JPH0583370B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a vibration-damping metal plate with excellent post-processability, and more specifically, as a component of an intermediate layer sandwiched between two metal plates, it can be copolymerized with a polymerizable monomer. By containing 1 to 90% by weight of a rubber component modified in this way, it is possible to perform post-processing such as stretching, bending, and deep drawing of vibration-damping metal plates using this as an intermediate layer extremely well. It relates to vibration-damping metal plates, and is used for various types of equipment such as automobiles, trains, aircraft, etc., office equipment, and electrical products.
This is a vibration-damping metal plate with excellent vibration-damping properties that reduces noise from vibrating members in a temperature range of 100°C, especially around room temperature. Prior Art In recent years, with the spread of vehicles such as automobiles, trains, and airplanes, as well as office equipment and electrical products, noise countermeasures for these devices have become an urgent issue, and many vibration control methods have been developed to date. Metal plates have been proposed or commercially available. However, when conventional vibration damping metal plates are evaluated against market demands, the following various deficiencies have been raised, and as a result, the scope of application is currently extremely limited. One of the major drawbacks is that the intermediate layer material used in commercially available vibration-damping metal plates is mostly a type of thermoplastic self-adhesive, so it is susceptible to impact stress during post-processing. , cracks occur in the intermediate layer material, buckling occurs during shrinkage deformation, and flange wrinkles are likely to occur. Furthermore, since the adhesion to metal is extremely poor, peeling and misalignment with the metal plate occur. Therefore, the overhang
Press forming involving bending, drawing, etc. becomes extremely difficult. That is, it is difficult to apply it to automobile parts, office equipment, metal processing machines, etc., which are in high demand and require complicated press formability. In addition, even in very simple press-formed parts, intermediate layer substances may flow out during the paint baking or drying process, decomposition and carbonization may occur, and even creep may occur under static stress at actual operating temperatures. or peeling from the metal plate may occur.
There are various problems in practical use. In addition, from the point of view of spot weldability, the intermediate layer in conventional vibration-damping metal plates is simply made of polymeric organic material and has no electrical conductivity, so it cannot be used as an automotive component for which a large amount of demand is expected. There is also the problem that it is difficult. OBJECTS OF THE INVENTION An object of the present invention is to provide a vibration damping metal plate which has both vibration damping ability and excellent post-processability, and which improves the above-mentioned drawbacks of conventional vibration damping metal plates. That is, as a result of intensive research, the present inventors found that α, β-
The present invention has been completed by discovering an intermediate layer whose main components are 1 to 90% by weight of a rubbery polymer having unsaturated carboxylate groups and 99 to 10% by weight of a polymerizable monomer. Structure of the Invention The gist of the present invention is that (A) the general formula

【formula】

【formula】 or ()

[Chemical ^formula ] ⁽ wherein ^, (B ) 99 to 10% by weight of polymerizable monomers alone or as a mixture, and (C) inorganic and organic fillers in an amount of 0 to 100 parts by weight per 100 parts by weight of (A) + (B) (D) Adhesive (A)
+ (B) A vibration damping material with excellent post-processability, made by sandwiching an intermediate layer containing 10 to 150 parts by weight to 100 parts by weight between two metal plates and hardening the intermediate layer into one piece. exists in the metal plate, and the above (A)+
(B) A vibration-damping metal plate with excellent spot weldability, which contains 1 to 50 parts by weight of conductive particles per 100 parts by weight. The two metal plates used in the present invention are iron,
Copper, aluminum, etc. or various alloys,
These metals are used in combination of the same or different metals. The thickness of the intermediate layer sandwiched between the metal plates is adjusted to 0.01 to 1 mm, preferably 0.05 to 0.5 mm. Rubbery polymers in the present invention include natural rubber, polyisobutylene, polybutadiene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylotrile copolymer, vinylpyridine-butadiene-styrene copolymer, and isobutylene-isoprene copolymer. , acrylic acid-butadiene copolymer, methacrylic acid-butadiene copolymer, methyl acrylate-butadiene copolymer,
Methyl methacrylate-butadiene copolymer,
Ethylene-propylene-cyclopentadiene copolymer, ethylene-propylene-5-ethylidene-
It is a wide range of polymer elastomers that have unsaturated bonds in their molecules, such as 2-norbornene copolymer, ethylene-propylene-1,4,hexadiene copolymer, conjugated diene butyl rubber, and syndiotactic 1,2-polybutadiene norbornene rubber. . The molecular weight of these molecular substances is not limited in any way, and may be selected as appropriate depending on the purpose of use or conditions of use, but those with a molecular weight of approximately 500 or more are preferred for the purpose of maintaining the main physical properties of the raw material polymer elastomer. It is preferable to use Also,
Two or more types of polymers may be used in combination. The rate of introduction of α,β-unsaturated carboxylate groups is usually 1 per molecular weight of rubber from 100 to 10,000, preferably 1 per molecular weight of rubber from 100 to 8,000. Examples of methods for introducing these α,β-unsaturated carboxylate groups include a method using N-haloamide or alkyl hypohalide (Japanese Patent Application Laid-open No. 84307/1983). Introduction rate is molecular weight
If the number is less than 1 per 100 to 10,000, satisfactory physical properties after curing, especially mechanical strength during stretching during bending, will not be obtained. In addition, the intermediate layer (A) + excluding inorganic and organic fillers
The content of the modified rubber in (B) is 1 to 90% by weight, preferably 3 to 80% by weight. Content is 1% by weight
If it is less than 90% by weight, cracks will occur in the intermediate layer due to impact stress during post-processing, especially during press forming, and if it exceeds 90% by weight, mechanical properties will deteriorate. Examples of the polymerizable monomer used in the present invention include styrene, α-methylstyrene, β-methylstyrene, styrene derivatives such as divinylbenzene, methyl acrylate, methyl methacrylate, tridecyl methacrylate, cyclohexyl methacrylate, and methacrylate. Acrylic acid derivatives such as tetrahydrofurfuryl acid, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, lauryl methacrylate, stearyl methacrylate, glycidyl methacrylate, ethyl dimethacrylate, 1,3-butylene dimethacrylate, vinyl acetate , acrylonitrile, vinylpyridine, etc., and at least one of these is used, which enables design in a wide range of vibration damping ability, mechanical properties, etc. The content in the intermediate layer composition (A)+(B) excluding these inorganic and organic fillers is 9 g to 10% by weight, preferably 97 to 20% by weight. Content is 99% by weight
If it exceeds 10% by weight, cracks will occur in the intermediate layer due to impact stress during post-processing, especially during press forming, and if it is less than 10% by weight, mechanical properties will deteriorate. As the inorganic and organic fillers used in the present invention, the total amount of polymerizable monomers ( Add 0 to 100 parts by weight per 100 parts by weight of A)+(B). Examples of the tackifier used in the present invention include rosin, hydrogenated rosin glycerin ester, polyterpene resin, terpene/phenol resin, _C5 petroleum resin, _C9 petroleum resin, alicyclic hydrogenated petroleum resin, etc. solid semi-polymer resins, fluid semi-polymer resins such as Hercorin, butone, xylene resin, epoxy resin, polyester, polyacrylic acid ester, phthalate ester, aromatic polybasic acid ester, aliphatic dibasic acid ester and other plasticizers, and low-molecular polymers such as polybutene and polyisobutylene. By adding within the range of 10 to 150 parts by weight, it becomes possible to freely set the temperature range in which the vibration damping ability is exhibited. In the present invention, the intermediate layer sandwiched between two metal plates is cured to integrate the whole, and the curing agent is methyl ethyl ketone peroxide,
Ketone peroxides such as cyclohexane peroxide and acetylacetone peroxide;
1,1-bis(tertiary-butyl peroxide)
-3,3,5-trimethylcyclohexane, 1,
1-bis(tertiary-butyl peroxide)-peroxyketal such as cyclohexane; tertiary-
Butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-
Hydroperoxides such as 2,5-dihydroperoxide; dialkyl peroxides such as di-tertiary-butyl peroxide and dicumyl peroxide; diacyl peroxides such as acetyl peroxide, isobutyl peroxide, and benzoyl peroxide; Peroxydicarbonates such as diisopropyl peroxydicarbonate and dimyristyl peroxydicarbonate;
Tertiary-butyl peroxyacetate, tertiary-
Examples include peroxy esters such as butyl peroxybenzoate, tertiary-butylperoxymaleic acid, and tertiary-butylperoxyisopropyl carbonate. B) Add 0 to 5 parts by weight per 100 parts by weight. However, when a monomer other than acrylic is used as component (B), curing is performed simply by heating without adding a curing agent.
The objectives of the invention are achieved. The damping metal plate of the present invention has extremely good adhesion between the intermediate layer and the two metal plates, and has excellent heat aging resistance and impact resistance, so spot welding for reinforcement is unnecessary. , which greatly contributes to productivity. However, when spot welding the damping metal plate of the present invention and other metal members, iron powder, mill scale,
By adding 1 to 50 parts by weight of conductive particles such as aluminum powder, copper powder, and carbographite,
Spot welding can be performed satisfactorily. The intermediate layer composition used in the present invention may contain commonly used polymerization inhibitors, curing catalysts, and co-catalysts as necessary, and various other additives and fillers depending on the purpose. There is no problem with adding wood. Manufacturing method of modified polymer: 28 g of polybutadiene (manufactured by Nippon Gosei Rubber Co., Ltd., trade name: BR-01) is sufficiently swollen with 21 g of methacrylic acid and 21 g of methyl methacrylate, then kneaded uniformly with a roll, and then t-butyl hypochloride is added to this. 1.01 g was kneaded with a roll and left at room temperature overnight to produce a modified polymer. Example 1 Modified polymer 100 produced by the above method
20 parts by weight, 40 parts by weight, and 60 parts by weight of a tackifier (manufactured by Arakawa Chemical Co., Ltd., alicyclic hydrocarbon resin, trade name: Alcon M-100) were added to each part by weight, and and t-butylperoxymaleic acid (manufactured by NOF Corporation,
Three intermediate layer compositions were manufactured by blending 1.0 part by weight of Perbutyl MA (trade name: Perbutyl MA) (Test Nos. 1 and 2).
and 3). Regarding the intermediate layer compositions of test numbers 1 to 3, the thickness
The shear adhesive force and peel adhesive force to a 0.8 mm steel plate were measured based on JIS-K-6850 and ISO-4578, respectively. In addition, the thickness of the intermediate layer compositions of test numbers 1 to 3 was
Adjusted to 0.1mm, each width 25mm, length 300mm, thickness
Sandwiched between two 0.8mm steel plates, heated to 30℃ at a temperature of 130℃.
The test pieces were heated for a minute, and the temperature dependence of the loss coefficient, which is a measure of vibration damping ability, was measured for each test piece using the mechanical impedance method. These results are shown in Table 1 and FIG. Example 2 Styrene-butadiene copolymer rubber (manufactured by Asahi Kasei Corporation, product name: Solblen 414) 20 parts methacrylic acid 10 parts ethyl methacrylate 70 parts Tackifier (manufactured by Yasushi Oil Industries Co., Ltd., terpene resin, product Name: YS Resin Px900) 35 parts Cumene hydroperoxide (manufactured by Nippon Oil & Fats Co., Ltd., product name: Parkmil H) 1 part The above formulation was mixed uniformly in the same manner as in Example 1 to produce an intermediate composition. This was used as the intermediate layer composition of Test No. 4. Regarding the intermediate layer composition of Test No. 4, Example 1
The shear adhesion, peel adhesion and loss coefficient were measured in the same manner as in Table 1 and Figure 1. Comparative Examples 1 and 2 For comparison, a conventional damping steel plate mainly composed of polyisobutylene and a conventional damping steel plate mainly composed of vinyl acetate were used as Comparative Examples 1 and 2, and the adhesive strength was measured for them. The results were as shown in Table 1.

[Table] In general, adhesive strength serves as a guideline for determining the quality of post-processability, and according to previous research by the present inventors, in order to obtain good post-processability, shear adhesive strength of 50 kg/ ^cm2 or more, preferably 80Kg/cm2 ^or more, peel adhesive strength of 8Kg/25mm or more, preferably 10Kg/25
It is necessary to satisfy both conditions of mm or more.
Comparative Examples 1 and 2, which are made of conventional damping metal plates that are difficult to post-process, have shear adhesion strengths of 4 Kg/cm ² and 13 Kg/cm ² , respectively, and peel adhesion strengths of 7 Kg/cm 2 and 7 Kg/cm 2 respectively.
Kg/25mm and 5Kg/25mm are at a low level, whereas the shear adhesive strength of test numbers 1, 2, and 3, which are control metal plates according to the present invention, are 145, 140, and 140, respectively.
139Kg/cm ² , which is more than 10 times higher than the comparative example, and the peel adhesion strength was 32, 39, and 28, respectively.
Kg/25mm, which is a very high value, and test numbers 1 to 3
It was shown that the material has excellent post-processability. Regarding the loss coefficient, it is desirable to be able to freely set the maximum value of the loss coefficient over a wide temperature range, and from the perspective of vibration damping ability, the loss coefficient that is usually effective in reducing vibration is said to be 0.05 or more. There is. In test numbers 1 to 3, the vibration damping metal plate according to the present invention exhibited a vibration damping effect in an extremely wide temperature range of 60°C, and the maximum value of the loss coefficient was an extremely large value of 0.3. It is clear that he is very capable. Test No. 4 according to the present invention also showed higher values for both shear adhesive strength and peel adhesive strength than the comparative examples, and was excellent in post-processability.Furthermore, the maximum value of the loss coefficient was 0.2, and the vibration damping ability was high. It was also shown that there is sufficient Example 3 An intermediate layer composition prepared by uniformly mixing 10 parts by weight of carbon graphite with Test No. 2 in Example 1 was used as Test No. 5, and the shear adhesive strength before and after spot welding was measured. The results were as shown in Table 2. The spot welding was performed using a semi-synchronous resistance welding machine manufactured by Osaka Transformer Co., Ltd.
This is two-point spot welding of 1.2mm thick steel plates together under the following welding conditions.

