Laminate

Abstract

A laminate of a rubber layer (A) and a fluororesin layer (B) on the rubber layer (A), wherein the rubber layer (A) is a layer made of a rubber composition for vulcanization, the rubber composition for vulcanization contains an unvulcanized rubber (a1); at least one compound (a2) selected from the group consisting of a 1,8-diazabicyclo(5.4.0)undec-7-ene salt, a 1,5-diazabicyclo(4.3.0)-non-5-ene salt, 1,8-diazabicyclo(5.4.0)undec-7-ene, and 1,5-diazabicyclo(4.3.0)-non-5-ene; magnesium oxide (a3); and silica (a4), the amount of the compound (a2) is larger than 1.0 part by mass and not larger than 5.0 parts by mass, for each 100 parts by mass of the unvulcanized rubber (a1), the fluororesin layer (B) is a layer made of a fluoropolymer composition, and the fluoropolymer composition contains a fluoropolymer (b1) having a copolymer unit derived from chlorotrifluoroethylene.

Claims

1. A laminate comprising a rubber layer (A) and a fluororesin layer (B) on the rubber layer (A), wherein the rubber layer (A) is a layer made of a rubber composition for vulcanization, the rubber composition for vulcanization contains an unvulcanized rubber (a1) which is acrylonitrile-butadiene rubber or its hydride; at least one compound (a2) selected from the group consisting of a 1,8-diazabicyclo(5.4.0)undec-7-ene salt, a 1,5-diazabicyclo(4.3.0)-non-5-ene salt, 1,8-diazabicyclo(5.4.0)undec-7-ene, and 1,5-diazabicyclo(4.3.0)-non-5-ene; magnesium oxide (a3); and silica (a4), the amount of the compound (a2) is larger than 1.0 part by mass and not larger than 5.0 parts by mass, for each 100 parts by mass of the unvulcanized rubber (a1), the amount of the magnesium oxide (a3) is 3 to 20 parts by mass, for each 100 parts by mass of the unvulcanized rubber (a1), the amount of the silica (a4) is 10 to 40 parts by mass for each 100 parts by mass of the unvulcanized rubber (a1), the fluororesin layer (B) is a layer made of a fluoropolymer composition, and the fluoropolymer composition contains a fluoropolymer (b1) which is chlorotrifluoroethylene copolymer, wherein the chlorotrifluoroethylene copolymer contains only a chlorotrifluoroethylene unit, tetrafluoroethylene unit and perfluoro(alkylvinylether) unit, the ratio between the chlorotrifluoroethylene unit and the tetrafluoroethylene unit in the chlorotrifluoroethylene copolymer is chlorotrifluoroethylene unit/tetrafluoroethylene unit =15-90/85-10 (mol %), the amount of the perfluoro(alkylvinylether) unit is not smaller than 0.5 mol % and not larger than 5 mol % of all the monomer units.

2. The laminate according to claim 1, wherein the rubber composition for vulcanization further contains at least one vulcanizing agent (a5) selected from the group consisting of a sulfur vulcanizing agent and a peroxide vulcanizing agent.

3. The laminate according to claim 1, wherein the rubber composition for vulcanization further contains at least one metal salt (a6) selected from the group consisting of a metal carbamate and a thiazole metal salt.

4. The laminate according to claim 1, wherein the unvulcanized rubber (a1) is acrylonitrile-butadiene rubber.

5. The laminate according to claim 1, wherein the compound (a2) is at least one compound selected from the group consisting of 1,8-diazabicyclo(5.4.0)undec-7-ene, 1,8-benzyl-1,8-diazabicyclo(5.4.0)-7-undecenium chloride, 1,8-diazabicyclo(5.4.0)undec-7-ene naphthoate, 1,8-diazabicyclo(5.4.0)undec-7-ene phenoxide, 1,8-diazabicyclo(5.4.0)undec-7-ene orthophthalate, and 1,8-diazabicyclo(5.4.0)undec-7-ene formate.

6. The laminate according to claim 1, wherein the rubber layer (A) is laminated on both faces of the fluororesin layer (B).

7. The laminate according to claim 1, wherein the fluororesin layer (B) is laminated on both faces of the rubber layer (A).

8. The laminate according to claim 1, further comprising a polymer layer (C) other than the rubber layer (A) and the fluororesin layer (B), on the rubber layer (A) or the fluororesin layer (B).

