JP2846415B2 - Vibration damping composite metal plate - Google Patents

Description

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

[Conventional technology and its problems]

In recent years, along with the tightening of noise regulations for houses, automobiles, etc., various methods have been studied as countermeasures, but the tendency to use damping materials mainly for sound sources or parts that sound due to the vibration of these sound sources is increasing. Heretofore, various vibration damping composite metal plates have been proposed.

For example, Japanese Patent 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. This utilizes a known fact that vibration energy is absorbed as heat energy. This viscoelastic resin changes its viscoelasticity sensitively with the change of temperature, and it is expected that the vibration damping ability will be lost depending on the temperature range during use.

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 and an asphalt type is considered to be effective. However, these have sufficient vibration damping ability, but have poor adhesion to a metal plate and poor workability for being sandwiched between two metal plates, and must be completely satisfied up to the present. No material found.

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.

[Means for solving the problem]

Therefore, the present inventors have interposed a resin composition in which the above-mentioned disadvantages of the viscoelastic substance have been improved between metal plates, and made intensive studies to produce a vibration damping composite metal plate having high vibration damping ability. Reached.

That is, the present invention provides a rubber-based resin composition obtained by mixing an olefin / epoxy group-containing acrylate copolymer with butyl rubber, an olefin / acrylate copolymer and a polyoctenylene resin as an intermediate layer between two metal plates. A vibration-damping composite metal plate characterized by having a vibration-damping ability over a wide temperature range; and a rubber-based resin layer comprising butyl rubber, olefin / acrylate copolymer and polyoctenylene resin;
A vibration damping composite metal plate characterized by having a multilayer film or sheet composed of an epoxy group-containing acrylate copolymer resin layer as an intermediate layer and being adhered between two metal plates, and having a vibration damping ability over a wide temperature range. To provide.

The olefin / epoxy group-containing acrylate copolymer used in the present invention is obtained by copolymerizing or graft-polymerizing an olefin and an epoxy-containing acrylate by a commonly used known method. Is more preferably in the range of 1 to 25% by weight. If the epoxy group-containing acrylate content is less than 0.1% by weight, sufficient adhesiveness cannot be obtained.
Poor compatibility with the acrylate copolymer and polyoctenylene resin, and sufficient mechanical strength cannot be obtained.

The butyl rubber used in the present invention is a chemically stable rubber produced by blending a small amount of isoprene monomer with isobutylene monomer and copolymerizing the mixture by cationic polymerization. These include chlorinated chlorobutyl rubber, brominated bromobutyl rubber, and the like.

The olefin / acrylate copolymer used in the present invention is obtained by blending a small amount of an acrylate or methacrylate with an olefin monomer such as ethylene, propylene or butylene, and copolymerizing the mixture by a known method. The acrylate or methacrylate content is preferably in the range of 1 to 50% by weight,
More preferably, it is in the range of 3 to 30% by weight. If the ester content is 1% by weight or less, sufficient strength cannot be obtained, and if it is 50% by weight or more, compatibility with butyl rubber and oriooctenylene resin is poor, and sufficient mechanical strength cannot be obtained.

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

Various methods can be used for synthesizing cyclooctene, which is a base material of 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 a face wash, various stabilizers, a filler,
Plasticizers, antioxidants, ultraviolet absorbers, nucleating agents, antistatic agents, flame retardants, and the like can be added as necessary.

Also, among these additives, butyl rubber, olefin / acrylate copolymer and polyoctenylene resin for peroxides, sulfur compounds, phenol resins,
Also included are ordinary vulcanizing agents for rubber, such as process oils and alicyclic epoxy resins, vulcanization accelerators, and various additives.

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

Further, the rubbery resin comprising the olefin / epoxy group-containing acrylate copolymer, butyl rubber, olefin / acrylic ester copolymer and polyoctenylene resin of the present invention can be prepared by using a conventionally known T-die film production apparatus or blown film production apparatus After being used to form a film or sheet, it is sandwiched between two metal plates and heated and compressed for bonding. A casting film can also be formed directly on a metal plate by a casting method. The film or sheet at that time is 10 μm to 1 mm, especially 20 to 1 mm.
Those having a thickness of 50 μm are preferred.

