JP4731331B2 - Anti-vibration structure - Google Patents

Description

  The present invention relates to a vibration isolating structure, and more particularly to a vibration isolating structure in which a vibration isolating material main body made of a member having elasticity is bonded and fixed to a metal substrate or a resin substrate via a urethane adhesive.

  An anti-vibration structure is generally a structure that is provided between a vibrating side and a side that receives vibration, and that prevents vibrations from being transmitted between them. Specifically, an elastic member An anti-vibration material body made of is bonded and fixed to a metal substrate or a resin substrate.

  In such a vibration-proof structure, the vibration-proof material body absorbs vibrations to prevent vibration transmission. Therefore, it is preferable that the vibration isolator body is firmly bonded to the metal substrate or the resin substrate. Research for improving the performance of the adhesive used for bonding, specifically, the adhesive strength of the adhesive Research to make it bigger is underway. Hereinafter, Patent Documents 1 to 5 will be cited and some of the research will be shown.

  Patent Documents 1 and 2 disclose an adhesive mainly composed of an epoxy resin. The adhesive disclosed in Patent Document 1 is an adhesive having good swaying properties. Specifically, an epoxy resin includes colloidal silica, an alkoxysilane having an organic polar group, a metal oxide, and a curing agent. Added adhesive. Patent Document 1 describes the action of the alkoxysilane, and the action of the organic polar group and the alkoxysilane group increases the connection between the epoxy resin and the curing agent, the colloidal silica, and the metal oxide. As a result, the swingability of the adhesive is improved.

  The adhesive disclosed in Patent Document 2 is a vulcanized adhesive, and 20 to 80 parts by mass of an organoalkoxysilane hydrolyzate or partial condensate and 1 to 30 parts by mass with respect to 100 parts by mass of an epoxy resin. Part of colloidal silica is an adhesive. This document describes the critical significance of the hydrolyzate or partial condensate content of organoalkoxysilane, and the critical significance is inferior in adhesion to a stainless steel plate when the content is less than 20 parts by mass. If the content exceeds 80 parts by mass, the adhesion to rubber is poor.

  Patent Document 3 discloses an adhesive mainly composed of a polyester resin, and the disclosed adhesive is 5 to 50% by weight of hydrophobic silica with respect to 50% by weight or more of the polyester resin. And 0.1 to 50% by weight of a polyisocyanate compound. This document describes the critical significance of the content of the polyisocyanate compound, and the critical significance is that if the content is less than 0.1% by weight, a crosslinking effect between the polyester resin and the hydrophobic silica can be expected. If the content exceeds 50% by weight, the adhesive strength after the boiling water resistance test is lowered due to the influence of the unreacted polyisocyanate compound.

  Patent Document 4 discloses a technique for bonding a vibration-proof rubber body to a metal fitting. In the technique disclosed in this document, an anodized film, an organic silane compound film, and a thermosetting resin are sequentially formed on the surface of the metal fitting, and a vibration-proof rubber body is placed on the thermosetting resin. Thereby, the vibration-proof rubber body is bonded to the metal fitting. In such a technique, it is described that the adhesive stability of the adhesive layer to the metal fitting surface can be obtained by the organosilane compound film.

Patent Document 5 discloses an adhesive for a rubber composition. The adhesive for rubber compositions disclosed in this document is an adhesive made of a copolymer containing urea or urethane groups, and specifically, a reaction product of polyisocyanate and a functional polymer.
Special Notice No. 46-038914 JP 2004-250463 A Japanese Unexamined Patent Publication No. 63-270782 Japanese Patent Application Laid-Open No. 06-171012 JP 2002-173660 A

  In the adhesive disclosed in Patent Document 1, an epoxy resin is bonded to colloidal silica via an alkoxysilane, and the adhesive force of the adhesive is increased by this connection. Similarly, in the adhesive disclosed in Patent Document 2, an epoxy resin is bonded to colloidal silica through a hydrolyzate or partial condensate of alkoxysilane. In the adhesive disclosed in Patent Document 3, polyisocyanate is used. The polyester resin is bound to the hydrophobic silica through the compound. As described above, in the adhesives disclosed in Patent Documents 1 to 3, a binder for binding the main agent of the adhesive such as an epoxy resin or a polyester resin and colloidal silica or hydrophobic silica is essential, and the amount of the binder added Is preferably 20 parts by mass or more based on 100 parts by mass of the main component of the adhesive. However, such a binder is often expensive, and therefore there is a possibility that the manufacturing cost of the adhesive cannot be kept low.