9. A laminate obtained by vulcanizing the laminate according to claim 1, wherein a vulcanized rubber layer (A 1) produced from the rubber layer (A) and the fluororesin layer (B) are adhered by vulcanization.

Description

EXAMPLES

(1) The present invention is now described with reference to Examples, but is not limited only to these Examples.

(2) Hereinafter, a fluororesin used in Examples and Comparative Examples and evaluation methods thereof are described.

(3) (1) Composition of Polymer

(4) The composition was measured by .sup.19F-NMR analysis.

(5) (2) Melting Point

(6) The melting point was obtained as a temperature corresponding to the maximum value of the melting peaks measured by a SEIKO DSC device (product of Seiko Instruments Inc.) when the temperature was increased at 10° C./min.

(7) (3) MFR (Melt Flow Rate)

(8) The MFR was obtained by measuring the weight (g) of the polymer exiting from the nozzle having a diameter of 2 mm and a length of 8 mm per unit time (10 minutes) under a load of 5 kg at various temperatures with use of a melt indexer (product of TOYO SEIKI SEISAKU-SHO, LTD.).

(9) (4) Measurement of Fuel Permeability Coefficient of Monolayer

(10) Resin pellets were each placed in a die having a diameter of 120 mm and set in a press machine heated to 300° C. The pellets were respectively melted and pressed at a pressure of about 2.9 MPa to give sheets having a thickness of 0.15 mm. The sheets were each placed in a SUS 316 cup for the fuel permeability coefficient measurement (40 mmφ of internal diameter, 20 mm of height) containing 18 mL of CE 10 (fuel containing a mixture of isooctane:toluene=50:50 (volume ratio) added with 10% by volume of ethanol). The mass change was measured at 60° C. for 1000 hours. Based on the time rate of the measured mass change and the surface area and thickness of the sheet in a wetted part, the fuel permeability coefficient (g.Math.mm/m.sup.2/day) was calculated.

(11) Table 2 shows fluororesins used in Examples and Comparative Examples.

(12) TABLE-US-00002 TABLE 2 Melting MFR (g/10 min.) Thickness of point (Measured Fuel permeability fluororesin sheet Fluoropolymer (° C.) temperature) (g .Math. mm/m.sup.2/day) (μm) Fluororesin (1) CTFE/TFE/PPVE copolymer 246 29.2 0.4 120 21.3/76.3/2.4 (mol %) (297° C.) Fluororesin (2) ETFE 253 20.0 2.5 120 (product of Daikin Industries, Ltd., (297° C.) Neoflon EP-7000) Fluororesin (3) ETFE 258  6.0 2.5 100 (product of Daikin Industries. Ltd., (297° C.) Neoflon EP-543) Fluororesin (4) EFEP 195 25.0 6.5 1000 (product of Daikin Industries, Ltd., (265° C.) Neoflon RP-5000) Fluororesin (5) FEP 260 27.0 0.4 100 (product of Daikin Industries, Ltd., (297° C.) Neoflon NP-102) Fluororesin (6) PCTFE 210 — 4.7 100 (product of Daikin Industries, Ltd., Neoflon M-300)
(Rubber composition A to O and a to h for vulcanization)

(13) Materials shown in Tables 3 and 4 were separately compounded using a 8-inch open roll mixer to give rubber compositions A to 0 and a to h in a sheet shape having a thickness of about 3 mm. Numerical values in Tables 3 and 4 are each expressed in units of “part by mass”.

(14) The optimal vulcanizing time (T.sub.90) was determined by measuring a maximum torque value (M.sub.H) and a minimum torque value (M.sub.L) at 160° C. using a curelastometer type II (model: JSR curelastometer, product of JSR Trading Co., Ltd.) for each of the rubber compositions A to 0 for vulcanization. Table 5 shows the measurements. Here, T.sub.90 is calculated using a formula {(M.sub.H)-(M.sub.L)}×0.9+M.sub.L and M.sub.H and M.sub.L are measured in accordance with JIS K 6300-2.

