO_Three・ WH_TwoO, Mg_ThreeZnAl_Two(OH)₁₂
CO_ThreeAnd the like. These hydrotal
Sites may be used alone or as a mixture of two or more.
Rukoto can. Also, such hydrotalcite
Are 100 parts by weight of the epichlorohydrin rubber material.
On the other hand, it is used in the range of 1 to 20 parts by weight.
If the amount used is too small, the vulcanization will be sweet, while
If the amount used exceeds the above range, the elongation at break is small.
Cause problems such as

The epichlorohydrin rubber composition using such a vulcanized system may contain various anti-aging agents, fillers, reinforcing agents, and the like employed in the technical field, if necessary.
A plasticizer, a processing aid, a pigment, a flame retardant, and the like are appropriately compounded. Particularly, in the present invention, at least one of a metal oxide and a metal hydroxide contains an epichlorohydrin-based compound. 0.1 per 100 parts by weight of rubber material
-3 parts by weight, preferably 0.3-1.5 parts by weight, whereby properties such as heat resistance, compression set and elongation set can be further improved. In addition, this metal oxide or metal hydroxide is
If the total amount exceeds 3 parts by weight, physical properties such as sour gasoline resistance, adhesiveness, storage stability and the like will be reduced. Therefore, it is desirable to avoid excessively large amounts thereof. As such a metal oxide or metal hydroxide, an oxide or hydroxide of an alkaline earth metal such as magnesium or calcium is advantageously used.

In the process of manufacturing a hose including a fuel hose, one method of vulcanizing an unvulcanized hose molded product obtained by extrusion or the like using an unvulcanized rubber composition. As a known method, a lead vulcanization method in which steam vulcanization is performed in a state in which the outer surface of a hose is covered with lead is known.
As shown in the above, in the case of producing a hose in which the outermost layer of the hose is substantially the second layer, stearic acid is blended in the rubber composition that provides such an outermost layer, and the workability of rubber processing is improved. In addition to the improvement, measures will be taken to prevent lead from adhering to the outer surface of the hose and enhance the removability of the lead coating layer after vulcanization. The amount of stearic acid is reduced to 0.5 part by weight or less with respect to 100 parts by weight of the epichlorohydrin-based rubber material as the base rubber component, since the adhesiveness to the first layer is reduced when the content increases. It is desirable to stop.

In addition, the epichlorohydrin-based rubber composition according to the present invention has the following properties for the purpose of adjusting the vulcanization rate.
The addition of a known vulcanization accelerator or vulcanization retarder or the like is also appropriately employed, and each of them is selected from known ones according to the purpose.

In order to obtain a laminate or a hose and further a fuel hose according to the present invention, a first layer made of a predetermined fluororubber or fluororesin can be obtained according to a well-known ordinary lamination technique or extrusion technique. A layer (2) is formed, and a second layer (4) composed of epichlorohydrin rubber as described above is directly formed on the first layer by using the rubber composition described above to form a laminate. As a laminate, further formed in a molded article as a hose, and then vulcanized according to normal vulcanization techniques,
Further, if necessary, prior to the formation of the first layer and the second layer, or at the same time as the formation thereof, or after the formation thereof, further other layers are formed in the same manner as in the related art. A laminated body or a hose having the laminated structure described above is obtained.

[0025]

EXAMPLES Hereinafter, some examples of the present invention will be described to clarify the present invention more specifically. However, the present invention imposes some restrictions by the description of such examples. It goes without saying that you don't receive anything. In addition, the present invention, in addition to the following examples, in addition to the above specific description, various modifications based on the knowledge of those skilled in the art, unless departing from the spirit of the present invention,
It should be understood that modifications, improvements and the like can be made.