  Moreover, generally the adhesive agent which consists of a urethane resin single-piece | unit does not have sufficient adhesive force in order to adhere the member which has elasticity to a metal base material or a resin base material.

  The present invention has been made in view of such points, and the object of the present invention is to fix the vibration isolator body to a metal substrate or a resin substrate using an adhesive that can be manufactured at a relatively low cost. An object of the present invention is to provide an anti-vibration structure.

The anti-vibration structure of the present invention is formed by adhering and fixing an anti-vibration material body made of a material having elasticity to at least one of a metal substrate and a resin substrate via an adhesive. Specifically, this adhesive contains an isocyanate-based urethane resin that is a reaction product of a polyol and a polyisocyanate, and colloidal silica. Furthermore, content of colloidal silica is 1 mass part or more and 40 mass parts or less with respect to 100 mass parts of isocyanate type urethane resin. The isocyanate-based urethane resin is produced by reacting 100 parts by mass or more and 1000 parts by mass or less of polyisocyanate with respect to 100 parts by mass of polyol.

  Since the adhesive to be used is formed by adding colloidal silica to an isocyanate-based urethane resin, it has a larger adhesive force than the adhesive of a urethane resin alone.

  In the adhesive used, the isocyanate-based urethane resin is bonded to the colloidal silica surface through a physical bond or a chemical bond. Therefore, even if it does not contain the binder for linking the isocyanate-based urethane resin and the colloidal silica, the vibration-proof material body can be adhered to the metal substrate or the resin substrate.

  In the vibration-proof structure of the present invention, the adhesive preferably further contains a silane coupling agent, and the content of the silane coupling agent is 0 with respect to 100 parts by mass of the isocyanate-based urethane resin. It is preferably 1 part by mass or more and 5 parts by mass or less.

  In such a configuration of the adhesive, since the silane coupling agent is bonded to the colloidal silica surface via a chemical bond, the adhesive force of the adhesive can be increased. Therefore, by including a silane coupling agent in the adhesive, the heat resistance of the adhesive can be improved, and as a result, the vibration-proof structure bonded through the adhesive is exposed to a high temperature. However, there is no possibility that the vibration isolator main body is peeled off from the metal base material or the resin base material. Therefore, a very stable vibration-proof structure can be provided by bonding using this adhesive.

  In preferred embodiments described later, the isocyanate-based urethane resin is produced by reacting 100 parts by mass or more and 1000 parts by mass or less of polyisocyanate with respect to 100 parts by mass of polyol. Moreover, the hydroxyl value of a polyol is 50 KOHmg / g or more and 150 KOHmg / g or less.

  Further, in a preferred embodiment described later, the vibration isolator body is made of vulcanized rubber, and the metal base is made of at least one of iron, aluminum, and aluminum alloy.

  The resin base material is preferably made of a thermoplastic resin. In a preferred embodiment described later, the resin base material is made of at least one of polyamide and glass fiber reinforced polyamide, and may be made of a thermoplastic resin other than polyamide, such as polypropylene, polycarbonate, and high specific gravity polyethylene.

  According to the present invention, since the vibration isolator main body is bonded and fixed to the metal base or resin base using an inexpensive adhesive, the vibration isolator main body is bonded and fixed to the metal base or resin base. The structure can be manufactured at low cost.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The present invention is not limited to the matters described below.

Embodiment 1 of the Invention
In the first embodiment, a bush-type vibration isolation structure 10 is taken as an example of the vibration isolation structure, and the configuration and manufacturing method of the vibration isolation structure 10 will be described with reference to FIG. FIG. 1 is a cross-sectional view showing the configuration of the vibration isolation structure 10.

