JPS613747A - Rubber laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a rubber laminate formed by directly adhering an shrimp halohydrin vulcanized rubber and a thermoplastic polyurethane copolymer.

(Prior art and problems) Vulcanized ebihalohydrin rubber is widely used mainly in automobile-related rubber parts as an excellent rubber material with well-balanced physical properties such as heat resistance, oil resistance, weather resistance, and cold resistance. ing.

Furthermore, as part of efforts to improve the quality of rubber materials, many rubber laminates are being used. For example, functional rubber materials for automobiles range from chloroprene-acrylonitrile-butadiene rubber, which has traditionally been mainly used, to chlorosulfonated polyethylene-acrylonitrile-butadiene rubber, and chlorinated polyethylene-acrylonitrile-butadiene rubber. These include acrylic-shrimp-halohydrin rubber, shrimp-herrohydrin-fluorinated rubber, bihalohydrin-acrylonitrile/butadiene-fluorinated rubber laminates, etc. Even expensive rubber materials can be used in various forms. It is being said.

Particularly in fields where abrasion resistance is required, shrimp halohydrin rubber is used as a rubber laminate such as chlorinated polyethylene-epihalohydrin rubber or chlorsulfonated polyethylene-epihalohydrin rubber.

However, these laminates have problems such as insufficient adhesive strength, or the gasoline resistance of chlorinated polyethylene or chlorosulfonated polyethylene, which significantly deteriorates the adhesive strength when soaked in gasoline. .

(Object of the Invention) In view of the above circumstances, the present inventors aimed to obtain a rubber laminate that is relatively easily manufactured, maintains strong adhesive strength, and has excellent abrasion resistance and gasoline resistance. We conducted a thorough study.

As a result, a rubber laminate made by directly adhering bihalohydrin vulcanized rubber and thermoplastic polyurethane copolymer is strongly bonded, and has superior heat resistance, cold resistance, abrasion resistance, and oil resistance. In particular, it has been discovered that h can fully achieve the objectives, such as exhibiting gasoline resistance.

(Structure of the Invention) The present invention is a rubber laminate characterized in that it is formed by directly adhering an shrimp halohydrin vulcanized rubber and a thermoplastic polyurethane copolymer.

The shrimp halohydrin rubber used in the present invention refers to a shrimp halohydrin homopolymer and a copolymer of shrimp halohydrin and alkylene oxide. Typical examples include: Bichlorohydrin homopolymer, epibromhydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epichlorohydrin-allyl glycidyl ether copolymer, epichlorohydrin-ethylene oxide -propylene oxide copolymer, (2) bichlorohydrin-ethylene oxide-allyl glycidyl ether copolymer, and the like.

Vulcanized shrimp halohydrin rubber is an excellent rubber material with well-balanced physical properties such as heat resistance, oil resistance, weather resistance, and cold resistance.

The vulcanizing agent for vulcanizing the shrimp halohydrin rubber of the present invention is:
There are no particular restrictions as long as the rubber can be vulcanized.

The shrimp halohydrin-based vulcanized rubber, which is a component of the present invention, includes a vulcanizing agent and various compounding agents added as necessary to the shrimp halohydrin rubber, such as reinforcing materials, fillers, plasticizers, acid acceptors, Anti-aging agent, processability improver, additive, flame retardant 1
It is either vulcanized and molded by a conventional method after appropriately blending a foaming agent, etc., or it is preformed and vulcanized and molded when it is directly bonded to a thermoplastic polyurethane copolymer.

The thermoplastic polyurethane copolymer constituting another component of the present invention is (△) polyoxyethylene glycol, polyoxy 10
Polyether glycols such as pyrene glycol and polyoxytetramethylene glycol, or mixtures thereof, as well as polyether glycols copolymerized with these polyether components, aliphatic or alicyclic dicarboxylic acids having 2 to 12 carbon atoms, and carbon Consisting of 2 to 10 aliphatic or alicyclic glycols, such as polyethylene adipate, polytetramethylene adipate, polyethylene sebacate,
Polyneopentyl sebacate.

Polytetramethylene dotecanate, polytetramethylene azelate, polyhexamethylene azelate, poly-
Aliphatic polyester such as ε-cabu lactone, aliphatic copolyester consisting of two types of aliphatic dicarboxylic acids and two types of glycols.

