JP2520002B2 - Vibration damping composite metal plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a rubber composition composed of a butyl rubber and a polyoctenylene resin in a film form or a sheet form between two metal plates and an olefin / epoxy group-containing acrylate copolymer. The present invention relates to a vibration-damping composite metal plate having a rubber-based resin composition mixed therein and having a vibration damping ability in a wide temperature range.

<Prior art and problems> In recent years, various methods have been studied as a countermeasure against the tightening of noise regulations for houses, automobiles, etc., but damping materials are mainly used for sound sources or parts that are generated by the vibration of these sound sources. There is an increasing tendency to do so, and various vibration damping composite metal plates have been proposed so far.

For example, Japanese Examined Patent Application Publication No. 39-12451 discloses a vibration damping metal plate having an intermediate layer of a copolymer such as vinyl acetate and maleic acid diester, vinyl chloride and ethylhexyl acrylate, which uses a resin having viscoelasticity. It utilizes the known fact that vibration energy is absorbed as heat energy. It is also expected that the viscoelasticity of the resin having this viscoelasticity changes sensitively as the temperature changes, and the vibration damping ability disappears in the operating temperature range.

In general, the vibration absorbing performance can be expressed by a physical quantity that is a loss coefficient, and it is said that if the value is 0.05 or more, there is an effect as a vibration absorbing material. As such a material, a viscoelastic substance such as a rubber type, a copolymer resin type or an asphalt type is considered to be effective. However, even though they have sufficient vibration damping ability, they have poor adhesion to a metal plate and poor workability for sandwiching between two metal plates, so they should be completely satisfied to the present day. The material is missing.

Butyl rubber, on the other hand, has a very good vibration damping ability due to its high hysteresis properties, and is ideal for improving the impact strength of other materials at low temperatures, but it has good moldability, compatibility, adhesion, etc. Has difficulties.

Therefore, the present inventor diligently studied to make a vibration-damping composite metal plate having a high vibration-damping ability by interposing a resin composition in which the various drawbacks of the viscoelastic substance are improved between the metal plates. Arrived

<Means for Solving the Problems> That is, according to the present invention, a rubber-based resin composition obtained by blending butyl rubber and a polyoctenylene resin with an olefin / epoxy group-containing acrylate copolymer is bonded between two metal plates as an intermediate layer. And a vibration damping composite metal plate having a vibration damping ability in a wide temperature range, and a multi-layer film composed of a rubber resin layer made of butyl rubber and polyoctenylene resin and an olefin / epoxy group-containing acrylate copolymer resin layer. Alternatively, it is a vibration-damping composite metal plate which is formed by adhering a sheet as an intermediate layer between two metal plates and has a vibration damping ability in a wide temperature range.

The olefin / epoxy group-containing acrylate copolymer used in the present invention is obtained by copolymerizing or grafting an olefin and an epoxy group-containing acrylate by a commonly used known method, and the epoxy group-containing acrylate content is 0.1 to 45%. It is preferably in the range, and more preferably in the range of 1 to 25%. If it is 0.1% or less, sufficient adhesiveness cannot be obtained, and if it is 45% or more, compatibility with butyl rubber and polyoctenylene resin is poor and sufficient mechanical strength cannot be obtained.

The butyl rubber used in the present invention is a chemically stable rubber produced by mixing a small amount of isoprene monomer with isobutylene monomer and copolymerizing the same by cationic polymerization. Among these, chlorinated chlorobutyl rubber and brominated chlorobutyl rubber are also included.

The polyoctenylene resin used in the present invention is obtained by polymerizing cyclooctene, has one double bond per eight carbon atoms, has a molecular weight of 10,000 or more, and has a trans content of 50%. At least, preferably at least 60%,
The crystallinity is preferably in the range of 10% or more. Further, the polyoctenylene resin has a melting point of usually 40 ° C. or higher, preferably in the range of 50 ° C. to 60 ° C., and has a glass transition point of −
It is preferably in the range from 75 ° C to -30 ° C.

Although various methods can be adopted as a method for synthesizing cyclooctene, which is a base material constituting the polyoctenylene resin, for example, after dimerizing butadiene, one of the remaining two double bonds is hydrogenated. It is obtained by doing.

