DE4020512A1 - VIBRATION DAMPING SHEET - Google Patents

Description

The present invention relates to a vibration-damping composite metal sheet, the two Metal fins and an intermediate layer comprising between the two metal slats is inserted, containing one on Rubber based resin composition in film or Foil form, the rubber-based Resin composition comprises a rubber composition containing a butyl rubber, a copolymer of a Olefin and an acrylic ester and a polyoctenylene resin and mixes a copolymer of an olefin and one epoxy-containing acrylic ester, and that over a wide Temperature range has vibration damping capabilities.

The past few years have been increasing Tightening of noise regulations for apartments, Motor vehicles etc. different methods for Countermeasures examined. A steadily increasing trend is primarily in vibration damping materials Sound sources or parts of the sound source that swing accompanying sound, use, and various Vibration-damping composite metal sheets have so far been used suggested.

For example, JP-OS 12 451/1964 discloses a vibration-damping metal sheet, in which a copolymer made of vinyl acetate and a maleic acid diester, a copolymer from vinyl chloride and ethylhexyl acrylate or the like as an intermediate layer is used. This invention applies a known fact that vibrational energy by the Use of a resin with viscoelasticity as Heat energy is absorbed. In the resin with the Viscoelasticity changes Viscoelasticity sensitive to a change in  Temperature so that it is expected that the vibration damping ability in an area of Operating temperature will be lost.

Generally, the vibration absorbing ability can be as physical quantity, called operational damping (loss factor), and it is common knowledge that the material has a vibration absorbing ability if the operational damping is 0.05 or more. Viscoelastic substances such as rubber, copolymer resins and asphalt, were considered effective when considered as the material described above can be used. you are but satisfactory in the vibration damping ability poor adhesion to the metal sheet or the Processibility for insertion between the Metal slats, so far so far not really satisfactory Material is known from the prior art.

Butyl rubber is excellent in the ability to Vibration damping due to its high hysteresis and is best suited to the impact resistance of others Improve materials at a low temperature. However, it has disadvantages in terms of ductility, Tolerability and adherence.

JP-OS 2 91 930/1989 discloses:

• 1) a vibration-damping composite metal sheet, thereby characterized in that it comprises two metal fins and one intermediate intermediate layer, the one A rubber resin composition comprising one Contains butyl rubber and a polyoctenylene resin and a copolymer of an olefin and a mixed therewith Acrylic acid copolymer, and that over a wide range  Temperature range a vibration damping ability owns; and
• 2) a vibration-damping composite metal sheet, thereby characterized in that it comprises two metal fins and one intermediate adhesive layer comprising an multilayer film or sheet containing one Resin layer containing a butyl rubber and a Contains polyoctenylene resin, and a resin layer, the one Contains copolymer of an olefin and acrylic acid, and that over a wide temperature range has anti-vibration ability.

In view of the above, intense Research carried out in terms of development a vibration-damping composite metal sheet with a high vibration damping ability by inserting a Resin composition between the metal fins, in which the Various disadvantages of viscoelastic substances have been eliminated.

A vibration damping sheet according to the present Invention comprises two metal blades and one Intermediate layer between the two metal slats is inserted, comprising a rubber composition, which is a butyl rubber, polyoctenylene and a copolymer from an olefin and an epoxy-containing acrylic ester contains.

The rubber composition may further contain a Copolymer of an olefin and an acrylic ester.

The sheet can be two metal fins and three Include intermediate layers, the two outer  Layers of the three intermediate layers comprise a copolymer from an olefin and an epoxy-containing acrylic ester and the other layer that is between the two outer layers is inserted, a butyl rubber and polyoctenylene includes.

The sheet can be two metal fins and three Include intermediate layers, the two outer Layers of the three intermediate layers comprise a copolymer from an olefin and an epoxy-containing acrylic ester and the another layer inserted in between, one Butyl rubber, polyoctenylene and a copolymer of one Olefin and an acrylic ester.

The olefin copolymer used in the present invention and an epoxy-containing acrylate comprises an olefin which is associated with an epoxy-containing acrylate in a known manner is copolymerized or grafted, and the content of epoxy-containing acrylate is preferably 0.1 to 45%, particularly preferably 1 to 25%. If the salary is less than 0.1%, can not be sufficient liability be achieved. On the other hand, if the content is 45% compatibility with the Butyl rubber, the copolymer of an olefin and a Acrylic ester and the polyoctenylene resin poor, so that none sufficient mechanical strength can be achieved.

The butyl rubber used in the invention is a chemically stable rubber made by mixing one Isobutylene monomer with a small amount of one Isoprene monomer and subjecting the mixture to cationic Copolymerization is made. The butyl rubber also contains chlorine and bromobutyl rubber.  