  The anti-vibration structure 10 is widely used in the field of automobiles and the like, and as shown in FIG. 1, a metal inner cylinder (metal base) 11 and an outer cylinder (metal base) 12 and meat A thick cylindrical anti-vibration material body 13, the inner cylinder 11 and the outer cylinder 12 are arranged on a concentric circle, and the anti-vibration material main body 13 is disposed between the inner cylinder 11 and the outer cylinder 12. They are interposed and bonded to each other. That is, in the vibration isolating structure 10, the inner peripheral surface of the vibration isolator main body 13 is bonded to the outer surface of the inner cylinder 11 via the adhesive 17, and a part of the outer peripheral surface of the vibration isolator main body 13 is the adhesive 17. It is formed by being bonded to the inner surface of the outer cylinder 12 via

  In addition, although it is preferable that the outer peripheral surface of the vibration isolator main body 13 and the cylinder inner surface of the outer cylinder 12 are mutually adhere | attached via the adhesive agent 17, the inner peripheral surface of the vibration isolator main body 13 and the inner cylinder 11 are attached. The cylinder outer surface may be bonded to each other via an adhesive different from the adhesive 17. For example, the inner cylinder 11 and the vibration isolator body 13 may be vulcanized and bonded. At that time, a phenolic resin adhesive (for example, trade name Chemlock 205 manufactured by US Road Co., Ltd.) is applied as a lower layer to the adhesive surface (outer peripheral surface) of the inner cylinder 11 and dried, and then the upper layer is a chlorinated rubber adhesive. An unvulcanized rubber composition that becomes the vibration isolator body 13 is applied so as to cover the inner cylinder 11 to which the two layers of adhesive are applied (for example, trade name Chemlock 220 manufactured by US Road Co., Ltd.) and dried. The inner cylinder 11 and the vibration isolator body 13 can be vulcanized and bonded by providing and vulcanizing the inner cylinder 11.

  Specifically, the inner cylinder 11 and the outer cylinder 12 are made of iron, aluminum, or an aluminum alloy. On the adherend surfaces of the inner cylinder 11 and the outer cylinder 12, that is, on the outer surface of the inner cylinder 11 and the inner surface of the outer cylinder 12, a metal coating (not shown) such as a zinc phosphate coating or a non-chrome coating is formed. It is preferable. The aluminum alloy refers to an alloy containing 50% by mass or more of aluminum as a main component and, for example, containing copper, magnesium, manganese, and the like.

  The vibration isolator body 13 is obtained by vulcanizing and molding an unvulcanized rubber composition into a thick cylindrical shape. Natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), chloroprene rubber. (CR), acrylonitrile-isoprene rubber (NIR), butadiene rubber (BR) and the like alone or a blended rubber thereof.

  The adhesive 17 is an adhesive having a gelation start temperature of 100 ° C. or higher and a curing temperature of 180 ° C. or lower, and is an adhesive obtained by adding colloidal silica to an isocyanate-based urethane resin. That is, the adhesive 17 is produced by mixing polyol, polyisocyanate, and colloidal silica. In such an adhesive, it is considered that the isocyanate group of the isocyanate-based urethane resin or the hydroxyl group in the polyol is bonded to the colloidal silica surface through a physical bond or a chemical bond. That is, since the main agent of the adhesive is directly bonded to the colloidal silica, the adhesive 17 may not contain a binder for connecting the main agent of the adhesive and the colloidal silica. Moreover, since the adhesive 17 contains colloidal silica, it has a larger adhesive force than the adhesive of a urethane resin alone.

  The isocyanate-based urethane resin is a product of an addition reaction between a hydroxyl group of a polyol and an isocyanate group of a polyisocyanate. That is, some of the isocyanate groups of the polyisocyanate are added to the hydroxyl groups of the polyol to produce an isocyanate-based urethane resin, while some or all of the unreacted isocyanate groups are physically or chemically bonded. To the surface of the colloidal silica. Specifically, the polyisocyanate content is preferably 100 parts by mass or more and 1000 parts by mass or less, more preferably 120 parts by mass or more and 800 parts by mass or less, with respect to 100 parts by mass of the polyol. Most preferably, it is 180 parts by mass or more and 300 parts by mass or less. In addition, all mass parts are numerical values when converted into solid content. The same applies to the following.