A polyester polyether block copolymer, which is a combination of an aliphatic polyester and an aliphatic polyether, has a hydroxyl group at the end and has a molecular weight of 400 to 5,000. Component 1.0 mol (B) selected from diols with an acid value of 10 or less 4.4-diphenyl diisocyanate, diphenyl methane diisocyanate, dimethyl diphenylmethane diisocyanate, diphenyl ether diisocyanate t-, dichlorodiphenylmethane diisocyanate, bibenzyl diisocyanate, vitriol Component 1.1 selected from diphenyl diisocyanates having an isocyanate group in each phenyl nucleus such as diisocyanate
~3.1 mol (C) 0.3 to 2.0 mol of the component selected from saturated fatty free glycols having 2 to 6 carbon atoms and having a hydroxyl group bonded to the terminal carbon atom (A) The three components of ~(C) are mixed so that the ratio of hydroxyl groups and isocyanate groups in each component is substantially stoichiometric, so that substantially no unreacted glycol or unreacted diisocyanate remains in the reaction product. The total mole m of each component (A) and (C) is expressed as (
[3] A polyurethane copolymer obtained by reacting components in molar amounts substantially equal to each other.

The copolymer is a highly flexible thermoplastic lastomer with excellent heat resistance, oil resistance, weather resistance, cold resistance, and abrasion resistance.

In carrying out the present invention, the thermoplastic polyurethane copolymer is used by molding it into a sheet or film. The thickness varies depending on the shape of the vulcanized Ebihalo 1 = Dorin rubber or the type of copolymer, but it is usually o, 02
A range of 3 fi is suitable, and a range of 0.1 to 1 ga is more preferable. If the thickness is less than 0.02, the film thickness will not be sufficient and it will be difficult to obtain sufficient oil resistance, especially washing and machining resistance, of the rubber laminate of the present invention.

Moreover, if it exceeds 3-, the hardness of the laminate will be too high, causing
A rubber laminate with elasticity cannot be obtained.

For adhesion, the copolymer sheet or film is layered on the vulcanized shrimp-halohydrin rubber, and the copolymer sheet or film is heated at a temperature higher than the softening temperature of the copolymer, e.g. 150 to 250°C, under slight pressure, e.g. 501J10iQ or higher, for several seconds to several tens of seconds. It is bonded by applying pressure for a few seconds. In the case of unvulcanized rubber, it is vulcanized and bonded by applying pressure for several tens of seconds to several tens of minutes.

In carrying out the present invention, not only unvulcanized rubber but also vulcanized rubber can be used as required.

In the former case, the molding operation is easy and the adhesive strength is high.

In the latter case, it is possible to adhere to assembled objects, and a sufficiently large adhesion effect can be obtained. Such bonding devices include electric heating, steam press machines, irons,
There are vulcanizing cans, ultrasonic or high frequency thunders, etc.

(Examples) Examples 1 to 3 Comparative Examples 1 to 7 Each of the formulations shown in Table 1 was kneaded for 15 minutes with a 7″ roll at 10°C, taken out into a sheet, and then kneaded at 160°C using an electric press. Vulcanize and mold for 30 minutes at 120X120
A vulcanized rubber flat plate of ×1 to 1.5 wI was obtained.

Next, thermoplastic polyurethane copolymer (Elastane E
190FNA, T, E 198. FNAT, E5
85FNAT Memoto Nilaston product name) 3 types of pellets]
- respectively 180℃, 210℃, 180℃r 80
- to 9, /c+ (GX 1 minute preforming condition, cooled and then heated to 180℃, 210℃, 180℃F80 respectively 9/ca?GX 30 seconds condition to form to a thickness of 0.5~
Film a, film b and film C of 0.7n were obtained.

The above-mentioned vulcanized rubber flat plate was cut into a size of 60 x 30 m, and each of the films described above was stacked and bonded with heat and pressure (film a).
, c: 180℃, 10kg/adG x 5 minutes,
7-r room b (7) case c210℃, 10k11/c
dG x 2 minutes).

The obtained rubber laminate was cut into 10w5 width pieces and kept at 23°C.

A T-peel test was conducted at a tensile rate of 5 (hn/min), and the adhesive strength is shown in Table 3-1.

As an oil resistance test, shell regular gasoline was heated at 40°C.
A T-peel test (oil resistance: gasoline) after immersing for 70 hours at 40°C and a T-peel test (oil resistance: detergent) after immersing for 3 hours at 40°C in TriClene/Perclene = 50150 were conducted, and the adhesive strength was determined in Table 3-1. It was shown to.

Further, as a heat resistance test, the results of a T peel test after heat treatment at 120'C for 70 hours are also shown in Table 3-1.

As a comparative example, a laminate was manufactured in the same manner as in the above example except that a different rubber compound shown in Table 2 was used, and the results of a T-peel test conducted under the same conditions are shown in Table 3-2. Indicated.

