COMPOSITION FOR LAMINATES

Abstract

A composition for laminates, comprising: (a) an epichlorohydrin polymer; (b) a compound having a vinyl group; (c) at least one compound selected from the group consisting of a 1,8-diazabicyclo(5.4.0)undecene-7 salt, a 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 (d) a metal salt hydrate.

Claims

1. A composition for laminates, comprising: (a) an epichlorohydrin polymer; (b) a compound having a vinyl group; (c) at least one compound selected from the group consisting of a 1,8-diazabicyclo(5.4.0)undecene-7 salt, a 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 (d) a metal salt hydrate.

2. The composition for laminates according to claim 1, wherein the compound (b) has at least two vinyl groups in the molecule.

3. The composition for laminates according to claim 1, wherein the content of the compound (d) is 0.1 to 10 parts by weight relative to 100 parts by weight of the epichlorohydrin polymer (a).

4. The composition for laminates according to claim 1, further containing an epoxy resin (e).

5. The composition for laminates according claim 1, further containing a copper salt (f).

6. The composition for laminates according to claim 1, further containing a vulcanizing agent (g).

7. The composition for laminates according to claim 6, wherein the vulcanizing agent (g) comprises at least one vulcanizing agent selected from a quinoxaline-type vulcanizing agent, a thiourea-type vulcanizing agent, a mercaptotriazine-type vulcanizing agent, a bisphenol-type vulcanizing agent, a sulfur-containing vulcanizing agent and a peroxide-type vulcanizing agent.

8. The composition for laminates according to claim 1, wherein the content of the compound (c) is 0.3 to 3.0 parts by weight relative to 100 parts by weight of the epichlorohydrin polymer.

9. A laminate produced using a composition for laminates as recited in claim 1.

10. A tube or hose comprising a laminate as recited in claim 9.

11. An automotive fuel pipeline comprising a tube or hose as recited in claim 10.

Description

EXAMPLES AND COMPARATIVE EXAMPLE

[0121] Materials shown in Table 1 were kneaded at a blend ratio shown in Table 1 with a kneader and an open roll. In this manner, sheet-like compositions for laminates (i) each having a thickness of 2 to 2.5 mm were produced.

(Laminates)

[0122] Each of the sheets (i) and a low-gas-permeable polymer layer (ii) having a thickness of 0.3 to 0.5 mm were bonded together to produce a bonded body, and then the bonded body was pressurized at 170 C. and 20 to 25 kg/cm.sup.2 for 15 minutes to produce a rubber-resin laminate having a thickness of 2.0 to 2.5 mm.

[0123] As the low-gas-permeable polymer layer (ii), a CTFE/TFE/PPVE (21.3/76.3/2.4 (mol %)) copolymer fluororesin was used.

(Evaluation of Initial Adhesiveness)

[0124] Each of the vulcanized laminates was cut into a strip-shaped specimen having a size of 1.010 cm to produce a test specimen for adhesiveness test use. The test specimen was subjected to a T peel test at 25 C. at a tension speed of 50 mm/min, and the peeled state was observed with naked eyes. The results of the peel test are shown in Table 2.

(Evaluation of Adhesiveness after Thermal Aging Test)

[0125] The strip-shaped test specimen for adhesiveness test use was subjected to an aging test in accordance with JIS K 6257 in a gear oven at 125 C. for 72 hours, and was then subjected to a T peel test at 25 C. at a tension speed of 50 mm/min. The peeled state was observed with naked eyes. The results of the peel test are shown in Table 2.

(Evaluation of Adhesiveness after Fuel Oil Immersion Test)

[0126] The strip-shaped test specimen for adhesiveness test use was immersed in a test fuel C, which was prepared in accordance with JIS K 6258, at 40 C. for 72 hours, and was then subjected to a T peel test at 25 C. at a tension speed of 50 mm/min. The peeled state was observed with naked eyes. The results of the peel test are shown in Table 2. The test fuel C contained isooctane and toluene at a ratio of 50:50 by volume.

(Ratings for Peeled State)

[0127] : The layers were strongly bonded together and the fracture of the rubber occurred at the interlayer part.

[0128] : The layers were bonded together although the fracture of the material did not occur.

[0129] x: The layers were not bonded to any extent, and delamination occurred at the interface.

[0130] The compounding materials used in Examples and Comparative Example are shown below.

[0131] *1: EPICHLOMER CG, manufactured by Osaka Soda Co., Ltd.

[0132] *2: Seast SO manufactured by Tokai Carbon Co., Ltd.

[0133] *3: BURGESS #30 manufactured by Burgess Pigment Company

[0134] *4: ADK CIZER RS-107 manufactured by ADEKA Corporation

[0135] *5: SPLENDER R-300 manufactured by KAO Corporation

[0136] *6: NOCRAC NBC manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.

[0137] *7: NOCCELER TTCu manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.

[0138] *8: KYOWAMAG #150, manufactured by Kyowa Chemical Industry Co., Ltd.

[0139] *9: DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.

[0140] *10: JER828 manufactured by Mitsubishi Chemical Corporation

[0141] *11: U-CAT SA-1 manufactured by San-Apro Ltd.

[0142] *12: Retarder CTP manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.

[0143] *13: DAISONET XL21-S manufactured by Osaka Soda Co., Ltd.

[0144] *14: DAISO DAP MONOMER manufactured by Osaka Soda Co., Ltd.

TABLE-US-00001 TABLE 1 Comparative Compounding (unit: part(s) by weight) Example 1 Example 2 Example 3 Example 4 Example 1 Epichlorohydrin polymer *1 100 100 100 100 100 FEF Carbon *2 (filler) 50 50 50 50 50 Hard clay *3 20 20 20 20 20 Di(butoxyethoxy)ethyladipate *4 10 10 10 10 10 Sorbitan monostearate *5 3 3 3 3 3 Nickel dibutyldithiocarbamate *6 1 1 1 1 1 Copper dimethyldithiocarbamate *7 0.1 0.1 0.1 0.1 0.1 Magnesium oxide *8 3 3 3 3 3 Synthetic hydrotalcite *9 3 3 3 3 3 Epoxy resin *10 1.5 1.5 1.5 1.5 1.5 Triallyl isocyanurate 5 3 10 Diallyl orthophthalate *14 5 DBU phenol salt *11 1 1 1 1 1 Magnesium sulfate decahydrate 5 5 5 5 5 N-Cyclohexylthiophthalimide *12 1 1 1 1 1 Quinoxaline-type vulcanizing agent *13 1.7 1.7 1.7 1.7 1.7

TABLE-US-00002 TABLE 2 Comparative Example 1 Example 2 Example 3 Example 4 Example 1 Initial After thermal aging test (125 C., 72 hr) After immersion in fuel oil (40 C., 72 hr) X

[0145] As shown in Table 2, in laminates produced using the compositions for laminates of Examples, strong adhesiveness was confirmed in all of the initial adhesiveness evaluation, the evaluation of adhesiveness after thermal aging test and the evaluation of adhesiveness after immersion in fuel oil. In a laminate produced using the composition for laminates of Comparative Example, on the other hand, sufficient adhesiveness was not confirmed in the evaluation of adhesiveness after immersion in fuel oil.

INDUSTRIAL APPLICABILITY

[0146] The present invention can provide a composition for laminates, which has such a property that a cured product of the composition has excellent adhesiveness to another substance (e.g., another polymer). The composition can be used in a laminate with, for example, a fluorine-containing polymer and the like.