First, the respective components shown in the following Tables 1 to 5 are blended in the amounts shown in the respective tables.
Knead evenly, Examples 1 to 12 and Comparative Examples 1 to 9
Various rubber compositions according to the above were prepared. In each table, ECO is an epichlorohydrin-ethylene oxide copolymer (Epichromer C manufactured by Daiso Corporation) as an epichlorohydrin rubber material, and GECO
Is a terpolymer of epichlorohydrin-ethylene oxide-allyl glycidyl ether as an epichlorohydrin rubber material (Epichromer CG manufactured by Daiso Corporation)
-104), DBU is 1,8-diazabicyclo (5,
4,0) undecene-7, hydrotalcite DHT-
4A is Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂
O, hydrotalcite DHT-4A-2 is Mg _4.5
Al ₂ (OH) ₁₃ CO ₃ is shown respectively. Alkamizer 4 and Alkamizer 4.2
Are Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ .w
H ₂ O (where w is a real number) and Mg ₃ ZnAl ₂
(OH) ₁₂ CO ₃ .

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

[Table 5]

Next, the various unvulcanized rubber compositions obtained above or test specimens obtained by vulcanizing the same were evaluated for their unvulcanized properties (scorch properties) and vulcanized properties (normal conditions) according to the following evaluation methods. Physical properties), compression set, extension set, heat resistance, and sour gasoline resistance were evaluated, and the results are shown in Tables 6 to 10 below.

-Unvulcanized physical property (scorch property)-This unvulcanized physical property is evaluated for storage stability, and is based on the method described in JIS-K-6300.
Each rubber composition was evaluated. That is, initially, after dry heat (40 ° C. × 72 hours), and after wet heat (50 ° C. × 95% R)
H × 24 hours), Mooney viscosity: ML121 ° C. (1 + 3), and scorch time (St. 5p) were measured.

-Vulcanized Physical Properties (Physical Properties at Normal State)-The initial performance of a vulcanized rubber specimen obtained by press-vulcanizing each rubber composition at 160 ° C. for 45 minutes is shown in J.
It measured according to the method of IS-K-6301.
In the table, TB indicates tensile strength (MPa), EB indicates tensile elongation at break (%), and Hs indicates JIS-A hardness, respectively.

-Compression set-Based on the method described in JIS-K-6301, the above vulcanized rubber test specimens were used under the conditions of 100 ° C x 72 hours or 120 ° C x 72 hours, respectively. ,It was measured. In Comparative Examples 1 to 5, the primary vulcanized product (16
The pressure was measured at 0 ° C. × 45 minutes for press vulcanization, and the secondary vulcanized product was further subjected to secondary vulcanization (150 ° C. × 2 hours).

-Permanent set of elongation-Using a dumbbell test piece of JIS No. 1 made of the above vulcanized rubber, drawing a 40 mm mark line, giving an elongation of 50% elongation, and applying a temperature of 135 ° C for 72 hours After aging, the test piece was removed and allowed to stand at room temperature for 30 minutes, and the strain rate (%) was calculated by the following equation. Strain rate (%) = (L ₁ −40) × 100/40 (where, L ₁ : length between marked lines after aging, mm)

-Heat resistance- According to the method described in JIS-K-6301, TB, EB and Hs of each of the vulcanized rubber test pieces after heat treatment at 120 ° C for 168 hours were measured. The initial performance obtained at the time of the measurement of the vulcanized physical properties was shown as a rate of change with respect to the physical properties. That is, in each table, ΔT
B is the change rate of the tensile strength after heat treatment with respect to the tensile strength in the vulcanized property, ΔEB is the change rate of the elongation at break after heat treatment with respect to the elongation at break, and ΔHs is the change in hardness after heat treatment with respect to the hardness in the vulcanized property. The amounts are indicated respectively.

-Sour gasoline resistance- This evaluation was performed according to the method described in JIS-K-6301. That is, after each rubber composition was molded into a sheet, it was vulcanized under the conditions of 160 ° C. × 45 minutes to obtain a tensile strength,
When measuring the elongation and the change in hardness, a dumbbell-shaped No. 3 test piece is punched from the obtained vulcanized sheet, and lauroyl peroxide is added at a ratio of 3% by weight. Immersed in FUEL-B [isooctane / toluene = 70/30 (volume%)]
Left for 2 hours. In addition, the liquid amount was set to 15 for three samples.
The volume was 0 ml. Also, when measuring the volume change rate,
Width: 20 mm, length: 50 mm, thickness: 2.00 ± 0.
Three 15 mm test pieces were immersed in 100 ml of the same FUEL-B as described above. Then, the tensile strength, elongation, hardness change, and volume change of each test piece obtained by the immersion were examined. In the table,
ΔTB is the rate of change of the tensile strength after immersion to the vulcanized property, ΔEB is the rate of change of the elongation at break after immersion to the elongation at break, ΔHs is the change in hardness after immersion to the hardness in the cured properties. The amount and ΔV indicate the rate of volume change after immersion, respectively. The appearance was also examined for the state, and the results are shown in the table.