[Table] In the above spot welding, the nugget part did not contain any residue of the intermediate layer material, and the weldability was good. In addition, as shown in Table 2 above, the shear adhesive strength before spot welding is extremely large, so
Spot welding for the purpose of reinforcing vibration-damping metal plates conventionally used in automobile parts and the like is no longer necessary, and it has been found that this greatly contributes to improved productivity.

【table】

[Table] Effects of the Invention The vibration damping metal plate according to the present invention can be designed to have its maximum vibration damping ability at any temperature within the temperature range of 0 to 100°C, and exhibits extremely high vibration damping ability over a wide temperature range. Its excellent adhesion makes it possible not only to bend and cut, but also to perform complex press forming that combines stretching, bending, deep drawing, etc., as well as vibration-damping metal plates that also have good spot weldability. It is something that can be obtained. By using the damping metal plate according to the present invention,
It has become possible to expand its application to a wide range of products, including automobile parts with various complex shapes (mainly ceilings, floors, etc.), office equipment, and home appliances, making it an extremely effective means of reducing vibration and noise in various fields. It is what it is.

[Brief explanation of drawings]

Attached Figure 1 shows a vibration-damping metal plate (steel plate) according to the present invention.
3 is a graph showing the relationship between temperature and loss coefficient.

Claims (1)

[Scope of Claims] 1 (A) General formula [Formula] [Formula] or () [Formula] (wherein, X is a halogen atom selected from Cl, Br and I, R ¹ , R ² and R ³ are all hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, n is an integer of 2 to 5, m is an integer of 1 to 4, and 1 is an integer of 1 to 30), 1 to 90% by weight of a rubbery polymer having β-unsaturated carboxylate groups, alone or in a mixture; (B) 99 to 10% by weight of a polymerizable monomer, alone or in a mixture; and (C) inorganic and organic fillers. , 0 to 100 parts by weight per 100 parts by weight of (A) + (B) and (D) an adhesion agent, 10 parts by weight per 100 parts by weight of (A) + (B).
A vibration-damping metal plate made by sandwiching an intermediate layer containing ~150 parts by weight between two metal plates, and hardening and integrating the intermediate layer. 2 Add 20 to 100 parts of tackifier to 100 parts by weight of (A) + (B).
The damping metal plate according to claim 1, in which 80 parts by weight is added. 3. Add 1 to 100 parts by weight of conductive particles to 100 parts by weight of (A) + (B).
The vibration damping metal plate according to claim 1 or 2, in which 50 parts by weight is added.