  The polyol is preferably a polyol having a hydroxyl value of 40 KOH mg / g or more and 150 KOH mg / g or less, more preferably a polyol having a hydroxyl value of 50 KOH mg / g or more and 130 KOH mg / g or less, and a polyol having a hydroxyl value of 80 KOH mg / g or more and 120 KOH mg / g or less. Most preferably, it is preferably a polyester polyol. In addition, it is preferable that the hydroxyl value of a polyol is selected according to content of polyisocyanate.

  Polyisocyanate is a compound having two or more isocyanate groups in one molecule, and examples thereof include polymethylene polyphenyl polyisocyanate.

  Colloidal silica is formed by, for example, colloidal dispersion of silica particles having a particle size of 10 μm to 20 μm in water. The content of the colloidal silica is 1 part by mass or more and 40 parts by mass or less, preferably 2 parts by mass or more and 30 parts by mass or less, with respect to 100 parts by mass of the isocyanate-based urethane resin. More preferably, it is at most parts. If the colloidal silica content is below the above range, the adhesive strength of the adhesive may be reduced, and the adhesive layer having low adhesive strength will be destroyed. Therefore, it is not preferable because it causes peeling. On the other hand, if the content exceeds the above range, the manufacturing cost of the adhesive 17 cannot be kept low, which is not preferable.

  The manufacturing method of such an adhesive 17 is to mix a polyol, polyisocyanate, and colloidal silica in a predetermined mixing ratio.

  The adhesive 17 preferably contains a silane coupling agent in addition to colloidal silica. The silane coupling agent is preferably, for example, at least one of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. It is preferably contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass. In the adhesive in which the silane coupling agent is added to the adhesive 17, the silane coupling agent is bonded to the colloidal silica through a chemical bond. Has adhesive strength. Therefore, when exposing the vibration isolating structure 10 to a high temperature of about 150 ° C., it is preferable to use an adhesive containing a silane coupling agent.

  Next, a method for manufacturing the vibration isolating structure 10 will be described.

  First, the vibration isolator body 13, the inner cylinder 11, and the outer cylinder 12 are prepared. Specifically, the vibration proof material body 13 is formed by vulcanizing and molding an unvulcanized rubber composition into a thick cylindrical shape. Also, a small-diameter and long metal cylinder is prepared, and a chemical conversion treatment is performed on the outer surface of the cylinder to form the inner cylinder 11. Also, a large-diameter and short metal cylinder is prepared, and the same process is applied to the cylinder inner surface to form the outer cylinder 12. Here, the chemical conversion treatment is, for example, to form a zinc phosphate coating or the like on the surface after removing dirt such as an oxide coating and oil and fat by performing an etching treatment.

  Next, the adhesive 17 is applied to the bonding surface of the vibration isolator body 13. Specifically, each of the inner peripheral surface and a part of the outer peripheral surface of the vibration isolator body 13 is subjected to surface treatment for degreasing, cleaning, and removal of the oxide film, and then the above-described adhesive 17 is applied. To do. Here, the surface treatment is, for example, applying a sodium hypochlorite solution or a chlorinated cyanuric acid solution to the inner peripheral surface and a part of the outer peripheral surface.

  Subsequently, the inner cylinder 11 and the outer cylinder 12 are placed under the curing temperature of the adhesive 17. Specifically, the inner cylinder 11 and the outer cylinder 12 are arranged concentrically at intervals, and the temperature of the space region between the inner cylinder 11 and the outer cylinder 12 is equal to or higher than the curing temperature of the adhesive 17 described above. After raising the temperature to a temperature (for example, 180 ° C. to 230 ° C.), the mixture is allowed to cool for 1 to 10 seconds. Thereby, the temperature of the said space area turns into the gel-like temperature from which the adhesive agent 17 will be in a gel state.

  Then, the vibration isolator body 13 is press-fitted into the space area. At this time, since the space region is under the gel-like temperature described above, when the vibration isolator body 13 is press-fitted into the space region, it is applied to the inner peripheral surface and a part of the outer peripheral surface of the vibration isolator body 13. The adhesive 17 is in a gel state. As a result, the inner peripheral surface of the vibration isolator main body 13 is bonded to the outer surface of the inner cylinder 11, and the outer peripheral surface of the vibration isolator main body 13 is bonded to the inner surface of the outer cylinder 12. Thereby, the vibration isolating structure 10 can be manufactured.