(15) TABLE-US-00003 TABLE 3 Rubber composition for vulcanization Compounding agent Materials Manufacturer A B C D E F G H Base polymer NIPOL DN101 Zeon Corporation 100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  Stearic acid Stearic acid 50S New Japan Chemical 1.0  1.0 1.0 1.0 1.0 1.0 1.0 1.0 Co., Ltd. MgO Kyowa Mag #150 Kyowa Chemical 10.0  10.0 10.0  10.0  10.0  10.0  10.0  10.0  Industry Co., Ltd. ZnO Zinc oxide #2 Mmitsui Mining & — — — — — — — — Smelting Co., Ltd. DBU naphthoate DA-500 Daiso Co., Ltd. 1.0  3.1 1.0 1.0 — 1.0 1.0 1.0 DBU DBU-B Wako Pure Chemical 2.1 — — — 1.5 2.1 2.1 2.1 benzyl chloride Industries., Ltd. DBU orthophthalate SA-810 SAN-APRO LIMITED — — 2.1 — — — — — DBU phenoxide SA-1 SAN-APRO LIMITED — — — 2.1 — — — — DBU formate SA-603 SAN-APRO LIMITED — — — — — — — — DBU octoate SA-102 SAN-APRO LIMITED — — — — — — — — DBU DBU Wako Pure Chemical — — — — — — — — Industries., Ltd. Carbon black SEAST S TOKAI CARBON CO., 50.0  50.0 50.0  50.0  50.0  50.0  50.0  50.0  LTD. Silica Carplex 1120 DSL Japan Co., Ltd. 20.0  20.0 20.0  20.0  20.0  20.0  20.0  20.0  Silica Nipsil VN3 TOSOH SILICA — — — — — — — — CORPORATION Plasticizer TP-95 ROHM ANS HAAS 25.0  25.0 25.0  25.0  25.0  25.0  25.0  25.0  Sulfur Sulfur powder Hosoi Chemical 1.5  1.5 1.5 1.5 1.5 1.5 1.5 1.5 Industry Co., Ltd Vulcanizing agent VULNOC R OUCHI SHINKO — — — — — — — — CHEMICAL INDUSTRIAL CO., LTD. Thiazole NOCCELER OUCHI SHINKO 1.0  1.0 1.0 1.0 1.0 1.0 1.0 1.0 vulcanization MSA-G CHEMICAL INDUSTRIAL accelerator CO., LTD. Thiazole metal salt NOCCELER MZ OUCHI SHINKO 0.2  0.2 0.2 0.2 0.2 — — — CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER PZ OUCHI SHINKO — — — — — 0.2 — — CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER EZ OUCHI SHINKO — — — — — — 0.2 — CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER BZ OUCHI SHINKO — — — — — — — 0.2 CHEMICAL INDUSTRIAL CO., LTD. Rubber composition for vulcanization Compounding agent Materials Manufacturer I J K L M N O Base polymer NIPOL DN101 Zeon Corporation 100.0  100.0  100.0  100.0  100.0  100.0  100.0  Stearic acid Stearic acid 50S New Japan Chemical 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Co., Ltd. MgO Kyowa Mag #150 Kyowa Chemical 10.0  10.0  10.0  10.0  10.0  10.0  10.0  Industry Co., Ltd. ZnO Zinc oxide #2 Mmitsui Mining & — — — — — — — Smelting Co., Ltd. DBU naphthoate DA-500 Daiso Co., Ltd. 1.0 — — — 1.0 — — DBU DBU-B Wako Pure Chemical 2.1 — — — 2.1 — — benzyl chloride Industries., Ltd. DBU orthophthalate SA-810 SAN-APRO LIMITED — 2.0 — — — — — DBU phenoxide SA-1 SAN-APRO LIMITED — — 2.0 — — — — DBU formate SA-603 SAN-APRO LIMITED — — — — — 2.0 1.5 DBU octoate SA-102 SAN-APRO LIMITED — — — — — — — DBU DBU Wako Pure Chemical — — — 1.5 — — — Industries., Ltd. Carbon black SEAST S TOKAI CARBON CO., 50.0  50.0  50.0  50.0  50.0  50.0  50.0  LTD. Silica Carplex 1120 DSL Japan Co., Ltd. — 20.0  20.0  20.0  20.0  20.0  20.0  Silica Nipsil VN3 TOSOH SILICA 20.0  — — — — — — CORPORATION Plasticizer TP-95 ROHM ANS HAAS 25.0  25.0  25.0  25.0  25.0  25.0  25.0  Sulfur Sulfur powder Hosoi Chemical 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Industry Co., Ltd Vulcanizing agent VULNOC R OUCHI SHINKO — — — — — — — CHEMICAL INDUSTRIAL CO., LTD. Thiazole NOCCELER OUCHI SHINKO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 vulcanization MSA-G CHEMICAL INDUSTRIAL accelerator CO., LTD. Thiazole metal salt NOCCELER MZ OUCHI SHINKO 0.2 0.2 0.2 0.2 — 0.2 0.2 CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER PZ OUCHI SHINKO — — — — — — — CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER EZ OUCHI SHINKO — — — — — — — CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER BZ OUCHI SHINKO — — — — — — — CHEMICAL INDUSTRIAL CO., LTD.