The rubber-like resin composition, which is the intermediate layer of the vibration-damping composite metal plate in the present invention, includes dyes and pigments, various stabilizers, fillers,
If necessary, a plasticizer, an antioxidant, an ultraviolet absorber, a nucleating agent, an antistatic agent, a flame retardant, etc. may be added. Further, among these additives, vulcanizing agents for rubber such as peroxides, sulfur compounds and process oils for butyl rubber and polyoctenylene resins, vulcanization accelerators, and various known additives are also included. .

The resin composition of the present invention is prepared by melt-mixing with various methods such as a roll and an extruder. For example, the olefin / epoxy group-containing acrylate copolymer may be melted and the remaining butyl rubber and polyoctenylene resin may be added thereto, or the three components may be mixed at the same time. At any of these stages, the above additives, for example, fillers, plasticizers, antioxidants and the like can be added as necessary. Alternatively, the three components may be dissolved in an appropriate organic solvent and mixed in a solution.

Furthermore, the rubber-like resin made of the resin comprising the olefin / epoxy group-containing acrylate copolymer of the present invention, butyl rubber and polyoctenylene resin can be formed into a film or sheet by using a conventionally known T-die film manufacturing apparatus or inflation film manufacturing apparatus. After molding, the two metal plates are sandwiched and bonded by thermocompression bonding. Further, the casting film can be directly formed on the metal plate by the casting method. In that case, the film or sheet preferably has a thickness of 10 μm to 1 mm, particularly 20 to 150 μm.

Further, the rubber-like resin comprising the olefin / epoxy group-containing acrylate copolymer, butyl rubber and polyoctenylene resin, which is the intermediate layer of the vibration damping composite metal plate of the present invention, is melt-mixed by various methods and then formed into a film or sheet. Alternatively, a coextrusion molding machine may be used to directly form a two-layer or multi-layer film. At that time, it is preferable to interpose an olefin / epoxy group-containing acrylate copolymer as an adhesive layer between the metal plate and the rubber-like resin made of butyl rubber and polyoctenylene resin.

The metal plate used in the present invention, iron, nickel,
Metal plates such as titanium, aluminum, magnesium, copper, zinc and tin, and various alloy plates mainly composed of the metal plate,
For example, a stainless steel plate may be used. The thickness of these metal plates is not particularly limited as long as it is within a range in which secondary processing such as bending and squeezing of the obtained vibration damping composite metal plate can be performed, but generally a thickness of 0.01 to 5 mm If These metal plates are commercially available, but since fats and oils are generally attached to them, it is preferable to use degreased ones, and any degreasing method known in the art may be used.

As the method for producing the vibration damping composite metal plate in the present invention, a film or sheet of a rubber-like resin composed of an olefin / epoxy group-containing acrylate copolymer, butyl rubber and polyoctenylene resin is interposed between the same or different metal plates, It is preferable to heat and compress the above using a compression molding machine or a roll. At that time, it is possible to adopt various methods such as a method of cutting the metal plate and the rubber-like resin into a suitable size and shape convenient for the next secondary processing and then adhering them, a continuous manufacturing method shown in FIG. it can. In the case of manufacturing by the continuous manufacturing method of FIG. 1, it is more preferable to degrease the metal plate in advance in the process as shown in FIG. 2 because good adhesiveness can be obtained.

<Effects of the Invention> The vibration damping composite metal plate provided by the present invention is
Not only does it show good vibration damping properties over a wide temperature range, but the rubber-like resin consisting of olefin / epoxy group-containing acrylate copolymer, butyl rubber and polyoctenylene resin in the intermediate layer is easy to form into a film or sheet, so
The composite processing becomes very easy and good adhesion is exhibited.

<Examples> Next, the present invention will be specifically described with reference to Examples. The adhesiveness between the resin and the metal was evaluated by the adhesive strength, T peel strength was measured according to JIS K6854, and tensile shear strength was measured according to JIS K6850.