  In addition, you may adhere | attach the inner peripheral surface of the vibration-proof material main body 13 and the cylinder outer surface of the inner cylinder 11 using the adhesive agent different from the adhesive agent 17. FIG. For example, the inner cylinder 11 and the vibration isolator body 13 may be vulcanized and bonded, and the specific method of vulcanizing and bonding is as described above.

  Below, the effect which the vibration isolator structure 10 show | plays is put together.

  In the vibration isolation structure 10, the vibration isolation main body 13 is bonded to the inner cylinder 11 and the outer cylinder 12 via an adhesive 17. This adhesive 17 has a larger adhesive force than that of a single urethane resin adhesive. Therefore, the vibration isolator body 13 can be strongly bonded to the inner cylinder 11 and the outer cylinder 12 as compared with the vibration isolator structure bonded using an adhesive made of a single urethane resin. The stability of the can be improved.

  Moreover, in the adhesive 17, since the main agent of the adhesive is not an epoxy resin or a polyester resin but an isocyanate-based urethane resin, a binder for binding the main agent of the adhesive to the colloidal silica may not be included. Further, in the adhesive 17, the content of colloidal silica relative to the isocyanate-based urethane resin is small. From the above, the use of a compound that can be directly linked to colloidal silica as the main agent of the adhesive and the low content of colloidal silica can reduce the production cost of the adhesive 17. Therefore, the manufacturing cost of the vibration proof structure 10 can be kept low.

<< Embodiment 2 of the Invention >>
In the second embodiment, a bracket is taken as another example of the vibration isolation structure, and the configuration of the vibration isolation structure 20 is shown using FIG. FIG. 2 is a cross-sectional view of the vibration-proof structure 20.

  The anti-vibration structure 20 is widely used in the field of automobiles and the like, like the anti-vibration structure 10 of the first embodiment. As shown in FIG. 2, the small attachment hole 30 and the large attachment hole 40 are used. Are formed in parallel.

  A metal inner cylinder (metal base material) 31 is inserted in the small mounting hole 30 with the opening direction aligned, and a vibration isolating material is interposed between the inner cylinder 31 and the small mounting hole 30. A main body 33 is interposed and bonded. Specifically, the vibration isolator body 33 has an outer peripheral surface bonded to the inner wall surface of the small mounting hole 30 via an adhesive (not shown), and an inner peripheral surface attached to the inner cylinder 31 via an adhesive (not shown). It is adhered to the outer surface of the cylinder.

  In addition, it is preferable that the metal film (not shown) described in the first embodiment is formed on the outer surface of the inner cylinder 31. The above-described adhesive is substantially the same as the adhesive 17 described in the first embodiment. The inner wall of the small mounting hole 30 and the vibration isolator body 33 are preferably bonded to each other via the adhesive described in the first embodiment, but the inner cylinder 31 and the vibration isolator body 33 are They may be bonded to each other via an adhesive different from the adhesive described in the first embodiment. For example, the inner cylinder 31 and the vibration isolator body 33 may be vulcanized and bonded. At that time, a phenolic resin adhesive (for example, trade name Chemlock 205 manufactured by US Road Co., Ltd.) is applied as a lower layer to the adhesive surface (outer peripheral surface) of the inner cylinder 31 and dried, and then the upper layer is a chlorinated rubber adhesive. An unvulcanized rubber composition that becomes the vibration isolator body 33 is applied so as to cover the inner cylinder 31 to which the two layers of adhesive are applied (for example, trade name Chemlock 220 manufactured by US Road Co., Ltd.) and dried. The inner cylinder 31 and the vibration isolator body 33 can be vulcanized and bonded by providing and vulcanizing and molding the same.

  A resin cylinder (resin base material) 41 is inserted into the large mounting hole 40 with the opening direction aligned, and is bonded to the inner surface of the large mounting hole 40 via an adhesive (not shown). Further, inside the cylinder of the resin cylinder 41, a metal inner cylinder (metal base material) 42 is inserted with a gap in the opening direction, and between the inner cylinder 42 and the resin cylinder 41, An anti-vibration material body 43 is interposed and bonded. Specifically, the vibration isolator body 43 has an outer peripheral surface bonded to the inner surface of the resin cylinder 41 via an adhesive (not shown), and an inner peripheral surface of the inner cylinder 42 via an adhesive (not shown). Bonded to the outer surface of the cylinder.

