JPS6242784B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a vibration isolation method suitable for vibration isolation treatment of transportation equipment such as automobiles, railway vehicles, aircraft, etc., ceilings, internal walls, and other similar structural parts of buildings, and particularly relates to a vibration isolation method that has improved wide temperature range suitability, that is, ,
This invention relates to an anti-vibration method that can maintain a stable improved anti-vibration effect over a wider temperature range and also has improved cold resistance, heat resistance, adhesion, etc. More specifically, the present invention includes 100 parts by weight of a liquid diene polymer containing active hydrogen groups, about 50 to about 600 parts by weight of a bituminous material,
One side of a sheet-like molded article (A) containing an organic polyisocyanate compound in an amount such that the weight part and isocyanate group/active hydrogen group possessed by the diene polymer (equivalent ratio) is 0.5 to 0.95 is coated with a constraining layer ( B) and the other surface of the substrate (C) are integrally joined to the surface of the substrate (C) without using an adhesive to form a sanderch structure. For example, it is known that a vibration isolating material is used to perform vibration isolation treatment on a substrate such as a metal plate, and a vibration isolating material composition containing a large amount of a filler with a large specific gravity is applied thickly to the surface of the substrate. There is also a known method of bonding and integrating the base and the vibration isolator by attaching the vibration isolator formed into a sheet shape to the surface of the base using heat fusion or adhesive. There is. Furthermore, a copolymer resin having viscoelasticity is coated on the surface of a substrate such as a metal plate, and a restraining layer, such as another metal plate, is overlaid on the coated layer and joined together to form a metal plate/
A method of forming a so-called "Sandermanch structure" vibration isolation plate structure of a viscoelastic copolymer resin/metal plate is also known. In addition, various improvements have been made to the resin layer used as a cushioning intermediate for this anti-vibration composite metal plate with a sandwich structure. A proposal to use a copolymer resin from a combination of multiple types of different monomers (Japanese Patent Publication No. 39-12451)
), and other proposals using graft polymers derived from various specific combinations of monomers (Japanese Patent Publication No. 45-34703, Japanese Patent Publication No. 45-35662, Japanese Patent Publication No. 1973)
−31457, Special Publication No. 37898, Special Publication No. 1977-
37902 etc.) have also been made numerous times. Furthermore, a vibration isolating means having a butyl rubber vibration isolating material layer and an aluminum foil restraining layer provided thereon is used as a vibration isolating material provided on a ceiling board inside an automobile. However, the vibration-proofing effect of these conventionally known vibration-proofing materials can only be obtained in a relatively narrow temperature range around room temperature. There is a problem in parts such as ceilings and doors of transportation equipment where the temperature can rise to nearly 80℃ due to direct sunlight, where the vibration isolation effect is significantly impaired. A vibration-proofing method and vibration-proofing method that exhibits excellent vibration-proofing effects and is also excellent in terms of cold resistance, heat resistance, adhesion, ease of construction, conformability to the shape of the substrate surface (shapeability), economical efficiency, etc. Development of vibration materials is desired. The present inventors have conducted research to provide a vibration isolating method and vibration isolating material that can satisfy such demands for improvement. As a result, the active hydrogen group-containing liquid diene polymer, the bituminous substance, and the isocyanate group/the active hydrogen group possessed by the diene polymer (equivalence ratio) are in a certain range, especially in an amount of 0.5 to 0.95. A sheet-like molded body (A) containing a combination of organic polyisocyanate compounds, one side of which is a constraining layer (B),
It has been discovered that by bonding and integrating the other surface with the surface of the base (C), it is possible to easily achieve a vibration-proofing treatment that satisfies the above-mentioned improvement requests. It is therefore an object of the present invention to provide an improved vibration isolation method. The above objects and many other objects and advantages of the present invention will become more apparent from the above description. The sheet-like molded article (A) used in the method of the present invention comprises 100 parts by weight of a liquid diene polymer containing active hydrogen groups, about 50 to about 600 parts by weight of a bituminous material, and an isocyanate group/
Active hydrogen groups possessed by the diene polymer (equivalent ratio)
A sheet-shaped molded article containing an organic polyisocyanate compound in an amount of 0.5 to 0.95,
Its planar shape can be any shape depending on the planar shape of the base to be subjected to anti-vibration treatment. The active hydrogen group-containing liquid diene polymer is a polymer or copolymer that exhibits fluidity at room temperature and is derived from at least one diene monomer or a monomer containing this as a main component, and is a polymer or copolymer that exhibits fluidity at room temperature. Refers to something that has a group. For example, the number average molecular weight (n) is about 500 to about 20,000, and the viscosity is about
Preferred examples include liquid diene polymers containing active hydrogen groups of 2000 poise or less, more preferably about 500 poise or less. In terms of chemical structure, it is preferable to use one in which the content of 1,4 bond repeating units is about 50% or more. Such a liquid diene polymer is preferably a telechelic liquid diene rubber having an active hydrogen group at the end, and preferably has a functionality of 2 or around 2 containing active hydrogen per molecule. Examples of such active hydrogen groups are -OH, -CHO, -COOH, -OOH, -SH, -
Examples include active hydrogen-containing functional groups such as NH ₂ . It is undesirable to use excessively reactive functional groups that may cause trouble during storage or kneading with other ingredients, or functional groups that may produce harmful substances as by-products when reacting with the organic polyisocyanate compound. It is best to select and use the appropriate one, taking into consideration manufacturing costs and suitability for mass production.
Active hydrogen-containing functional groups such as OH and -COOH are preferred. Examples of such liquid diene polymers include:
An example is liquid polybutadiene having a terminal hydroxyl group, with a hydroxyl group content of about 0.75 to about 0.83 meq/g, a hydroxyl value of about 42.1 to about 46.6, and a number average molecular weight (n) of about
2800 liquid diene-based polymers are commercially available and can be utilized in the present invention. Examples of diene polymers or copolymers other than liquid polybutadiene include polyisoprene, butadiene-isoprene copolymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, etc. I can give an example. Examples of the bituminous substance that is the second component constituting the sheet-like molded product (A) used in the method of the present invention include straight asphalt, semi-brown asphalt,
Examples include blown asphalt and mixtures thereof, and preferably straight asphalt or a combination of straight asphalt and other asphalt. The bituminous substance as exemplified above is about 50 to 100 parts by weight based on 100 parts by weight of the active hydrogen group-containing liquid diene polymer.
It is utilized in an amount of about 600 parts by weight, more preferably about 100 to about 500 parts by weight. If the amount used is too small, it will be difficult to maintain a stable anti-vibration effect over a wide temperature range, and the adhesion strength will also decrease. Since the anti-vibration effect deteriorates, it is used within the above usage range. Furthermore, the organic polyisocyanate compound which is the third component constituting the sheet-like molded product (A) used in the method of the present invention is a polyisocyanate, that is, an organic compound having two or more isocyanate groups in one molecule. It has an isocyanate group that is reactive with the active hydrogen-containing functional group of the active hydrogen group-containing liquid diene polymer. Such organic polyisocyanate compounds are well known, and may be in the form of a prepolymer having isocyanate groups at the ends obtained by reacting a polyol and a polyisocyanate in advance. Examples of organic polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, Examples include methylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction product. The organic polyisocyanate compound acts as a curing or crosslinking component of the active hydrogen group-containing liquid diene polymer, and in the present invention, the isocyanate group/active hydrogen group possessed by the diene polymer (equivalent ratio) is used in an amount of 0.5 to 0.95. If this amount is equivalent to the equivalent ratio, for example
If it is too small (less than 0.4), the rubber elasticity of the sheet-like molded article (A) will be insufficient, and the vibration-proofing effect will be unsatisfactory. If the isocyanate group/active hydrogen group (equivalent ratio) is 1 or more, self-adhesiveness is lost, so it is necessary to use an adhesive for bonding and integration with the constraining layer (B) and the substrate (C). Therefore, if it is desired that the sheet-like molded article (A) has self-adhesive properties, the corresponding ratio should be less than 1, preferably 0.5 to 0.95. In such an equivalence ratio region, the sheet-like molded product (A)
There is an advantage that there is no need to use an adhesive to integrate the bonding layer (B) and the base (C). The sheet-like molded product (A) used in the method of the present invention can be provided by kneading the active hydrogen group-containing liquid diene polymer, bituminous material, and organic polyisocyanate compound, and molding the mixture into a sheet-like molded product in a desired shape. . The sheet-like molded article (A) can further contain various additives. Examples of such additives include viscosity reducers such as dioctyl phthalate, process oils, tackifiers such as petroleum resins, various stabilizers, fibrous or powder fillers such as mica, calcium carbonate, talc, etc. Agent, G-n
-butyltin laurate, stannath octoate, triethylenediamine, naphthenic acid metal salts,
Examples include urethane curing catalysts such as octylic acid metal salts. The amount of the additive used as exemplified above can be selected as appropriate, but for example, about 5 to about 50% by weight of a viscosity reducing agent, a vibration damping material, based on the weight of the molded object (A) forming composition; the same applies hereinafter. from about 5 to about 50% by weight based on the weight of the composition
of tackifier, based on the weight of the anti-vibration composition
Examples of amounts used include from about 30% by weight of fibrous or powdered filler, from about 0.005 to about 0.5% by weight of curing catalyst, based on the weight of the liquid diene polymer. According to the method of the present invention, one side of the structure made of the sheet-like molded body (A) as described above is bonded to the restraining layer (B), and the other side is bonded to the surface of the base body (C) without using an adhesive. By forming the sanderch structure of (B)/(A)/(C), excellent anti-vibration processing can be performed. On the spot, the sheet-shaped molded product (A) is sequentially placed on the base (C).
It is also possible to carry out such a vibration isolation method by integrally bonding the restraining layer (B) and the sheet-like molded body without using an adhesive. It is also possible to form a vibration damping material with a laminated structure consisting of (A) and to integrate the vibration damping material with a laminated structure onto a desired substrate (C) without using an adhesive. In this way, after the vibration-proofing treatment is performed by joining the restraining layer (B) to one side of the sheet-like molded body (A), the molded body
In an embodiment in which the other surface of (A) is bonded to the surface of the base (C), for example, a constraining layer (B) is formed on one side of the sheet-like molded product (A) having an arbitrary desired shape. A laminated vibration damping material with a release layer such as release paper on one side, or a long restraining layer, for example.
(B) On top of (A), a release layer is further laminated on the sheet-like molded product (A) which is extruded into a sheet-like shape with a desired thickness, and then a laminated structure vibration-damping material is used, which is cut into any desired shape. is possible and preferable. As the constraining layer (B), materials known per se can be used, such as metal flakes such as aluminum foil, resin-impregnated paper, resin-impregnated felt, resin-impregnated nonwoven fabric, and other similar materials having appropriate rigidity at room temperature. Any material that exhibits constrained layer functionality can be utilized. Such a constraint layer (B) may be a coating layer that can form a dry and cured film by heating to exhibit a constraint layer function.
Such a coating layer-forming composition may contain a coating-forming thermosetting synthetic resin or a thermosetting synthetic resin containing the resin as a main component, a thermoplastic synthetic resin such as polystyrene, a filler, a coloring agent, etc. A good film-forming composition can be used, and a sheet-shaped molded product can be used.