[0039]

[Table 6]

[0040]

[Table 7]

[0041]

[Table 8]

[0042]

[Table 9] Note) NS: No scorch CB: Chuck out

[0043]

[Table 10]

As is clear from the results of Tables 6 to 10, the rubber compositions according to Examples 1 to 12 according to the present invention
It has excellent storage stability and, in addition to vulcanizate properties, compression set, elongation set, heat resistance, and sour gasoline resistance, it is recognized that it has excellent vulcanized rubber properties overall, In particular, in a vulcanized rubber obtained from a rubber composition obtained by blending a predetermined amount of magnesium oxide, magnesium hydroxide or calcium hydroxide according to Examples 6 to 12, compression set, extension set, or heat resistance. And had excellent characteristics.

Further, various rubber compositions shown in the above Tables 1 to 5 were combined with fluoro rubber (FKM) or fluoro resin (F
CP), and evaluated the results.
The results are shown in Tables 11 to 15 below. The following two types were used for FKM, and the following one type was used for FCP.

-FKM-vinylidene fluoride-hexafluoropropylene binary copolymer (Viton E430, manufactured by DuPont, USA): 10
A composition having a composition of 0 parts by weight, 13 parts by weight of SRF carbon, 3 parts by weight of MgO, and 6 parts by weight of Ca (OH) ₂ was used.

-FKM- terpolymer of vinylidene fluoride-6-propylene-fluoride-tetrafluoroethylene (Daiel G555, manufactured by Daikin Co., Ltd.): 100 parts by weight, SRF carbon: 13 parts by weight,
A composition having a composition of 3 parts by weight of MgO and 6 parts by weight of Ca (OH) ₂ was used.

-FCP-tetrafluoroethylene-hexafluoropropylene-
A vinylidene fluoride terpolymer (THV500G, manufactured by 3M, USA) was used.

[0049] Such FKM or FCP
And the epichlorohydrin-based rubber based on the above various rubber compositions has an initial adhesion after heat aging (120 ° C.).
× 72 hours) and after immersion [FUEL-D (isooctane / toluene = 40 vol% / 60 vol%), 40 ° C.
× 48 hours], the following peeling force and interface state were evaluated, and the obtained results are shown in Tables 11 to 15 below.

-Peeling force-FKM plate (or FCP plate) having a thickness of 1.2 mm and unvulcanized epichlorohydrin rubber plate having a thickness of 2.2 mm (rubber composition of Examples 1 to 12 or Comparative Examples 1 to 9) Consisting of things)
Is sandwiched in a mold having a thickness of 3 mm,
After press vulcanization was performed under the conditions of a surface pressure of 20 kgf / cm ² and 160 ° C. × 45 minutes, the obtained vulcanized sheet was cut into a strip having a width of 1 inch. Next, when the strip-shaped vulcanized sheet is separated at a peeling speed of 50 mm / min using a strobe, the above-mentioned FKM plate (or FCP plate);
Peeling force from vulcanized epichlorohydrin rubber plate (kgf / i
nch) was measured.

-Interfacial State- The interfacial state was indicated by visually observing the peeled state between the peeled FKM plate (or FCP plate) and the vulcanized epichlorohydrin rubber plate in the peel force test. In the peeled surface of the FKM plate (or FCP plate) and the epichlorohydrin rubber plate, the entire surface is in a state of rubber destruction as "R destruction", and a part is in a state of rubber destruction and the remaining portion is in a state of interface delamination as "part R" The state in which the entire surface was peeled off at the interface was indicated as “interface” in the table.