In Table 2, (5) rJsR8BR#1502J manufactured by Japan Synthetic Rubber Co., Ltd. (
6) "Neoprene W" manufactured by Showa Neoprene Co., Ltd. (1) "Paiton E60" (8) [Daisolac RA October manufactured by Osaka Soda Co., Ltd. (9)
[Hypalon 40-1 Showa Neoprene Co., Ltd. (10) rJ
sRN 220SJ manufactured by Japan Synthetic Rubber Co., Ltd. (11) r Noxtite PA-302℃ manufactured by Nippon Mektron Co., Ltd. (12
) Vulcanization system of 1.0 parts by weight of 2-mercaptobenzothiazoledicyclohexylaminesulfenamide and 1.7 parts by weight of sulfur (13) 0.5 parts by weight of 2-mercaptoimidacillin and 0.5 parts by weight of tetramethylthiuram disulfide Vulcanization system with parts by weight (14) 3 parts by weight of 2-mercaptobenzothiazole dicyclohexylamine salt and 1 part by weight of trithiocyanuric acid
．． Vulcanization system (15) with 2 parts by weight of pentamethylene tetrasulfide (16) 2-mercaptobenzothiazole dicyclohexylamine sulfenamide 2.011 parts,
Vulcanized (17) ammonium benzoate with 1.5 parts by weight of tetramethylthiuram disulfide and 0.5 parts by weight of sulfur was used, respectively.

Table 3-1 Table 3-2 Examples 4 to 6 Comparative Examples 8 to 14 Each compound shown in Table 1 was kneaded with a 1″ roll at 70°C for 15 minutes, taken out into a sheet, and then placed in an electric heat press. J:
It was molded under the conditions of 80k11/CIjG x 3 minutes at 10°C, and after cooling, a flat plate of 120 x 120 x z ~ 2.5 m was obtained.

The unvulcanized rubber flat plate described above and the films a, b, and c produced in Examples 1 to 3 were stacked on each other, and the films a and C were heated at 180°C and 10 kg/aJX for 5 minutes, and the film b
The adhesive was bonded under heat and pressure at 210° C. and 10 g/dGx for 2 minutes.

The obtained rubber laminate was subjected to a T-peel test under the same conditions as in Examples 1 to 3, and the adhesive strength is shown in Table 4-1.

In addition, the results of the oil resistance test conducted in the same manner as in Examples 1 to 3 are also shown in Table 4-1.

Table 4-2 shows the results of a test carried out in the same manner as in the above example except that the other rubber compound shown in Table 2 was used as a comparative example.

Comparative Example 15.16 Each of the Δ, G, and l-1 formulations in Tables 1 and 2 was heated to 7″ at 70°C.
Knead with a roll for 15 minutes, take out a sheet with a thickness of 1.0 to 1.5 mm, stack Sheet A and Sheet G, and Sheet A and Sheet H, respectively, and heat to 80 to 9/c++? at 160°C.
Rubber laminates G/A and H/A were obtained by direct vulcanization and adhesion under the conditions of G. The test results were shown in Table 4-3, which were conducted in the same manner as in the above examples.

Table 4-1 Note: *mark indicates the value at the time of rubber failure.

Table 4-2 / Table /I-3 Examples 7 to 9 Comparative Example 17.18 In the same manner as in Examples 4 to 6, the shrimp-halohydrin rubber (compound A) and films a, b, and c of Table 1 were prepared. The rubber laminate produced using each was cut into a rectangle of 54 x 32 m in size, and soaked in Shell regular gasoline at 40°C for 24 hours.
After soaking for an hour, drying at 100°C for 24 hours, cooling with dry ice methanol at -40°C, and testing JIS K 63 using an electric low-temperature impact embrittlement tester manufactured by Toyo Seiki Co., Ltd.
A blow was applied from the opposite side of the cohydrin-based rubber (compound A) using Ebiha 01. The results are shown in Table 6.

As a comparative example, 2+9 produced in Comparative Examples 15 and 16, respectively.
Table 6 also shows the results of the test conducted in the same manner as above except that the rubber laminates G/A and H/A were used.

Table 6 Note: O indicates no damage, and × indicates cracks.

Examples 10-12 Comparative Example 19.20 In the same manner as in Examples 1-3 above, formulation A shown in Table 1,
Rubber laminates manufactured using C and films a and C, respectively, were subjected to an abrasion test according to JIS, K 7!04.

Using wear wheel C8-17, load 1000g, rotation speed 1
The polyurethane film side of the test piece was abraded under the conditions of 000 times, and the test results are shown in Table 7 as abrasion quality M.

As a comparative example, vulcanized rubber flat plates (size:
The test results were also shown in Table 7, which was conducted in the same manner as in the above example, except that the test was conducted using 120×, 120×2 m).

Table 7 (Effects of the invention) The rubber laminate of the present invention is a product in which a thermoplastic polyurethane copolymer and vulcanized rubber are firmly adhered, and has excellent heat resistance, cold resistance, abrasion resistance, and oil resistance. In particular, it has excellent resistance to fuel oils such as gasoline.

Claims (1)

[Claims] A rubber laminate characterized by directly adhering epihalohydrin vulcanized rubber and thermoplastic polyurethane copolymer.