Example 1 Olefin / epoxy group-containing acrylate copolymer resin (Lexpearl manufactured by Nippon Petrochemical Co., Ltd.), butyl rubber (butyl manufactured by Exxon), and polyoctenylene resin (HI)
VESTENAMER8012) manufactured by s Co., Ltd. was blended as shown in Table 1, melt-kneaded and pelletized by an ordinary Banbury mixer. Using this pellet, the thickness can be
A 60 μm film was molded. Use this film to evaluate the adhesiveness, and use a normal press molding machine at 200 ° C for 2
The sheets were sandwiched between iron plates and laminated by a press molding machine. These test pieces were allowed to stand in an air-conditioned room at 23 ° C. and 50% RH for 3 days, and then T peel strength, tensile shear strength and loss coefficient were measured.
The results are shown in Table 1 and FIG.

Example 2 Butyl rubber (Butyl manufactured by Exxon) and polyoctenylene resin (VESTENAMER8012 manufactured by Hls) were blended as shown in Table 1, kneaded by a roll, and then molded into pellets using a usual rubber cutting machine. These pellets were used together with an olefin / epoxy group-containing acrylate copolymer resin (Nippon Petrochemical Co., Ltd., Lexpearl) to form a 15 μm thick olefin /
Epoxy group-containing acrylate copolymer layer, 30 μm thick butyl rubber and polyoctenylene rubber-based resin layer, 15 μm thick olefin / epoxy group-containing acrylate copolymer layer 3 layers, olefin / epoxy group-containing acrylate 60μ thickness with the outer layer of the copolymer layer
m multilayer film was formed. Next, this multilayer film was sandwiched between two iron plates at 200 ° C. and laminated by a press molding machine. These test pieces were allowed to stand in an air-conditioned room at 23 ° C. and 50% RH for 3 days, and then T peel strength, tensile shear strength and loss coefficient were measured. The results are shown in Table 1 and FIG.

Comparative Example 1 In the same manner as in Example 1 except that the polyoctenylene resin was not added, the T peel strength,
Tensile shear strength and loss factor were measured. The results are shown in Table 1 and FIG. 3, but the molding workability was extremely poor.

Comparative Example 2 Example 2 except that the olefin / epoxy group-containing acrylate copolymer resin was not blended.
The T peel strength and the tensile shear strength were measured in exactly the same manner as in. The results are shown in Table 1 and FIG.

Example 3 In Example 2, when forming a multilayer film with butyl rubber and polyoctenylene resin, an olefin / epoxy group-containing acrylate copolymer was previously added with a conventional T
-Examples except that two types of films having a thickness of 10 µm are formed by using a die extruder, and a 30 µm film made of butyl rubber and polyoctenylene resin is sandwiched between them to form a multilayer film. The T peel strength, tensile shear strength and loss factor were measured in exactly the same manner as in 2. The results are shown in Table 1 and FIG.

[Brief description of drawings]

FIG. 1 shows a continuous method for producing a vibration-damping composite metal plate, FIG. 2 shows a continuous degreasing process for a metal plate, and FIG.
It is a result which shows the temperature dependence of the loss coefficient of the material used in Comparative Examples 1-2. 1, 1,1 'is a metal plate, 2,2', 3,3 'is a roll, 4,4', 8 is a leveler, 5,5 'is a preheating process, 6,6' is a roll, and 9 is a roll. Is a reheating step, 10 is a first cooling step, 11 is a second cooling step, 12 and 13 are slitters, 7 is a rubber-like resin film, and 14 is a vibration damping composite metal plate as a product. In FIG. 2, 15 is a roll, 16 and 18 are electrolytic solution tanks, 17 is a positive electrode plate, 19 is a negative electrode plate, 20 is a power source, 21 is a washing process, 22 is a drying process, and 23 is a metal plate before degreasing. , 24 shows the metal plate after degreasing.

Claims (2)

(57) [Claims] 1. A rubber-based resin composition obtained by blending a butyl rubber and a polyoctenylene resin with an olefin / epoxy-containing acrylate copolymer having an epoxy-containing acrylate content of 0.1 to 45% is bonded as an intermediate layer between two metal plates. The vibration damping composite metal plate is characterized by having a vibration damping ability in a wide temperature range. 2. A resin layer made of butyl rubber and polyoctenylene resin and having an epoxy-containing acrylate content of 0.1.
~ 45% olefin / epoxy-containing acrylate copolymer resin layer is a multilayer film or sheet as an intermediate layer, which is bonded between two metal plates and has a vibration damping ability in a wide temperature range. Damping composite metal plate.