The copolymer of an olefin and a Acrylic ester is made by mixing one Olefin monomers, such as ethylene, propylene or butylene, with a small amount of an acrylic ester or Methacrylic esters and subjecting the mixture to the Copolymerization by known methods, and Acrylic or methacrylic ester content is preferably 1 to 50%, particularly preferably 3 to 30%. If the Content is less than 1%, may not be sufficient Strength can be achieved. On the other hand, if the salary Exceeds 50%, is the compatibility with the Butyl rubber or polyoctenylene resin poor, so that insufficient mechanical strength can be achieved can.

The polyoctenylene resin used in the present invention becomes made by polymerizing cyclooctene and should have one double bond per 8 carbon atoms and have a molecular weight of not more than 10,000. The content of transisomer is 50% or more, preferably 60% or more, and the extent of Crystallinity is preferably 10% or more. The polyoctenylene resin has a melting point of usually 40 ° C or above, preferably from 50 to 60 ° C, and a glass transition point of -75 to -30 ° C.

The cyclooctene, which is the base material of polyoctenylene forms, can be synthesized by various methods be, e.g. B. by dimerizing butadiene and hydrogenating one of the remaining two double bonds.

If necessary, colors and pigments can be different  Stabilizers, fillers, plasticizers, antioxidants, Ultraviolet absorbers, nucleating agents, antistatic Agents and flame retardants of rubbery Resin composition of the intermediate layer of the Vibration-damping composite metal sheet according to the invention be added. Close the additives described above one that acts as a vulcanizing agent and Vulcanization accelerators are known, as well various additives, such as peroxides, sulfur compounds, Phenolic resins, plasticizer oils and alicyclic epoxy resins for Use with the butyl rubber, the copolymer of one Olefin and an acrylic ester and the polyoctenylene resin.

The resin composition of the present invention can be produced are made by melt-mixing the ingredients various processes, such as roll milling or extrusion. For example, the copolymer first from an olefin and an epoxy-containing acrylate melted, and the rest of the ingredients, that's the Butyl rubber, the copolymer of an olefin and a Acrylic ester and the polyoctenylene resin can then to be added. Alternatively, the above described three components simultaneously be mixed together. If necessary, it is also possible in each phase the additives described above, e.g. B. Fillers, plasticizers and antioxidants. Alternatively, the three components can be mixed in liquid form are by dissolving in a suitable solvent.

The rubbery resin of the present invention comprising a Copolymer of an olefin and an epoxy-containing acrylate, a butyl rubber, a copolymer of an olefin and an acrylic ester and a polyoctenylene resin becomes one  Shaped film or sheet using the conventionally known T-shape film making device or the device for inflation film - Manufacture, and then between the two metal fins inserted and laminated under pressure. Alternatively, a Cast film directly on the metal sheet Shedding are formed. In this case the thickness is the film or the film preferably 10 μm to 1 mm, particularly preferably 20 to 150 μm.

The rubbery resin as an intermediate layer comprising a copolymer of an olefin and a epoxy-containing acrylate, a butyl rubber, a copolymer from an olefin and an acrylic ester and a Polyoctenylene resin, can be produced by a process be melt-mixing the ingredients different methods and forms of mixing into one Includes film or foil. Alternatively, the Ingredients directly to a two or more layers Shaped using a film Coextrusion machine. In this case, if an adhesive Layer comprising a copolymer of an olefin and a epoxy-containing acrylate between the metal sheet and the rubbery resin film comprising a butyl rubber, a copolymer of an olefin and an acrylic ester and a polyoctenylene resin is inserted, which causes multilayer film no blocking between the Film surfaces themselves, while adhering well to that Metal sheet is retained, which is what laminating with a metal sheet advantageously facilitated.

Examples of the metal sheets used in the invention include those made of iron, nickel, titanium, aluminum, Magnesium, copper, zinc and tin and various  Alloy sheets, which essentially consist of the above assemble described metals, e.g. B. stainless Steel sheets. There is no specific limitation on the thickness of the metal sheets described above, as long as the Manufacture of the following vibration damping Composite metal sheets is possible, such as. B. bends or Pull. Generally the thickness can be 0.01 to 5 mm be. The metal sheets described above are available in the stores. However, since in general Have grease or oil on it, it is desirable use them after degreasing. Degreasing can be done after known methods are carried out.

Fig. 1 shows schematically a process for the continuous production of a vibration-damping composite metal sheet;

Fig. 2 shows schematically a continuous degreasing of a metal sheet;

FIGS. 3 and 4 are graphs showing the temperature dependence of the insertion loss of the material as used in Examples 1 to 6 and Comparative Examples 1 to 4.