[0052]

[Table 11]

[0053]

[Table 12]

[0054]

[Table 13]

[0055]

[Table 14]

[0056]

[Table 15]

As is clear from the results of Tables 11 to 15, when the rubber compositions of Examples 1 to 12 according to the present invention were used, the adhesion between FKM and FCP was good. On the other hand, when the rubber compositions of Comparative Examples 1 to 9 were used, it was recognized that the peeling force was small and thus the adhesiveness was poor.

[0058]

As is clear from the above description, in the present invention, as a new vulcanization system for epichlorohydrin rubber material, 2,3-dimercaptoquinoxaline derivative and 1,8-diazabicyclo (5 , 4,0) undecene-7 salt and a combination of hydrotalcites, whereby a fluororubber or a fluororesin and epichlorohydrin rubber can be used without using any lead compound in the vulcanization system. Can significantly increase the adhesion of
It is possible to provide a more effective laminate having an integrated structure, and further provide a hose comprising such a laminate, particularly a fuel hose useful for a fuel pipe. It is excellent in permanent set and has excellent sour gasoline resistance, and thus has a significant technical significance in that the effectiveness as a fuel hose can be significantly enhanced.

[Brief description of the drawings]

FIG. 1 is an explanatory perspective view showing an example of a fuel hose according to the present invention.

FIG. 2 is a perspective explanatory view showing another example of the fuel hose according to the present invention.

[Explanation of symbols]

 2 innermost layer 4 outer layer 6 outer tube layer 8 fiber reinforced layer

Claims (5)

[Claims] 1. A laminate comprising at least a first layer made of fluororubber or fluororesin and a second layer made of epichlorohydrin-based rubber laminated in contact with the first layer. An epichlorohydrin rubber material is used as a base rubber component for the two layers, and 0.1 to 5 parts by weight of a vulcanizing agent composed of a 2,3-dimercaptoquinoxaline derivative, A rubber composition comprising 0.1 to 5 parts by weight of diazabicyclo (5,4,0) undecene-7 salt and 1 to 20 parts by weight of hydrotalcites; Laminate. 2. The rubber composition according to claim 1, wherein the rubber composition contains at least one of a metal oxide and a metal hydroxide in a proportion of 0.1 to 3 parts by weight per 100 parts by weight of the epichlorohydrin rubber material. The laminate according to claim 1, wherein: 3. A hose having a laminated structure including at least a first layer made of fluororubber or fluororesin and a second layer made of epichlorohydrin rubber laminated in contact with the first layer, wherein the second layer Using an epichlorohydrin rubber material as a base rubber component, and with respect to 100 parts by weight thereof, 0.1 to 5 parts by weight of a vulcanizing agent comprising a 2,3-dimercaptoquinoxaline derivative, and 1,8-diazabicyclo (5,4,0) A rubber composition comprising 0.1 to 5 parts by weight of undecene-7 salt and 1 to 20 parts by weight of hydrotalcites. hose. 4. A method according to claim 1, wherein the first layer comprises a first layer made of a fluororubber or a fluororesin, and a second layer made of an epichlorohydrin-based rubber laminated in contact with the first layer. A fuel hose which is located on the inner side of the hose than the two layers and is the innermost layer which is in contact with the fuel flowing through the hose. The second layer is made of an epichlorohydrin rubber material as a base rubber component, and 100 parts by weight thereof. 0.1 to 5 parts by weight of a vulcanizing agent comprising a 2,3-dimercaptoquinoxaline derivative and 0.1 to 5 parts by weight of 1,8-diazabicyclo (5,4,0) undecene-7 salt A fuel hose formed from a rubber composition obtained by mixing 1 part by weight and 1 to 20 parts by weight of hydrotalcites. 5. The rubber composition according to claim 1, wherein at least one of a metal oxide and a metal hydroxide is contained in a proportion of 0.1 to 3 parts by weight per 100 parts by weight of the epichlorohydrin rubber material. The fuel hose according to claim 4, characterized in that: