JP3183738B2 - Vehicle damping reinforcement structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vibration damper for vehicles which is integrated by fusion molding on a wide-area substrate, such as a front panel, a fender panel, a door panel, or a ceiling panel, which is easily vibrated and has low rigidity. The present invention relates to a reinforcing structure.

[0002]

2. Description of the Related Art A heat-fusible reinforcing material containing epoxy resin as a main component is fused to a surface of a vibrating substrate, such as a front panel, a fender panel, a door panel, or a ceiling panel of a vehicle or the like, which is likely to vibrate. There are many. In recent years, a metal sheet such as a glass cloth or an aluminum plate is laminated as a constraining material on the upper surface of these epoxy resin-based reinforcing materials to improve rigidity as a constrained reinforcing structure. More recently, attempts have been made to further improve rigidity performance by foaming a reinforcing material sheet containing an epoxy resin as a main component. However, these reinforcement structures have the following problems. In other words, in a double-layered reinforcing structure in which a substrate is reinforced only with a heat-fusible reinforcing sheet mainly composed of epoxy resin, it is necessary to increase the thickness in order to improve the reinforcing performance. Despite the increase, the level of improvement in the rigidity of the structure is not so great. Recently, a technique for suppressing the increase in weight by using a foaming material for the reinforcing material sheet mainly containing the epoxy resin has begun to be used recently, but the actual foaming ratio is 1.5 to 2.0.
It is about twice, and the improvement of the reinforcing performance in the practical weight range is not great. In addition, a metal sheet such as a steel plate or an aluminum plate or an uncured thermosetting resin sheet is placed as a restraining sheet on an epoxy resin-based reinforcing sheet on a reinforcing sheet mainly containing epoxy resin. When both are integrated by heating to form a sandwich type reinforcement structure, the rigidity is improved compared to the double layer type reinforcement structure, but a considerable thickness of the restraint sheet is required to greatly improve the performance Therefore, even in this case, the vehicle weight is increased. In the range of practical thickness, more effective reinforcement performance, that is, rigidity, can be obtained than the double-layer reinforcement structure. However, since these reinforcement structures have almost no vibration damping performance, noise reduction in the recent vehicle interior has been reduced. From the point of view of the situation, the current situation is that there is a shortage of performance.

[0003]

SUMMARY OF THE INVENTION In order to solve these problems, a foaming composition comprising a liquid epoxy resin and a heat-activated curing agent in a composition comprising a vinyl chloride resin for a paste, a plasticizer, a foaming agent, and the like. There is also a proposal of a so-called thermosetting foamed spacer-equipped vibration damping reinforcement structure using a semi-gelled sheet as a spacer (for example, Japanese Patent Application No. 4-7313).
9). Although this is a lightweight and excellent vibration damping reinforcement structure despite having high vibration damping properties and rigidity, it contains a vinyl chloride resin in its composition. At a high temperature such as an electrodeposition coating process, there is a problem that thermal decomposition of the resin may occur. Under the above circumstances, the present invention provides a vehicle structure that is lightweight and has high vibration damping performance and high rigidity, has good heat resistance, and can withstand, for example, an electrodeposition coating process. It is an object of the present invention to provide a vehicle structure having a desired composition.

[0004]

According to the present invention, a spacer layer (I) comprising a foamable thermosetting resin sheet laminated on a wide area vibration substrate in a vehicle and a vibration damper laminated on the spacer layer are provided. A vehicle comprising three layers of a material sheet layer (II) and a constraining material sheet layer (III) laminated on the vibration damping material layer, wherein the spacer layer (I) is foamed. In the vibration damping reinforcement structure for use, the spacer layer (I) comprises: (A) 100 parts by weight of a liquid epoxy resin containing one or more epoxy groups in one molecule, and (B) methacrylic having an average particle diameter of 300 μm or less. 10-200 parts by weight of a base resin, (C) 0.5-20 parts by weight of a curing agent for an epoxy resin, (D) a decomposition gas generation temperature of 10
0.5 to 20 parts by weight of a blowing agent at 0 to 220 ° C and (E)
A sheet comprising 0.05 to 5 parts by weight of a surfactant, which is semi-gelled by heating at a temperature not higher than the decomposition gas generation temperature of the foaming agent (D), wherein the vibration-damping material sheet layer (II) has 100 parts by weight of butyl rubber At least 10 to 100 parts by weight of a tackifier having a viscosity of 10 ³ to 10 ⁵ cps at 20 ° C. based on the composition of the binding material sheet layer (III) containing the tackifier resin. The present invention provides a vibration damping reinforcement structure for a vehicle, which is made of a thermosetting plastic, or a metal sheet.

Further, the present invention provides a structure for a vehicle which can be fused and integrated with a vibration substrate of a vehicle to provide excellent vibration damping performance and improve rigidity in a range where the weight increase of the vehicle is small. It provides a structure. Furthermore, for this type of vehicle structure, it is necessary to complete the reaction, foaming, fusion, etc. of each layer by a heat treatment in a drying process such as coating, and a material that does not significantly decrease in physical properties even at a relatively high temperature. Although required as preferred properties, the structure according to the present invention correctly meets these requirements.

Hereinafter, each constituent layer according to the present invention will be described. The spacer layer (I) used in the present invention is a foamable thermosetting resin sheet, which imparts a function as a spacer in the vibration damping reinforcement structure, and is preferable as a spacer in the vehicle vibration damping reinforcement structure. Is
Light weight, high rigidity, little change in physical properties due to temperature change,
In addition, it is in close contact with and fixed to the vibrating substrate in a coating drying step or the like, and has a high magnification foaming action in this step. In the spacer composition of the present invention, the liquid epoxy resin used as the component (A) contains one or more epoxy groups in the molecule, and examples thereof include bisphenol A and bisphenol F. Or glycidyl ether based on resorcinol, polyglycidyl ether of phenol novolak resin or cresol novolak resin, glycidyl ether of hydrogenated bisphenol A, glycidylamine type, linear aliphatic epoxide type, phthalic acid, hexahydrophthalic acid or tetrahydro The preferred epoxy equivalent is glycidyl ether of phthalic acid, etc.
One. These liquid epoxy resins may be used alone or in combination of two or more. In order to impart toughness to the obtained foam, ethylene oxide or propylene oxide addition type phenol A type is used. A flexible epoxy resin such as an epoxy resin, a dimer acid type epoxy resin, and an epoxy-modified NBR may be used in combination.

In the spacer composition of the present invention, a methacrylic resin having an average particle diameter of 300 μm or less is used as the component (B). As the methacrylic resin, polymethyl methacrylate or a copolymer resin of methyl methacrylate having a superior amount of methyl methacrylate and a copolymerizable monomer such as ethyl acrylate and acrylonitrile is used. The preferred degree of polymerization of the methacrylic resin is such that the degree of polymerization in terms of polymethyl methacrylate is in the range of 2,000 to 30,000. If the degree of polymerization is less than 2,000, the melt viscosity during processing becomes low, and it becomes difficult to form a dense cell structure due to flow breakage of the foam cells. On the other hand, if the degree of polymerization exceeds 30,000, the meltability during processing deteriorates and a high expansion ratio cannot be obtained, and the effect of the present invention is undesirably reduced. Also,
The present methacrylic resin has an average particle diameter of 300 μm or less,
Preferably it is 100 μm to 1 μm. If it exceeds 300 μm, the uniform dispersibility with other compositions becomes poor, which is not preferable. The methacrylic resin is added in an amount of 10 to 2 per 100 parts by weight of the liquid epoxy resin (A).
It is in the range of 00 parts by weight, preferably 20 to 100 parts by weight. When the amount is less than 10 parts by weight, the viscosity at the time of processing becomes too low, depending on the viscosity and the like of the epoxy resin of the component (A).
If the amount exceeds 200 parts by weight, the meltability during processing deteriorates, and it becomes difficult to obtain a high expansion ratio.

In the composition of the present invention, 0.5 to 20 parts by weight of a curing agent for epoxy resin is used as the component (C). The curing agent preferably has an exothermic peak temperature in the range of 100 to 220 ° C. in combination with an epoxy resin. Examples of such a curing agent include dicyandiamide, 4,4′-diaminodiphenylsulfone, and 2-n.
Imidazole derivatives such as heptadecyl imidazole, isophthalic dihydrazide, N, N′-dialkyl urea derivatives, N, N′-dialkyl thiourea derivatives, acid anhydrides such as tetrahydrophthalic anhydride, isophorone diamine, N-amino Ethyl piperazine, boric acid trifluoride complex compound, trisdimethylaminomethylphenol and the like can be mentioned. One of these curing agents may be used, or two or more of them may be used in combination. The amount of the curing agent is 0.5 to 20 parts by weight per 100 parts by weight of the epoxy resin (A). Range of parts. If the amount is less than 0.5 part by weight, the curing is insufficient and the rigidity of the foam is insufficient. If the amount exceeds 20 parts by weight, the rigidity of the foam is not improved for the amount, which is economically disadvantageous. Not only does it have any technical significance. The curing temperature here refers to a temperature of a medium at which heat generated by curing when a mixture of an epoxy resin and a curing agent at room temperature is heated by an oil bath, a heater, or the like has a peak. In addition, a preferable combination of the amounts and types of the epoxy resin and the curing agent according to the heating conditions can be easily determined by conducting a test in advance. In the present invention, together with the curing agent of the component (C), if necessary, as a curing accelerator, for example, alcohol-based, phenol-based, mercaptan-based, dimethylurea-based, aliphatic-based, imidazole-based, monuron, Chlorotoluene or the like can be used.

In the present invention, a foaming agent having a decomposition gas generation temperature of 100 to 220 ° C. is used as the component (D). As such a high-temperature decomposition type foaming agent, an organic foaming agent, an inorganic foaming agent, a high-temperature expansion type microcapsule and the like can be used. When the decomposition gas generation temperature is less than 100 ° C., foaming starts before producing a semi-gelled sheet,
During the heating and foaming, the resin is insufficiently melted, gas is released, and the expansion ratio does not increase, or it is difficult to obtain a uniform foam. On the other hand, when the temperature exceeds 220 ° C., the processing temperature of the composition becomes too high, and deterioration occurs, so that it is difficult to obtain a foam having good quality. Examples of the organic blowing agent include azodicarbonamide, p-toluenesulfonylhydrazide, dinitrosopentamethylenetetramine, and 4,4′-
Oxybisbenzenesulfonyl hydrazide and the like can be mentioned. The decomposition temperature of these organic foaming agents can be arbitrarily adjusted by adding an appropriate amount of urea, a zinc compound, a lead compound and the like. Examples of the inorganic foaming agent include sodium hydrogencarbonate and sodium borohydride, and examples of the high-temperature expandable microcapsules include, for example, those obtained by encapsulating a low-boiling hydrocarbon with a vinylidene chloride resin.

As the component (D) of the present invention, any of the above-mentioned organic foaming agents, inorganic foaming agents, and high-temperature expandable microcapsules can be used. Is preferred. These foaming agents may be used alone or in a combination of two or more. The amount of the foaming agent is determined by the amount of the liquid epoxy resin 10 as the component (A).
It is selected in the range of 0.5 to 20 parts by weight with respect to 0 parts by weight. If the addition amount is less than 0.5 part by weight, the expansion ratio is insufficient, and if it exceeds 20 parts by weight, the expansion ratio does not improve for the added amount, which is economically disadvantageous. In order to obtain a dense foam having a uniform foam cell diameter and a rigid cell membrane, it is advantageous to use a foaming agent having a small particle diameter, for example, to obtain a 0.5 mm cell diameter. It is preferable that the foaming agent has an average particle diameter of 20 μm or less, preferably 1.0 μm or less, and a uniform particle diameter distribution. In the present invention, a foaming accelerator can be used together with the foaming agent, if necessary. Examples of the foaming accelerator include zinc oxide, zinc stearate, lead stearate, calcium stearate, barium stearate, sodium and potassium compounds, and urea.

In the present invention, a surfactant is used as the component (E). This surfactant plays a role in improving the foam cell structure. Examples of the surfactant include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate; alkyl allyl sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate; sodium dioctyl sulfosuccinate; and dihexyl sulfosuccinate. Anionic surfactants such as sulfosuccinate salts such as sodium silicate, ammonium laurate, fatty acid salts such as potassium stearate, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl allyl sulfate salts, and rosinate salts are preferred. Sorbitan esters such as sorbitan monooleate and polyoxyethylene sorbitan monostearate; and polyoxyethylene. Alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters of the nonionic surfactant and cetyl pyridinium chloride, cationic surfactants such as cetyltrimethylammonium bromide may also be used.

These surfactants may be used alone or in combination of two or more, and the amount of the surfactant is 0.05 to 100 parts by weight of the liquid epoxy resin (A). It is 5 parts by weight, preferably 0.2 to 3 parts by weight. If the addition amount is less than 0.05 part by weight, the effect of homogenizing the foam cells is poor. If the addition amount exceeds 5 parts by weight, not only does the foam cell not homogenize, but also the amount of the resin increases. It is not preferable because thermal stability is reduced. Further, in the present invention, a plasticizer can be added as necessary to adjust the melt viscosity and to adjust the affinity between the epoxy resin (A) and the methacrylic resin (B). . Examples of the plasticizer include phthalic acid esters such as di-2-ethylhexyl phthalate and dibutyl phthalate, phosphoric acid esters such as tricresyl phosphate, fatty acid esters such as dioctyl adipate, and adipic acid condensation of ethylene glycol. Known substances such as a product, trimellitates, glycolates, chlorinated paraffins, alkylbenzenes and the like can be used.

In the present invention, for the purpose of facilitating the initial mixing and increasing the amount of the filler and the like,
If necessary, an epoxy resin diluent may be added. As this diluent, for example, reactive diluents such as butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, glycidyl ether persatic, dibutyl phthalate, tricresyl phosphate, butyl benzyl phthalate, Acetyl tributyl citrate, aromatic process oil, pine oil,
Non-reactive diluents such as 2,2,4-trimethyl-1,3-pentadiol isobutyrate can be mentioned.
These diluents are generally used in an amount of 5 to 150 parts by weight, preferably 1 to 100 parts by weight of the liquid epoxy resin (A).
It is selected in the range of 0 to 100 parts by weight. In the present invention, a thixotropic agent, a filler, a pigment, and the like may be added as necessary for adjusting coating properties such as processability and viscosity and reducing costs. Examples of the thixotropic agent include silicic acids such as silicic anhydride and hydrated silicic acid, bentonites such as organic bentonite, asbestos such as thylodex, and organic such as dibenzylidene sorbitol. These thixotropic agents are usually used in an amount of 1 to 2 per 100 parts by weight of the liquid epoxy resin of the component (A).
It is selected in the range of 0 parts by weight. Examples of the filler include calcium carbonate, mica, talc, kaolin clay, celite, asbestos, perlite, baryta, silica, silica sand, flaky graphite, gypsum, and metal powder.

In the structure of the present invention, the foamable thermosetting resin sheet composition is used as a semi-gelled sheet. That is, the above-prepared composition is preliminarily formed into a semi-gelled sheet at a temperature lower than the decomposition temperature of the foaming agent, usually at a relatively low temperature of about 100 to 150 ° C., and then the vibration damping sheet (II) and the restraining material sheet (III)
Are laminated and then foamed at 120 ° C. to 200 ° C. in the next heating step, for example, a coating and drying step, and are cured by crosslinking the epoxy resin. The expansion ratio of such an expandable thermosetting resin sheet is 2 to 30 times, preferably 3 to 10 times. Those having an expansion ratio of not more than 2 times can of course fulfill the function as a spacer, but are not the object of the present invention from the viewpoint of lightness and heat insulation.
If the expansion ratio is twice or more, the strength of the foamed cells may be insufficient, and depending on the use site of the vehicle, the compressive strength may be insufficient and may not be practical. The thickness of the spacer layer after foaming is 1 to 50 mm, preferably 2 to 30 mm.
It is. When it is 1 mm or less, it cannot perform an effective function as a spacer, and when it is 50 mm or more, in a vehicle application which is the object of the present invention, the space inside the vehicle becomes narrow and impractical, and a heating process such as a coating drying process is performed. In such a case, when it is adhered to a vertical surface such as a door panel, a shift occurs and a uniform foaming property cannot be obtained.

The vibration-damping material sheet (II) provided to the structure of the present invention has a vibration-damping function in the present structure, and has a viscosity at 20 ° C. of 10 ^{3 with} respect to 100 parts by weight of butyl rubber. It is obtained by adding at least a tackifier of 〜１０10 ⁵ cps. The butyl rubber used here is not particularly limited, and may be one having a generally used degree of unsaturation of about 0.5 to 3.0, and may be a halogenated butyl rubber. Of course, it can be used. 20 used in the present invention
Tackifiers viscosity 10 ³ to 10 ⁵ cps at ℃ is
A function as a plasticizer for setting the temperature distribution of the loss coefficient to a predetermined temperature range is provided, and at the same time, the viscoelasticity suitable for the purpose of the present invention and the close contact between the spacer sheet layer (I) and the restraining material sheet layer (III) It imparts properties and adhesiveness to prevent displacement in the heating step even when the film is attached to a vertical surface of a door panel or the like.

The viscosity of the tackifier is 10 ³ to 10 ⁵ cps at 20 ° C. When the viscosity is 10 ³ cps or less, it depends on the type and the amount of addition, but is 40 to 50 ° C.
The loss coefficient in the high-temperature region described above decreases, and the adhesiveness and adhesion that prevent displacement during heating when attached to a vertical surface such as a door panel become insufficient. Further, when the viscosity is 10 ⁵ cps or more, this also depends on the type and the amount of addition, but the loss coefficient at low temperature decreases. Examples of such tackifiers include petroleum hydrocarbons such as polybutene, polymerized polyester, atactic polypropylene, liquid polybutadiene, and low molecular weight butyl rubber;
Rosin derivatives such as hydrogenated rosin methyl ester, hydrogenated rosin triethylene glycol ester and the like, turpentine and the like can be mentioned. In addition, the amount added
Although there is a relationship between the viscosity and the type, butyl rubber 100
10-100 parts by weight per part by weight, preferably 20-7 parts by weight
0 parts by weight. When the amount is less than 10 parts by weight, the loss coefficient at low temperature is reduced, and the adhesion and adhesion to the spacer sheet layer (I) and the restraining material sheet layer (III) may be insufficient. The function for preventing displacement during the heating step is insufficient. Further, when the amount is 100 parts by weight or more, the loss coefficient at a high temperature is reduced, and the viscosity of the composition is reduced, so that it is difficult to obtain a good damping material sheet having a uniform thickness by a normal processing method. .

Although the thickness of the vibration-damping material sheet is not particularly limited, it is preferably 3 mm or less, preferably 1 mm or less in consideration of being formed as a structure for a vehicle. At a thickness of 3 mm or more, it is economically disadvantageous because an effective loss factor cannot be obtained in dividing the thickness, contrary to one of the objects of the present invention, which is weight reduction.
When affixed to a vertical panel such as a door, the weight tends to cause slippage in the heating process. There is no lower limit on the thickness. This is because the structure of the present invention has a constrained vibration damping structure, so that the function can be exhibited even if the vibration damping material sheet layer (II) is thin. In the composition of the vibration-damping material sheet of the present invention, in addition to the composition, the function as a vibration-damping material is not impaired. For the purpose of improvement, other softeners, reinforcing agents such as carbon, inorganic fillers such as calcium carbonate, talc, clay, and calcium sulfate, halogen compounds, antimony oxide, zinc borate hydrate, aluminum hydroxide, etc. Flame retardants, heat stabilizers, lubricants, anti-blocking agents, coloring agents, UV inhibitors and the like can be used.
Further, in order to improve the durability, a vulcanizing agent such as sulfur may be added to the extent that it does not hinder baking on the vibration substrate during molding. The method of forming the damping material sheet according to the present invention is not particularly limited, but generally, it may be formed by kneading with a Banbury mixer or the like and then using a calender or the like.

The restraining material sheet (III) provided for the structure of the present invention restrains the deformation of the vibration damping material sheet (II) due to the vibration, and imparts a large loss coefficient by applying shear deformation to the vibration damping sheet. As well as imparting high rigidity. It is preferable that the material provided for the restraining material sheet has a high elastic modulus and does not impair the function as a vehicle material. Materials satisfying such conditions include rosin resin, terpene resin, aliphatic petroleum resin,
Thermosetting using a thermoplastic resin sheet containing a tackifier such as an aromatic petroleum resin, an alkylphenol-acetylene resin, a xylene resin, a coumarone indene resin, or a rubber such as butadiene rubber or styrene-butadiene rubber as a base polymer. A flexible plastic sheet and a metal sheet such as a steel plate and an aluminum plate are suitable. The thermoplastic resin sheet containing the tackifier resin has a relatively high elastic modulus in the temperature range of about 0 to 60 ° C. which is the usage state of the vehicle depending on the type and content of the tackifier resin, and the paint drying of the vehicle. It is possible to design the material so that it becomes a low-viscosity melt in the temperature range of about 120 to 200 ° C., which is the temperature of the process, and can follow complicated uneven shapes together with the spacer layer (I) and the damping material sheet layer (II). Easy. The thickness of the restraint sheet is not particularly limited, and the preferred thickness may vary depending on the type of material. However, the sheet formed on a vertical surface of a door panel or the like has high shear resistance at high temperatures. Considering the weight that affects the thickness of the resin restraining material sheet, from the same viewpoint as the spacer layer (I) and the vibration damping material sheet layer (II), it is about 0.5 to 3 mm, and the metal restraining material is Is in the range of about 0.05 to 1 mm. Metal restraint sheets, such as steel plates and aluminum sheets, originally have a high elastic modulus, and therefore have favorable characteristics when applied to restraint sheets.

The production of such a structure according to the present invention comprises the step of forming a spacer sheet layer (I) and a damping material sheet layer (I).
I), each layer of the restraining material sheet layer (III) is individually affixed on a wide-area vibration substrate of the vehicle, and the substrate, the spacer sheet layer (I), and the damping material sheet layer (II) are heated by heating such as a coating and drying step. ), The constraining material sheet layer (III) may be mutually fused and foamed, or the spacer sheet layer (I), the damping material sheet layer (II), and the constraining material sheet layer (I
The laminate of II) may be fused and foamed to the substrate by heating in a coating drying step or the like. Of course, a combination of the spacer sheet layer (I) and the damping material sheet layer (II), or the damping material sheet layer (II) and the constraining material sheet layer (III) may be used.

[0020]

As described above, the vibration damping reinforcement structure for a vehicle according to the present invention is attached to a vertical vibration substrate surface having a relatively large area of a vehicle, such as a door panel, a front panel, and a fender panel of the vehicle. By heating, each layer and the substrate can be firmly fixed. The structure obtained in this way is a rigid, heat-resistant, restrained vibration-damping reinforcement structure with spacers that has a dense cell structure with a high foaming ratio in the lower layer, and thus has excellent vibration damping over a wide temperature range. The structure has both functions and high rigidity, and is not only suitable as a material for reducing vehicle interior noise, but also imparts robustness to a vehicle panel and has excellent heat insulation.

[0021]

The present invention will be described below with reference to examples and comparative examples. The materials used for the test and the test method are as follows. (1) Test material Vibrating substrate: steel plate having a thickness of 1.0 mm Spacer sheet A spacer composition was prepared by mixing for 20 minutes using a Hobart mixer at a compounding ratio shown in Table 1, and then applied on a release paper at a predetermined thickness. . This was heated at 120 ° C. for 100 seconds to produce a semi-gelled sheet.

[0022]

[Table 1]

Damping Material Sheet The damping material composition was kneaded in a kneader at the compounding ratio shown in Table 2, and further kneaded in a roll. The obtained roll sheet was pressed to a predetermined thickness.

[0024]

[Table 2]

Restriction Material Sheet The restriction material composition was melted and mixed in an autoclave at 200 ° C. at the compounding ratio shown in Table 3, and the obtained mixture was hot-pressed to a predetermined thickness.

[0026]

[Table 3]

In the case of a restraining sheet made of a thermosetting plastic sheet, a sheet having a compounding ratio shown in Table 4 was kneaded with a roll to have a predetermined thickness.

[0028]

[Table 4]

Further, the metal sheets shown in Table 5 were also used as restraining material sheets.

[0030]

[Table 5]

(2) Test method Shearing resistance of the structure during heating The unfoamed semi-gelled sheet, vibration damping sheet, restraint sheet and the like formed in (1) are placed on a 1.0 mm thick steel sheet. After mounting and producing an example structure as shown in Table 6 and a comparative example structure as shown in Table 7, it was fixed vertically and heated and foamed at 150 ° C. for 30 minutes. The degree of deviation generated between the foam, the vibration damping material, and the restraining material was determined according to the following criteria. The dimensions of the test specimens used for this test were 70 × 110 mm. ：: The deviation is within 1 mm, and there is almost no deviation from the initial sticking position. ：: The deviation is 1 to 2 mm, and there is no problem in use although there is some deviation. Δ: The deviation is 2 to 5 mm, which may cause a problem in use depending on the part. X: The deviation is 5 mm or more, which causes a problem in use. XX: Completely peeled.