The rubbery resin comprising the olefin / epoxy-containing acrylate copolymer, butyl rubber, olefin / acrylate copolymer 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. In addition to the method of forming a film or a sheet after that, a co-extrusion molding machine may be used to directly form a two-layer or multilayer film. At that time, between a metal plate and a rubber-like resin film composed of butyl rubber, olefin / acrylate copolymer and polyoctenylene resin,
When an olefin / epoxy group-containing acrylate copolymer is interposed as an adhesive layer film, this multi-layer film has good adhesion to the metal plate, but does not cause blocking between the film surfaces. This is preferable because it is easy.

As 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 including the metal plates,
For example, a stainless steel plate or the like can be used. The thickness of these metal plates is not particularly limited as long as it is within a range where secondary processing such as bending and squeezing of the obtained vibration-damping composite metal plate is not particularly limited, but is generally 0.01 to 5 mm in thickness. Should be fine. These metal plates are commercially available, but since they generally have fats and oils attached thereto, it is preferable to use degreased ones, and any conventionally known degreasing method may be used.

The method for producing a vibration-damping composite metal plate according to the present invention includes a rubber-like resin comprising an olefin / epoxy group-containing acrylate copolymer, butyl rubber, an olefin / acrylate copolymer and a polyoctenylene resin between the same or different metal plates. It is preferable to interpose a film or a sheet and heat-compress it using a compression molding machine or a roll. At this time, it is possible to adopt various methods such as a method of cutting the metal plate and the rubber-like resin into an appropriate size and shape convenient for the next secondary processing and then bonding them, and a continuous manufacturing method shown in FIG. it can.

FIG. 1 is a schematic view showing a continuous production method of a vibration damping composite metal plate according to the present invention. In FIG. 1, 1,1 'is a metal plate, 2,
2 ', 3,3' are rolls, 4,4 ', 8 are levelers, 5,5' are preheating steps, 6,6 'are rolls, 9 is a reheating step, 10 is a first cooling step, and 11 is a This is a two-cooling step. 12,13 are slitters,
7 is a rubber-like resin film, and 14 is a vibration damping composite metal plate as a product.

In FIG. 1, the metal plates 1, 1 'pass through the rolls 2, 3, 2', 3 ', pass through the preheating steps 5, 5', sandwich the rubber-like resin film 7 between the rolls 6, 6 ', and The resin film is pressure-bonded. Thereafter, the reheating step 9 strengthens the bonding of the two, passes through the first cooling step 10 and the second cooling step 11, passes through the slitters 12 and 13, and becomes a vibration damping composite metal plate 14 as a product.

When the metal plate is manufactured by the continuous manufacturing method shown in FIG. 1, it is preferable to degrease the metal plate in advance as shown in FIG.

FIG. 2 is a schematic view showing a continuous degreasing process of a metal plate.
In FIG. 2, 15 is a roll, 16 and 18 are electrolyte layers, 17 is a positive electrode plate, 19 is a negative electrode plate, 20 is a power supply, 21 is a washing process, 22 is a drying process, 23 is a metal plate before degreasing, 24 shows a metal plate after degreasing.

In FIG. 2, the metal plate 23 before degreasing passes through a roll 15 through an electrolytic bath 16 containing a positive electrode plate 17 and an electrolytic bath 18 containing a cathode electrode plate 19, and is electrically degreased. It becomes a degreased metal plate 24 after a water washing process 21 and a drying process 22,
The vibration damping composite metal plate of the present invention is provided for production.

〔The invention's effect〕

The vibration damping composite metal plate provided by the present invention,
In addition to exhibiting good vibration damping properties over a wide temperature range, the intermediate layer olefin / epoxy group-containing acrylate copolymer, butyl rubber, olefin / acrylate copolymer and polyoctenylene resin rubber-like resin can be formed into a film or Since it is easy to form a sheet, the compounding process becomes very simple, and shows good adhesion to a metal plate.

〔Example〕

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition,
The adhesiveness between the resin and the metal was evaluated by the degree of adhesion, T peel strength was measured according to JIS K 6854, and tensile shear strength was measured according to JIS K 6850.

Example 1 Olefin / epoxy group-containing acrylate copolymer resin (Nippon Petrochemical Co., Ltd. Lexpearl), butyl rubber (Exxon Co., Ltd. butyl), olefin / acrylate copolymer (Nippon Petrochemical Co., Ltd. Lexlon) and polyoctenylene The resin (VESTENAMER8012 manufactured by Hls) was blended in an amount shown in Table 1, melt-kneaded with an ordinary Banbury mixer, and pelletized. Using this pellet, normal T-
A 60 μm thick film was formed using a die extruder.
This film was used for evaluation of adhesiveness, sandwiched between two iron plates at 200 ° C. using a normal press molding machine and bonded by a press molding machine to obtain a vibration-damping composite metal plate of the present invention.