(16) TABLE-US-00004 TABLE 4 Rubber composition for vulcanization Compounding agent Materials Manufacturer a b c d e f g h Base polymer NIPOL DN101 Zeon Corporation 100.0  100.0  100.0  100.0  100.0  100.0  100.0  100.0  Stearic acid Stearic acid 50S New Japan Chemical 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Co., Ltd. MgO Kyowa Mag #150 Kyowa Chemical 10.0  10.0  10.0  10.0  10.0  — 10.0  — Industry Co., Ltd. ZnO Zinc oxide #2 Mitsui Mining & — — — — — 5.0 — 5.0 Smelting Co., Ltd. DBU naphthoate DA-500 Daiso Co., Ltd. 1.0 — — — — 1.0 1.0 — DBU DBU-B Wako Pure Chemical — 1.0 — — — 2.1 1.9 2.0 benzyl chloride Industries., Ltd. DBU orthophthalate SA-810 SAN-APRO LIMITED — — 1.0 — — — — — DBU phenoxide SA-1 SAN-APRO LIMITED — — — 1.0 — — — — DBU formate SA-603 SAN-APRO LIMITED — — — — — — — — DBU octoate SA-102 SAN-APRO LIMITED — — — — 1.0 — — — DBU DBU Wako Pure Chemical — — — — — — — — Industries., Ltd. Carbon black SEAST S TOKAI CARBON CO., 50.0  50.0  50.0  50.0  50.0  50.0  50.0  50.0  LTD. Silica Carplex 1120 DSL Japan Co., Ltd. 20.0  20.0  20.0  20.0  20.0  20.0  — 20.0  Silica Nipsil VN3 TOSOH SILICA — — — — — — — — CORPORATION Plasticizer TP-95 ROHM AND HAAS 25.0  25.0  25.0  25.0  25.0  25.0  25.0  25.0  Sulfur Sulfur powder Hosoi Chemical 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Industry Co., Ltd. Vulcanizing agent VULNOC R OUCHI SHINKO — — — — — — — — CHEMICAL INDUSTRIAL CO., LTD. Thiazole NOCCELER MSA- OUCHI SHINKO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 vulcanization G CHEMICAL INDUSTRIAL accelerator CO., LTD. Thiazole metal salt NOCCELER MZ OUCHI SHINKO 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER PZ OUCHI SHINKO — — — — — — — — CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER EZ OUCHI SHINKO — — — — — — — — CHEMICAL INDUSTRIAL CO., LTD. Metal carbamate NOCCELER BZ OUCHI SHINKO — — — — — — — — CHEMICAL INDUSTRIAL CO., LTD.

(17) TABLE-US-00005 TABLE 5 Rubber composition for vulcanization A B C D E F G H I J K L M N O M.sub.L(N) 1.4 1.8 2.0 2.0 2.0 1.2 1.5 1.5 2.0 1.0 2.0 1.5 2.9 2.3 2.9 M.sub.H(N) 16.7 16.2 15.7 13.7 16.7 16.7 12.7 16.2 16.7 16.7 14.7 13.7 20.6 18.4 21.1 T.sub.90(min) 15.0 17.0 12.0 12.0 10.5 13.0 13.0 14.0 12.0 13.0 14.0 13.0 9.0 14.0 10.0

(18) Measurement of T.sub.90 clarified that the rubber composition E for vulcanization containing DBU-B and the rubber composition O for vulcanization containing DBU formate had short T.sub.90, though the DBU-B content and the DBU formate content were small. They were especially excellent in vulcanization properties.