[0032]

[Table 6]

[0033]

[Table 7]

Expanding Ratio, Foam Cell Shape, Cell Density An unfoamed semi-gelled sheet, vibration damping material sheet, restraining material sheet, etc. molded in (1) are placed on a steel plate having a thickness of 1.0 mm. , Tables 6 and 7
The shape and denseness of the foamed cell when this was fixed horizontally and foamed by heating at 150 ° C. for 30 minutes were determined according to the following criteria. A: The cells are uniform and dense, and most are closed cells. ：: The cells are relatively uniform and dense, with some open cells. Δ: The cells are relatively uneven and coarse, and most are open cells. ×: The cells are uneven and coarse, and most are open cells. The expansion ratio was determined by dividing the thickness of the entire foam layer by the thickness of the semigel sheet.

Loss Factor and Stiffness Ratio of Structural Body An unfoamed semi-gelled sheet, a damping material sheet, a restraining material sheet, etc., molded according to (1) are placed on a steel plate having a thickness of 1.0 mm. After creating a structure as shown in Table 7,
Heating, foaming, and adhesion between the layers were performed at 150 ° C. for 30 minutes to prepare a test structure. The specimen size at this time is 30
× 300 mm, the loss coefficient and the rigidity ratio were measured in an atmosphere of 20 ° C., 40 ° C., and 60 ° C. The loss coefficient was calculated from the half width at the resonance point of the mechanical impedance, and a 200 Hz loss coefficient was obtained by interpolation. The measurement frequency range is 1 to 1000 Hz. The rigidity was calculated by the following equation using the form of the ratio to the rigidity of the vibration substrate, that is, the rigidity ratio.

[0036]

Stiffness ratio = (f ₀ / f) ² · {(m ₁ + m ₂ ) / m ₁ }

Here, f ₀ : resonance frequency (Hz) when a multilayer structure is formed, f: resonance frequency (Hz) when a steel sheet is used alone, m ₁ : areal density (kg / m ² ) when a steel sheet is used alone m ₂ : is the area density (kg / m ² ) when a multilayer structure is formed.

(3) Test Results Table 8 shows the test results of the examples, and Table 9 shows the test results of the comparative examples.

[0039]

[Table 8]

[0040]

[Table 9]

As shown in Tables 8 and 9, all of the structures according to Examples 1 to 13 according to the present invention have a uniform and dense foam cell shape, most of which are composed of closed cells. There is almost no deviation in the slip property, and the soundproofing performance (loss coefficient) and the rigidity are both good. On the other hand, in the structure according to the comparative example, the structures according to Comparative Examples 1 and 2 have all the above-mentioned performances. Inferior, there is a problem that Comparative Example 3 has a soundproof property, Comparative Example 4 has rigidity, and structures according to Comparative Examples 5 to 8 all have extremely poor shear resistance.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigetoku Kazama 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Prefecture Inside Nissan Motor Co., Ltd. (72) Inventor Takamitsu Mikuni 1-2-1, Yoko, Kawasaki-ku, Kawasaki-ku, Kanagawa Japan Japan Zeon Corporation R & D Center (58) Fields surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B62D 29/04 F16F 15/00-15/30

Claims (2)

(57) [Claims] 1. A spacer layer (I) composed of a foamable thermosetting resin sheet laminated on a vibration substrate in a vehicle, a damping material sheet layer (II) laminated on the spacer layer, and the damping material layer The restraining material sheet layer (II
In the vibration damping reinforcement structure for a vehicle, which is composed of three layers of (I), wherein the spacer layer (I) is foamed, the spacer layer (I) contains (A) one molecule in one molecule. Liquid epoxy resin 100 containing one or more epoxy groups
(B) 10 to 200 parts by weight of a methacrylic resin having an average particle diameter of 300 μm or less, (C) 0.5 to 20 parts by weight of a curing agent for epoxy resin, and (D) a decomposition gas generation temperature of 100 to 100 parts by weight. It consists of 0.5 to 20 parts by weight of a foaming agent at 220 ° C. and 0.05 to 5 parts by weight of a surfactant (E), and is semi-gelled by heating at a temperature not higher than the decomposition gas generation temperature of the foaming agent (D). A damping material sheet layer (II) at 20 ° C. with respect to 100 parts by weight of butyl rubber.
Of a tackifier having a viscosity of 10 ³ to 10 ⁵ cps at 10
A vibration damping reinforcement structure for a vehicle, characterized by adding at least 100 parts by weight. 2. The vibration damping reinforcement structure for a vehicle according to claim 1, wherein the restraining material sheet layer (III) is any one of a tackifier resin sheet, a thermosetting plastic sheet, and a metal sheet. body.