JPH0791490A - Viscoelastic composition for damping material and resin complex type damping metallic sheet using the composition - Google Patents

Abstract

PURPOSE:To provide a viscoelastic resin composition for a damping material which has excellent adhesive properties and damping properties and excellent capability to be manufactured into a resin complex type metallic sheet and to provide a resin complex type metallic sheet using the composition. CONSTITUTION:A viscoelastic resin composition for a damping material is prepared such that at least one or more kinds of inorganic power components on which surface treatment is applied by using a titanate coupling agent or an aluminum coupling agent. The viscoelastic resin composition for a damping material of which a viscoelastic resin layer consists is a resin complex type damping metal containing at least one or more kinds of inorganic powder components on which surface treatment is applied by using a titanate coupling agent or an aluminum coupling agent. Thus, by the viscoelastic resin composition for a damping material, a high adhesive strength is compatible with high damping properties and desides, in a resin solution agitating process during manufacture of a resin complex type metallic sheet, an inorganic powder component is not aggregated and the sheet has excellent capability to be manufactured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to machines, buildings, vehicles,
In a composite damping material having a laminated structure used as a structural member for home electric appliances or a part thereof, a viscoelastic resin composition for a vibration damping material for forming a viscoelastic resin layer thereof, or a resin using the same The present invention relates to a composite type vibration damping metal plate.

[0002]

2. Description of the Related Art In recent years, with the development of transportation and the approach of houses to factories, the problems of noise and vibration have become social problems as pollution, and also for the purpose of improving the working environment in the workplace. It tends to regulate noise and vibration. Corresponding to such a tendency, the vibration damping performance of the metal material that is the noise source or the vibration source, that is, the vibration energy of the member itself that generates noise is exchanged for thermal energy, and the vibration speed or vibration amplitude is attenuated. Therefore, it is required to provide a function of reducing acoustic emission and further improve the function.

Based on such a demand, a composite type damping material having a laminated structure in which an intermediate layer having viscoelasticity is sandwiched between metal layers has been proposed as one of the damping materials exhibiting such performance. There is. This composite vibration damping material is a precision vibration damping member for automobile oil pans, engine covers, dash panels, chute parts of hoppers, home appliances, stoppers of transportation equipment, and other metal working machines, and vibration prevention. It has been studied and used in structural members of equipment.

Generally, the damping performance of such a composite damping material depends on the performance of the viscoelastic resin layer forming the intermediate layer thereof. When this damping performance is expressed by a loss coefficient, it is known that this damping performance exhibits a peak characteristic at a certain constant temperature, and that it is most effective to use in the vicinity of this peak characteristic temperature. Further, a resin having a low glass transition point has a low adhesive strength by itself, and therefore, in applications where high adhesiveness is required, an inorganic powder component is blended in the viscoelastic resin layer of the resin composite type vibration damping metal plate. It corresponds by that.

Conventionally, as a viscoelastic resin composition which constitutes the viscoelastic resin layer of such a composite type vibration damping material, polyester alone (Japanese Patent Laid-Open No. 50-143,880) or polyester is added with plasticity. Thing (JP-A-51-
No. 93,770), a polyurethane foam alone (JP-A-51-91,981), a polyamide alone (JP-A-56-159,160), an ethylene-vinyl acetate copolymer alone (JP-A-51). 57-34,949), polyvinyl butyral or a composition of polyvinyl butyral and polyvinyl acetate with a plasticizing or tackifying substance (Japanese Patent Publication No. 55-27,975), isocyanate prepolymer and vinyl. Copolymer of monomers (Japanese Patent Publication No. 55-27,975) or Japanese Patent Publication No. 3
The copolymers shown in 9-12,451, JP-B-45-34,703 and JP-B-62-74,645 are known.

[0006]

By the way, in the vibration damping resin solution of the resin composite type vibration damping metal plate, when the inorganic powder is mixed, the inorganic powder tends to settle and aggregate during long-term storage. . Further, when the resin composite type vibration damping metal plate is manufactured, if the viscosity of the vibration damping resin solution used is low, the inorganic powder will settle out as in the case of storage, and in the vibration damping metal plate manufacturing equipment such as a flow coater. Such a low-viscosity damping resin solution cannot be used. Furthermore, even when using a vibration damping metal plate manufacturing facility such as a roll coater to use a high-viscosity vibration-damping resin solution, it is necessary to constantly stir the resin solution in order to prevent precipitation of the inorganic powder. Also. The once settled inorganic powder is caked during storage and cannot be redispersed by simple stirring.

On the other hand, even in the step of producing the vibration damping resin solution for the resin composite type vibration damping metal plate, it is difficult to mix the inorganic powder component when it is mixed, and it takes a long time to produce the vibration damping resin solution. Requires. In addition, the inorganic powder component generally has hygroscopicity and may bring water into the vibration damping resin solution. Furthermore, the inorganic powder component varies depending on the production lot, and when mixed with the resin, it also affects the resin characteristics.

In view of such circumstances, the present inventors firstly perform various surface treatments on the inorganic powder component for the purpose of preventing the tendency of the inorganic powder to aggregate and caking during storage. Along with the investigation, the viscoelastic resin composition for a vibration damping material, to which at least one kind of the surface-treated surface-treated inorganic powder component was added, was earnestly studied.

Further, in the conventional technique, the adhesive strength of the resin alone is low, and in applications where high adhesiveness is required,
Since it is dealt with by adding an inorganic powder component to the viscoelastic resin layer of the resin composite type vibration-damping metal plate, the adhesive strength at room temperature is also high in the present invention (for example, shear adhesive strength of 80 kgf / cm ² or more). ) In addition, it is necessary that the viscoelastic resin composition for a vibration damping material has a high vibration damping performance at around room temperature (for example, a loss coefficient of 0.2 or more). The present invention has been completed by repeating the above.

Therefore, an object of the present invention is to add a viscoelastic resin composition for a vibration damping material, which contains an inorganic powder component and is capable of preventing the aggregation and caking of the inorganic powder during storage as much as possible. To provide. Further, another object of the present invention is to add an inorganic powder component to a viscoelastic resin to exhibit excellent adhesive strength at room temperature, and also a viscoelastic resin for vibration damping materials that exhibits excellent vibration damping performance at around room temperature. To provide a composition.

Still another object of the present invention is to incorporate an inorganic powder component so as to exhibit excellent adhesive strength at room temperature and also exhibit excellent vibration damping performance at around room temperature, and further, the inorganic powder during storage. To provide a resin composite type vibration damping metal plate having a viscoelastic resin layer formed by using a viscoelastic resin composition for a vibration damping material capable of preventing the occurrence of aggregation and caking of the resin as much as possible. is there.

[0012]

Means for Solving the Problems That is, the present invention provides a viscoelastic material for a vibration damping material containing at least one surface-treated inorganic powder component surface-treated with a titanate-based coupling agent or an aluminum-based coupling agent. It is a resin composition. Further, the present invention, at least one kind of surface-treated inorganic powder component obtained by subjecting the viscoelastic resin composition for damping material constituting the viscoelastic resin layer to a surface treatment with a titanate coupling agent or an aluminum coupling agent. It is a resin composite type damping metal plate including the above.

The viscoelastic resin composition for vibration damping materials of the present invention comprises
Basically, it is composed of a viscoelastic resin and a surface-treated surface-treated inorganic powder component mixed with the viscoelastic resin. In the present invention, the viscoelastic resin is preferably amorphous from the viewpoint of improving the vibration damping property when used in the viscoelastic resin layer of the resin composite type vibration damping metal plate.

Examples of the viscoelastic resin include amorphous polyester, amorphous polyamide, polyimide, polyurethane, polyurethane urea, polyurea, acrylic resin, epoxy resin, vinyl acetate resin, amorphous polyolefin resin, Alternatively, a blend of various resins, and further a copolymer and the like can be mentioned. In the present invention, a cross-linking agent such as polyfunctional isocyanate and epoxy may be used in consideration of the flow characteristics at high temperature.

The surface-treated inorganic powder component added to the viscoelastic resin has its surface subjected to a predetermined surface treatment, and the surface treatment of the inorganic powder is generally
The purpose of the present invention is to prevent the aggregation and caking of the inorganic powder during the long-term storage of the vibration damping resin solution, although the purpose is to improve the interfacial adhesion with the resin.

Here, a wide variety of inorganic powders can be used, but calcium carbonate, talc, silica, kaolin, alumina, titanium oxide, zinc white, mica and the like are desirable characteristics. Have. That is, these inorganic powders have little effect on the glass transition point of the viscoelastic resin and do not adversely affect the vibration damping performance.

The surface treatment agent used for the surface treatment of the inorganic powder is preferably a titanate coupling agent or an aluminum coupling agent, and more specifically, a titanate coupling agent is used as a functional group. Those having an alkoxy group, those having a hydroxyl group, and those having an acetate group and pyrophosphate are preferable. Others, such as silane coupling agents, fatty acids, amines, etc., are not preferable because they are hard to re-disperse when the resin is hardened or settles.

The amount of the coupling agent used in the surface treatment of the inorganic powder with the surface treatment agent is usually 0.4 to 1.2% by weight, preferably 0.6 to
It is 1.0% by weight. If the amount of the coupling agent used is less than 0.4% by weight, the tendency of agglomeration and caking occurs as in the case of the inorganic powder that has not been surface-treated, and
When the amount of the coupling agent used exceeds 1.2% by weight, the adhesive strength when forming the resin composite type vibration damping metal plate is significantly reduced.

Further, the method of surface-treating the above-mentioned inorganic powder is not particularly limited, and a wet method, a dry method, a spray method or the like which has been conventionally used as a surface treatment method of this kind is adopted. be able to. For example, a specific method will be described by taking a case of performing surface treatment by a wet method as an example. First, an inorganic powder is dispersed in a predetermined solvent, and a specified amount of a coupling agent is added to the dispersed solution, and then, Remove the solvent in the explosion-proof constant temperature bath, and then 80 ℃
And dried for 24 hours to obtain a surface-treated surface-treated inorganic powder component. By heating the inorganic powder for surface treatment in this way, the surface-treated inorganic powder component is dried, and the moisture content is additionally stabilized at that time.
As a result, there is an advantage that the variation in characteristics when blended with the resin becomes extremely small.

Further, in the viscoelastic resin composition for vibration damping materials of the present invention, the content of the surface-treated inorganic powder component subjected to the above-mentioned surface treatment is usually 5 to 45% by weight, which gives better adhesive strength and In order to obtain vibration damping performance, preferably 10 to 4
It is 0% by weight. If the blending amount of the surface-treated inorganic powder component is less than 5% by weight, the predetermined adhesive strength cannot be obtained, and if it exceeds 45% by weight, the vibration damping performance is significantly deteriorated.

In the viscoelastic resin composition for vibration damping materials of the present invention, a metal filler for welding is added in order to impart weldability such as spot weldability to the resin composite type vibration damping metal plate obtained by using the viscoelastic resin composition. As the metal powder, nickel powder, SUS powder, chromium powder, or other metal powder can be mixed.

Further, in the present invention, a viscoelastic resin composition for vibration damping material, which is obtained by adding at least one surface-treated inorganic powder component obtained by subjecting the viscoelastic resin to a surface treatment, is laminated as an adhesive layer. It has characteristics. That is, by using the viscoelastic resin composition of the present invention obtained by adding at least one kind of surface-treated inorganic powder component obtained by subjecting a viscoelastic resin to a surface treatment as an adhesive for the composite vibration damping material, The resin composition is dissolved or suspended in an appropriate organic solvent consisting of, for example, toluene, xylene, benzene, methyl ethyl ketone, acetone, cyclohexanone, or a mixed solvent thereof to form a vibration damping resin solution, which is used as an adhesive for composite vibration damping. At the time of producing the material, it has an action of preventing the aggregation of the inorganic powder during long-term storage of the damping resin solution, and even when the surface-treated inorganic powder component is precipitated in the damping resin solution, it is easy to It can be easily redispersed by stirring.

Moreover, in the present invention, the surface-treated inorganic powder component is used as the inorganic powder to be added to the viscoelastic resin, so that the surface-treated inorganic powder component as a raw material is secondarily added. The moisture content is stabilized, and the dispersion of properties when blended with a viscoelastic resin is extremely small, and the mixing is easy during the production of the viscoelastic resin composition, so that the production time is significantly shortened. You can also do it. Further, when the vibration damping resin solution is prepared, it has an action of preventing aggregation and caking of the inorganic powder in the vibration damping resin solution, so that it can be used in equipment such as a flow coater even if the viscosity is low, It is easy to stir on the line and save electricity.

Further, the present invention is a resin composite type vibration damping metal plate using the above viscoelastic resin composition for vibration damping material as a resin composition constituting a viscoelastic resin layer. This resin composite type vibration damping metal plate is basically based on a structure in which a viscoelastic resin layer formed of the above viscoelastic resin composition for vibration damping materials of the present invention is sandwiched between two metal plates. A structure such as a body, a two-layer body including a metal plate and a viscoelastic resin layer can also be adopted.

In the present invention, various materials such as a steel plate, an aluminum plate, a titanium plate, and a copper plate can be used as the metal plate, but the metal plate is generally a steel plate, and the kind of the steel plate is also particularly limited. Not something, for example,
Surface-treated steel sheets such as phosphate-treated steel sheets, chromate-treated steel sheets, zinc-treated steel sheets, stainless steel sheets, organic coated steel sheets, and ordinary steel sheets having a degreasing surface are also used. The thickness of this metal plate is not particularly limited, either,
3.2 mm or less is desirable in order to fully exhibit the vibration damping characteristics.

Further, in the present invention, the average particle size of the surface-treated inorganic powder component subjected to the surface treatment is preferably one third or less of the thickness of the viscoelastic resin layer. If the average particle size of the surface-treated inorganic powder component exceeds one-third of the thickness of the viscoelastic resin layer, the effect on the adhesive strength becomes small, which is not preferable. This is because as the average particle diameter of the surface-treated inorganic powder component approaches the thickness of the viscoelastic resin layer, the stress concentration at the interface between the particles of the inorganic powder and the viscoelastic resin increases when the resin layer undergoes shear deformation. As a result, it is considered that the interface between the viscoelastic resin and the particles of the inorganic powder is liable to be broken, peeled or even flowed, and the adhesive strength is lowered.

[0027]

EXAMPLES The present invention will be described in more detail based on the following examples and comparative examples.

Examples 1 to 13 and Comparative Examples 1 to 7 As shown in Table 1, an epoxy cross-linked polyelter resin was used as a basic resin, and a surface-treated inorganic powder component subjected to a surface treatment was added thereto to give Examples 1 to 1. 13 and the viscoelastic resin compositions of Comparative Examples 1 to 7 were prepared.

Next, cyclohexane and xylene 1: 1
The viscoelastic resin composition of each of the examples and comparative examples obtained above was added to the mixed solution so that the resin solid content concentration was 35% by weight, and this was mixed with a homomixer at 8,000 rpm for 1 minute. After stirring under the conditions to prepare a damping resin solution, about 10 ml of this damping resin solution was transferred to a test tube and allowed to stand for 24 hours to precipitate the surface-treated inorganic powder component. afterwards,
The operation of tilting the test tube and raising it was repeated 10 times, and the redispersibility of the surface-treated inorganic powder component was evaluated by the appearance of the vibration damping resin solution at that time. The evaluation criteria at this time were expressed as ◯ when the entire resin solution was almost uniformly clouded and mixed, and as x when the transparent resin solution layer remained. Furthermore, assuming long-term storage, the test tube was allowed to stand for 30 days, and the same test was performed to evaluate redispersibility.

Further, the viscoelastic resin composition of each of the above Examples and Comparative Examples is sandwiched between two phosphate-treated steel sheets having a thickness of 0.4 mm, and a composite type vibration control having a viscoelastic resin layer having a thickness of 50 μm. I made a metal plate. Regarding the obtained composite type vibration damping metal plates of each Example and Comparative Example, the shear adhesive strength (JIS
According to K 6850, measured at 20 ± 2 ° C.), T peel strength (measured at 20 ± 2 ° C. according to JIS K6854) and vibration damping performance were measured. As the damping performance, a loss coefficient at 30 ° C. at a vibration frequency of 500 Hz was obtained by a method using mechanical impedance. The above results are shown in Table 1.

Examples 1-7 and 9-13 are samples to which surface-treated calcium carbonate was added. Example 8 is a sample to which surface-treated talc is added. Examples 1-13
In Example 2, the improvement of the adhesive strength was recognized as compared with Comparative Example 21 in which the inorganic powder was not added, and the improvement of redispersion was compared with Comparative Example 22 in which the inorganic powder which was not surface-treated was added. Is recognized.

[0032]

[Table 1]

[0033]

INDUSTRIAL APPLICABILITY In the present invention, by using a viscoelastic resin composition containing at least one kind of surface-treated inorganic powder component subjected to surface treatment, the resin composite type vibration-damping metal plate has high temperature at room temperature. While ensuring adhesive strength and high vibration damping performance, it also has the effect of preventing aggregation and caking of the inorganic powder during long-term storage of the vibration damping resin solution, and furthermore, surface-treated inorganic powder in the vibration damping resin solution. Even if the components settle down, they can be easily redispersed by simple stirring because of their good redispersibility. Further, since it has the effect of preventing the aggregation and caking of the inorganic powder in the damping resin solution, it can be used in a flow coater or the like even when the viscosity is low, and it is easy to stir in the production line and save power. The productivity of the resin composite type vibration damping metal plate is remarkably improved.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Setsuo Sasaki 1778-31 Higashiyama, Tamura-cho, Kameyama-shi, Mie, Kyodo Yushi Co., Ltd. Kameyama factory (72) Inventor Shinichi Nagato 1778 Higashiyama, Tamura-cho, Kameyama-shi, Mie -31, Kameyama Factory, Kyodo Yushi Co., Ltd.

Claims (8)

[Claims] 1. A viscoelastic resin composition for a vibration damping material, comprising at least one surface-treated inorganic powder component surface-treated with a titanate coupling agent or an aluminum coupling agent. 2. The amount of the coupling agent used when surface-treating the inorganic powder according to claim 1 with a coupling agent is 0.4 to 1.2% by weight of the surface-treated inorganic powder component. A viscoelastic resin composition for a vibration damping material. 3. A viscoelastic resin for a vibration damping material, wherein the surface-treated inorganic powder component subjected to the surface treatment according to claim 1 or 2 is contained in an amount of 5 to 45% by weight based on the viscoelastic resin. Composition. 4. The average particle size of the surface-treated inorganic powder component subjected to the surface treatment according to claim 1 is 1 / thickness of the viscoelastic resin layer constituting the resin composite type damping metal plate. A viscoelastic resin composition for a vibration damping material, which is 3 or less. 5. A viscoelastic resin composition for a vibration damping material constituting a viscoelastic resin layer contains at least one surface-treated inorganic powder component surface-treated with a titanate coupling agent or an aluminum coupling agent. A resin composite type damping metal plate characterized by the above. 6. The resin composite type composition according to claim 5, wherein the amount of the inorganic powder treated with the coupling agent is 0.4 to 1.2% by weight of the surface-treated inorganic powder component. Swing metal plate. 7. A resin composite-type vibration-damping metal plate, characterized in that the surface-treated inorganic powder component subjected to the surface treatment according to claim 5 or 6 is compounded in an amount of 5 to 45% by weight with respect to the viscoelastic resin. . 8. A resin characterized in that the surface-treated inorganic powder component subjected to the surface treatment according to any one of claims 5 to 7 has an average particle diameter of 1/3 or less of the thickness of the viscoelastic resin layer. Composite type vibration control metal plate.