In Fig. 1, reference numerals 1 and 1 'a sheet metal, 2 , 2 ', 3 and 3 'a roller, 4 , 4 ' and 8 a straightener, 5 and 5 'a preheating stage, 6 and 6 ' a roller, 9 a reheating stage, 10 a first cooling stage, 11 a second cooling stage, 12 and 13 a slitter, 7 a rubber-like resin film and 14 a vibration-damping composite metal sheet as a product. In Fig. 2, 15 represents a roller, 16 and 18 an electrolytic cell, 17 an anode plate, 19 a cathode plate, 20 a power supply, 21 a washing step with water, 22 a drying step, 22 a metal sheet before degreasing and 24 a metal sheet after degreasing .

The vibration damping composite metal sheet of the present invention is preferably manufactured by inserting a film or a sheet of a rubbery resin comprising a copolymer of an olefin and an epoxy-containing acrylate, a butyl rubber, a copolymer of an olefin and an acrylic ester and a polyoctenylene resin between two metal plates thereof or various types and presses of the resulting assembly with heating and using a compression molding machine or rollers. In this case, various methods can be used, such as lamination after trimming the metal sheets and the rubber resin to a size and shape suitable for subsequent fabrication, and a continuous manufacturing method as shown in FIG. 1. If the vibration-damping composite metal sheet is produced by the continuous process as shown in FIG. 1, a preliminary degreasing of the metal sheets as shown in FIG. 2 is preferred since good adhesion can be achieved thereby.

The vibration-damping composite metal sheet, which through the present invention is made available not just good vibration dampening skills over you large temperature range, but the manufacture of the Composite sheet is very simple because of the rubbery resin Interlayer comprising an olefin copolymer  and an epoxy-containing acrylate, a butyl rubber Copolymer of an olefin and an acrylic ester and a Polyoctenylene resin, easily into a film or foil can be molded and also good adhesive Possesses properties.

Examples

The following examples illustrate the invention. The Adhesion between the resin and the metal was considered Expressed adhesive strength and the T-peel strength (T-peel strength) and the bending shear strength measured according to the methods as by JIS K 6854 and JIS K 6850 set.

example 1

A copolymer resin of an olefin and an epoxy-containing acrylate (Rexpearl; a product of Nippon Petrochemicals Co., Ltd.), a butyl rubber (Butyl; a product of Exxon), a copolymer of an olefin and an acrylic ester (Rexlon; a product of Nippon Petrochemicals Co., Ltd.) and a polyoctenylene resin (Vestenamer 8012; a product of Huls) were mixed together in the proportions as shown in Table 1, and the mixture was melted and kneaded in an ordinary Banbury mixer and then pelletized. The pellets were formed into a 60 µm thick film using an ordinary T-shape extruder. To evaluate the adhesive properties, this film was sandwiched between two iron sheets at 200 ° C to form a composite using an ordinary press molding machine. The test piece thus formed was kept in an air-conditioned room at a temperature of 23 ° C and a relative humidity of 50% for 3 days to measure the T-peeling strength, bending shear strength and the operational damping thereof. The results are shown in Table 1 and Fig. 1.

Example 2

A butyl rubber (butyl; a product of Exxon), a copolymer of an olefin and an acrylic ester (Rexlon; a product of Nippon Petrochemicals Co., Ltd.) and a polyoctenylene resin (Vestennamer 8012; a product of Hüls) were mixed together in proportions, as shown in Table 1, and the mixture was kneaded by rolling and then pelletized with a normal rubber shredder. A 60 µm thick multilayer film comprising three layers is a 15 µm thick layer of a copolymer of an olefin and an epoxy-containing acrylate, a 30 µm thick layer of a rubbery resin comprising a butyl rubber, a copolymer of an olefin and an acrylic ester and a polyoctenylene resin, and a 15 µm thick layer of a copolymer of an olefin and an epoxy-containing acrylate, in which the copolymer layers form the outer layers, was made from the pellets prepared above and a copolymer resin of an olefin and an epoxy-containing acrylate ( Rexpearl; a product of Nippon Petrochemicals Co., Ltd.) made with an ordinary filler extruder for multilayer films. The formed multilayer film was then inserted between two sheets of iron at 200 ° C to form a composite using a press molding machine. The test piece thus formed was kept in an air-conditioned room at a temperature of 23 ° C and a relative humidity of 50% for 3 days to measure the T-peeling strength, the bending shear strength and the operational damping thereof. The results are shown in Table 1 and Fig. 3.

Comparative Example 1

The T-peel strength, flexural shear strength and operational damping of comparative test pieces were measured in the same manner as in Example 1, except that the polyoctenylene resin was omitted. The results are shown in Table 1 and Fig. 3. As can be seen from the results, the moldability was poor.

Comparative Example 2

The T-peeling strength, bending shear strength, and operational damping of a comparative test piece were measured in the same manner as in Example 2, except that the copolymer resin of an olefin and an epoxy-containing acrylate was omitted. The results are shown in Table 1 and Fig. 3.