Examples 1 to 16 and Comparative Examples 1 to 12

(19) A sheet (about 3 mm thick) of a rubber composition for vulcanization shown in Table 3 or 4 and a fluororesin sheet having a thickness shown in Table 2 were stacked with a fluororesin film (10 μm thick, product of Daikin Industries, ltd., trade name: Polyflon PTFE M731 skive film) having a width of about 10 to 15 mm interposed therebetween on one end portion. The stack was inserted into a die containing a metal spacer so as to make a sheet having a thickness of 2 mm, and was pressed at 160° C. for 45 minutes to give a sheet-shaped laminate. The obtained laminate was cut into three sets of strip specimens (10 mm width X.sup.40 mm length) each with a grip that is a part where the fluororesin sheet is peeled. The adhesion strength of the specimens was measured by performing a peeling test at a tensile speed of 50 ram/min. at 25° C. using an autograph (product of Shimadzu Corporation, AGS-J 5kN) in accordance with the method disclosed in JIS-K-6256 (Adhesion test of cross-linked rubber). The average value of the obtained data (N=3) was calculated and determined as the adhesion strength. Further, the detachment was observed and evaluated based on the following criteria. Table 6 shows the results.

(20) (Evaluation of Adhesion)

(21) Good: Material corruption of the rubber layer or the fluororesin occurred on the interface of the laminate to allow no detachment.

(22) Poor: Detachment comparatively easily occurred on the interface of the laminate.

(23) TABLE-US-00006 TABLE 6 Adhesion Evaluation Rubber Fluororesin strength on layer layer (N/cm) adhesion Example 1 A (1) 24 Good Example 2 B (1) 21 Good Example 3 C (1) 24 Good Example 4 D (1) 22 Good Example 5 E (1) 21 Good Example 6 F (1) 22 Good Example 7 G (1) 22 Good Example 8 H (1) 26 Good Example 9 I (1) 28 Good Example 10 J (1) 23 Good Example 11 K (1) 23 Good Example 12 L (1) 25 Good Example 13 M (1) 25 Good Example 14 E (6) 25 Good Example 15 N (1) 24 Good Example 16 O (1) 23 Good Comparative a (1) 1 or less Poor Example 1 Comparative b (1) 16 Poor Example 2 Comparative c (1)  5 Poor Example 3 Comparative d (1)  5 Poor Example 4 Comparative e (1) 1 or less Poor Example 5 Comparative f (1) 1 or less Poor Example 6 Comparative g (1) 14 Poor Example 7 Comparative A (2) 1 or less Poor Example 8 Comparative A (3) 1 or less Poor Example 9 Comparative A (4) 1 or less Poor Example 10 Comparative A (5) 1 or less Poor Example 11 Comparative h (1) 1 or less Poor Example 12

Example 17

(24) The rubber composition for vulcanization and the fluororesin were continuously extruded by using an extrusion machine. Here, the inner-layer material was the rubber composition A for vulcanization, the middle-layer material was the fluororesin (1), and the outer-layer material was the rubber composition A for vulcanization. A DAITEPIC mandrel (product of Mitsubishi Cable Industries, Ltd.) having a diameter of 24.4 mm was used as a core material passed along with the materials through the forming line. The molded product obtained by extruding the rubber composition A for vulcanization and the fluororesin (1) was steam vulcanized in a vulcanizing autoclave to give a fuel hose having the above three-layer structure. In addition, CE10 was enclosed in the fuel hose and the permeation coefficient was determined based on the mass change at 60° C. The coefficient was 4.0 g/m.sup.2.Math.day.

(25) Conditions for extrusion and for steam vulcanization are listed below.

(26) 1) Setting of extruder for inner-layer NBR and outer-layer NBR

(27) Screw temperature: 60° C. Cylinder 1: 70° C. Cylinder 2: 70° C. Head: 80° C. Thickness of molded product: 2.4 mm (both inner layer and outer layer)
2) Setting of extruder for middle-layer fluororesin Cylinder 1: 260° C. Cylinder 2: 265° C. Cylinder 3: 270° C. Shell clamp: 270° C. Neck: 270° C. Die: 270° C. Head 270° C. Thickness of molded product: 0.15 mm
3) Condition for steam vulcanization of molded product 160° C.×60 minutes

INDUSTRIAL APPLICABILITY

(28) The laminate of the present invention, especially the vulcanized laminate, is favorably used for seals, bellows, diaphragms, hoses, tubes, and electric cables of gaskets and non-contact and contact type packings (self-seal packing, piston ring, split ring packing, mechanical seal, oil seal, and etc.) which are required to have thermal resistance, oil resistance, fuel resistance, LLC resistance, and steam resistance. They are used for engine body, main engine-driving system, valve gear system, lubricating/cooling system, fuel system, and intake/exhaust system; transmission system of driving gear system; steering system of chassis; braking system; standard electrical parts, electrical parts for control, and accessory electrical parts for automobiles.