The test piece was left in an air conditioning room at 23 ° C. and 50% RH for 3 days, and then the T-peel strength, the tensile shear strength and the loss factor were measured.

 The results are shown in Table 1 and FIG.

Example 2 Butyl rubber (butyl manufactured by Exxon), olefin / acrylate copolymer (Lexlon manufactured by Nippon Petrochemical Co., Ltd.) and polyoctenylene resin (VESTENAMER80 manufactured by Hls)
12) was blended in the amount shown in Table 2, kneaded with a roll, and formed into pellets using a usual rubber cutter.
Using these pellets, olefin / epoxy group-containing acrylate copolymer resin (Nippon Petrochemical Co., Ltd. Lexpearl)
A rubber system consisting of a 1.5 μm thick olefin / epoxy group-containing acrylate copolymer layer, a 30 μm thick butyl rubber, an olefin / acrylate copolymer and a polyoctenylene resin, using a conventional multilayer film inflation extruder. A 60 μm-thick multilayer film comprising a resin layer and an olefin / epoxy group-containing acrylate copolymer layer having a thickness of 1.5 μm and having an olefin / epoxy group-containing acrylate copolymer layer as an outer layer was formed. Next, the multilayer film was sandwiched between two iron plates at 200 ° C. and bonded by a press molding machine to obtain a vibration damping composite metal plate of the present invention.

The test piece was left in an air conditioning room at 23 ° C. and 50% RH for 3 days, and then the T-peel strength, the tensile shear strength and the loss factor were measured.

 The results are shown in Table 1 and FIG.

Comparative Example 1 The procedure of Example 1 was repeated, except that the polyoctenylene resin was not blended.
Tensile shear strength and loss factor were measured.

The results are shown in Table 1 and FIG. 3, but the molding workability was very poor.

Comparative Example 2 Example 2 was repeated except that the olefin / epoxy group-containing acrylate copolymer resin was not used.
The T-peel strength and the tensile shear strength were measured in exactly the same manner as described above.

 The results are shown in Table 1 and FIG.

Example 3 In Example 2, when forming a multilayer film together with butyl rubber, an olefin / acrylate copolymer and a polyoctenylene resin, a conventional T-die extruder was previously used using an olefin / epoxy group-containing acrylate copolymer. To form two 10 μm thick films,
30 μm consisting of butyl rubber, olefin / acrylate copolymer and polyoctenylene resin between them
Except that the film is sandwiched and laminated to form a multilayer film, the same as in Example 2,
The T peel strength, tensile shear strength and loss factor were measured.

 The results are shown in Table 1 and FIG.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a continuous production method of a vibration damping composite metal plate of the present invention, FIG. 2 is a schematic diagram showing a continuous degreasing process of a metal plate, and FIG. 3 is a vibration diagram obtained in Examples and Comparative Examples. It is a graph which shows the temperature dependence of the loss coefficient of a damping composite metal plate. 1,1 '... Metal plate 2,2', 3,3 '... Roll 4,4', 8 ... Leveler 5,5 '... Preheating process 6,6' ... Roll 7 ... Rubber resin Film 9: reheating step 10: first cooling step 11: second cooling step 12, 13: slitter 14: vibration-damping composite metal plate of the present invention 15: roll 16, 18: electrolytic solution Tank 17 Positive electrode plate 19 Negative electrode plate 20 Power supply 21 Rinsing process 22 Drying process 23 Metal plate before degreasing 24 Metal plate after degreasing

Claims (2)

(57) [Claims] (1) butyl rubber, olefin / acrylate copolymer and polyoctenylene resin
A vibration damping composite characterized in that a rubber resin composition containing an epoxy group-containing acrylate copolymer is bonded as an intermediate layer between two metal plates and has a vibration damping ability over a wide temperature range. Metal plate. 2. A multilayer film or sheet comprising a rubber-based resin layer comprising butyl rubber, an olefin / acrylate copolymer and a polyoctenylene resin and an olefin / epoxy group-containing acrylate copolymer resin layer as an intermediate layer between two metal plates. A vibration-damping composite metal plate, which is adhered to and has a vibration-damping ability over a wide temperature range.