The constraining layer (B) can be formed by coating or spraying on one side of (A) and then heating and curing it, or by forming it into a film in advance and laminating it. The type of such a constraining layer (B) can be appropriately selected depending on the surface shape of the base (C), the construction site, etc. For example, if we take a car as an example, the base surface is relatively flat in areas such as the ceiling inside the car and behind the doors, but thin pieces of aluminum foil etc. are used as a restraining layer in areas where the vibration isolating material is on the back of the car or on vertical surfaces. It is preferable to use it in combination with the upper layer at room temperature.In the case of parts where the base surface has an uneven shape, such as a floor surface, and the vibration isolating material is on the surface, it softens by heating and adapts to the shape, then hardens and becomes rigid. It is preferable to use a composition that forms a constraining layer having: In the method of the present invention, the thickness of the sheet-shaped molded body (A) layer and the thickness of the constraining layer may be arbitrary and there are no limitations. For example, the former is approximately 0.5 to 5 mm, and the latter is approximately
Any combination of materials from 30μ aluminum foil to approximately 10mm resin-impregnated felt can be used. The sheet-like molded product (A) used in the method of the present invention has an isocyanate group/active hydrogen group (equivalent ratio) of 0.5 to
It has an excellent adhesiveness of 0.95 and can be attached to the substrate surface without using any other adhesive means, and has excellent adhesive strength even when used at room temperature or heated. It is something that can be manifested. Examples are given below to explain embodiments of the present invention in more detail. Naturally, the present invention is not limited to the following examples. Examples and Comparative Examples The compositions shown in the upper row of Table 1 were heated and mixed at about 100° C. and extruded to a thickness of about 1.7 mm to obtain a sheet-like vibration-proof molded product. The obtained anti-vibration molded body (A) was attached to a 0.8 m/m steel plate with the restraining layer shown in the middle row of Table 1 as an upper layer, and tests were conducted on each item shown in the lower row of Table 1. As a result, the present invention was confirmed. It was found that the vibration isolating material with a sanderch structure formed by this method can exhibit extremely excellent vibration isolating performance over a wide temperature range, and is also extremely superior in various performances such as adhesive strength, cold resistance, and heat resistance. .

【table】

[Table] The test method and evaluation were as follows. Adhesion Test A vibration-proofing material having a restraining layer as an upper layer was cut to a width of 25 mm, adhered to an electrodeposited steel plate also having a width of 25 mm, and then lightly pressed to obtain a test piece. Using a Strograph T-type testing machine, the tensile speed
A 180° peel test was conducted at 200 mm/min. Heat resistance test: 250 x 250
After cutting to mm and pasting on a 300 x 300 mm electroplated steel plate, 1
One sheet is kept vertically and the other sheet is kept on its back with the sample facing down, and kept in a thermostat at 100°C for 30 days. 〇 No displacement or falling off △ 100mm or less displacement, scratching equivalent to 1/3 of the area x Misalignment or falling off Cold resistance test Using a test plate prepared in the same way as the test plate for heat resistance tests, under -40℃ conditions After holding for 3 hours, perform a slamming test below to check for cracks and peeling of the paint film. 〇 No cracking or peeling △ Peeling occurring in 1/3 or less of the sample area × 〃 2/3 or more 〃 Vibration damping performance test A 20 x 180 piece of vibration damping material with a restraining layer as the upper layer
It is cut to a size of mm and attached to a 0.8 x 20 x 200 mm steel plate, and then used for testing. Measurement is by resonance method (Japan Acoustic Materials Association publication "Noise Countermeasures Handbook")
(see page 438), the loss coefficient η was determined. The larger the value of η, the higher the vibration-proofing effect, and it is said that if it is 0.05 or more, there is a vibration-proofing effect. Further, the heat-curing type constraining layer used in Example 2 was as follows. A composition containing 35 parts by weight of polyester (Nippon Shokubai Chemical Industry Co., Ltd. Epolack), 49 parts by weight of heavy calcium carbonate, 15 parts by weight of asbestos, 0.2 parts by weight of zinc stearate, and 0.8 parts by weight of benzoyl peroxide was prepared to a thickness of 0.5 mm. I did it so that it would work. Heating was carried out at 130°C for 1 hour.

Claims (1)

[Scope of Claims] 1. 100 parts by weight of a liquid diene polymer containing active hydrogen groups, about 50 to about 600 parts by weight of a bituminous substance, and an isocyanate group/active hydrogen group possessed by the diene polymer (equivalent ratio) of 0.5. A sheet-shaped molded article (A) containing an organic polyisocyanate compound in an amount of ~0.95
One side is the constraining layer (B), the other side is the base (C) surface,
A vibration isolation method for a base body characterized by forming a sandwich structure by integrating the parts without using an adhesive. 2 The joining and integration process involves joining the constraining layer (B) to one side of the sheet-like molded body (A), and then attaching the other side to the base (C).
The vibration isolation method according to claim 1, which is carried out by bonding to a surface.