Example 3

The T-peel strength, flexural shear strength and operational damping of test pieces were measured in the same manner as in Example 2, except that when the copolymer was formed from an olefin and an epoxy-containing acrylate together with the butyl rubber, the copolymer from an olefin and an Acrylic ester and the polyoctenylene resin into a multilayer film, the copolymer of an olefin and an epoxy-containing acrylate was first molded into two 10 µm thick films by a normal T-shape extruder and a 30 µm thick film comprising a butyl rubber, a copolymer of a Olefin and an acrylic ester and a polyoctenylene resin for lamination were interposed therebetween, thereby forming a multilayer film. The results are shown in Table 1 and Fig. 1.

Table 1

Example 4

A copolymer resin of an olefin and an epoxy-containing acrylate (Rexpearl; a product of Nippon Petrochemicals Co., Ltd.), a butyl rubber (Butyl; a product of Exxon) and a polyoctenylene resin (Vestenamer 8012; a product of Hüls) were used in proportions, as shown in Table 2, mixed together, and the mixture was melted and kneaded in an ordinary Banbury mixer, and then pelletized. The pellets were formed into 60 µm thick films using an ordinary T-shape extruder. To evaluate the adhesive property, this film was inserted at 200 ° C between two iron sheets to form a composite using an ordinary press molding machine. The test piece thus formed was then kept in an air-conditioned room at a temperature of 23 ° C and a relative humidity of 50% for 3 days to measure the T-peeling strength, the bending shear strength and the operational damping thereof. The results are shown in Table 2 and Fig. 4.

Example 5

A butyl rubber (butyl; a product of Exxon) and a polyoctenylene resin (Vestenamer 8012; a product of Hüls) were mixed together in the proportions as shown in Table 2, and the mixture was kneaded by rolling and then pelletized with an ordinary rubber shredder. A 60 µm thick multilayer film comprising three layers, that is a 15 µm thick layer of a copolymer of an olefin and an epoxy-containing acrylate, a 30 µm thick layer of a rubbery resin comprising a butyl rubber and a polyoctenylene resin and a 15 µm thick A layer of a copolymer of an olefin and an epoxy-containing acrylate, in which the copolymer layers form the outer layers, was prepared from the above pellets and a copolymer resin of an olefin and an epoxy-containing acrylate by means of a conventional multi-layer film filler. The multilayer film formed was then inserted between two sheets of iron at 200 ° C to form a composite by means of a press molding machine. The test piece thus formed was kept in an air-conditioned room at a temperature of 23 ° C and a relative humidity of 50% for 3 days to measure the T-peeling strength, bending shear strength and operational damping thereof. The results are shown in Table 2 and Fig. 4.

Comparative Example 3

The T-peel strength, flexural shear strength and operational damping of comparative test pieces were measured in the same manner as in Example 4, except that the polyoctenylene resin was omitted. The results are shown in Table 2 and Fig. 4. As can be seen from the results, the formability was very poor.

Comparative Example 4

The T-peeling strength, flexural shear strength, and operational damping of comparative test pieces were measured in the same manner as in Example 5, except that the copolymer resin of an olefin and an epoxy-containing acrylate was omitted. The results are shown in Table 2 and Fig. 4.

Example 6

The T-peel strength, flexural shear strength and operational damping of test pieces were measured in the same manner as in Example 5, except that when the copolymer of an olefin and an epoxy-containing acrylate was molded together with the butyl rubber and the polyoctenylene resin into a multilayer film, the copolymer from an olefin and an epoxy-containing acrylate was previously formed into 10 µm thick films by an ordinary T-shape extruder and a 30 µm thick film including a butyl rubber and a polyoctenylene resin was interposed for lamination, thereby forming a multilayer film. The results are shown in Table 2 and Fig. 4.

Table 2

Claims (4)

1. Vibration-damping sheet comprising two Metal slats and an intermediate layer between the two metal slats is inserted, containing one A rubber composition comprising a butyl rubber, Polyoctenylene and a copolymer of an olefin and one epoxy-containing acrylic ester. 2. Sheet according to claim 1, characterized in that the Rubber composition further a copolymer of a Contains olefin and an acrylic ester.   3. Sheet according to claim 1, characterized in that it is the two Includes metal fins and three intermediate layers, the comprise two outer layers of the three intermediate layers a copolymer of an olefin and an epoxy Acrylic ester, the other, between the two outer layers inserted layer contains a butyl rubber and Polyoctenylene. 4. sheet according to claim 1, characterized in that it is the two Includes metal fins and three intermediate layers, wherein the two outer layers of the three intermediate layers comprise a copolymer of an olefin and a epoxy-containing acrylic ester, the other, between the two outer layer contains a layer Butyl rubber, polyoctenylene and a copolymer of one Olefin and an acrylic ester.