  The resin cylinder 41 is preferably a cylinder made of polyamide or glass fiber reinforced polyamide. Moreover, it is preferable that the metal coating (not shown) described in the first embodiment is formed on the outer surface of the inner cylinder 42. The above-described adhesive is substantially the same as the adhesive 17 described in the first embodiment. Further, it is preferable that the inner wall of the large mounting hole 40, the resin cylinder 41, and the resin cylinder 41 and the vibration isolator main body 43 are bonded to each other via the adhesive described in the first embodiment. It is also possible to simply press-fit the resin cylinder 41 into the inner wall of 40 without using this adhesive, and the adhesive between the inner wall of the large mounting hole 40 and the resin cylinder 41 can be omitted. Further, the inner cylinder 42 and the vibration isolator main body 43 may be bonded to each other via an adhesive different from the adhesive described in the first embodiment. For example, the inner cylinder 42 and the vibration isolator main body 43 may be vulcanized and bonded. In that case, a phenolic resin adhesive (for example, trade name Chemlock 205 manufactured by US Road Co., Ltd.) is applied as a lower layer to the adhesive surface (outer peripheral surface) of the inner cylinder 42 and dried, and then the upper layer is a chlorinated rubber adhesive. An unvulcanized rubber composition that becomes a vibration isolator body 43 is applied so as to cover the inner cylinder 42 to which the two layers of adhesive are applied (for example, trade name Chemlock 220 manufactured by US Road Co., Ltd.) and dried. The inner cylinder 42 and the vibration isolator main body 43 can be vulcanized and bonded by providing and vulcanizing this.

  The manufacturing method of such a vibration isolating structure 20 is the same as in the first embodiment, and the vibration isolating material main body 33 is interposed between the inner wall surface of the small mounting hole 30 and the inner cylinder 31 and bonded thereto. The resin cylinder 41 is adhered to the inner wall surface of the large mounting hole 40, and the vibration isolator main body 43 is interposed between the resin cylinder 41 and the inner cylinder 42 in the same manner as in the first embodiment. Is. The inner cylinder 31 and the vibration isolator main body 33 may be bonded using an adhesive different from the adhesive described in the first embodiment, and the inner cylinder 42 and the vibration isolator main body 43 are bonded. May be. For example, the inner cylinder 31 and the vibration isolator main body 33 may be vulcanized and bonded, or the inner cylinder 42 and the vibration isolator main body 43 may be vulcanized and bonded. It is as follows.

  In the vibration isolating structure 20 of the present embodiment, the vibration isolator main body 33 is bonded to the inner wall surface of the small mounting hole 30 and the cylinder outer surface of the inner cylinder 31 using the adhesive of the first embodiment. Since the main body 43 is bonded to the inner wall surface of the resin cylinder 41 and the outer surface of the inner cylinder 42, the same effect as that of the vibration isolating structure 10 of the first embodiment is obtained.

<< Other Embodiments >>
The present invention may be configured as follows for the first and second embodiments.

  Although the metal coating is formed on the cylinder outer surface of the inner cylinders 11, 31, and 42 and the cylinder inner surface of the outer cylinder 12, an inner cylinder and an outer cylinder on which no metal coating is formed may be used. In addition, in order to further strengthen the adhesive strength with respect to the vibration isolator body, it is preferable that a metal film is formed on the adherend surface.

  Needless to say, the shapes of the vibration-proof structures 10 and 20, that is, the shapes of the inner cylinders 11, 31, and 42 and the outer cylinder 12 are not limited to the shapes shown in FIGS. 1 and 2, respectively.

Examples of the present invention are shown below.
<Example 1-Test at room temperature (part 1)>
In Example 1, the optimal chemical species of the polyol which is a raw material of the isocyanate-based urethane resin was determined. Further, the relationship between the content of colloidal silica and the adhesive strength was examined. The compositions of Samples 1 to 15 are also described in Table 1 described later.
1. Preparation method of sample and comparative sample-Sample 1
Sample 1 was prepared by mixing a polyol (Kratite T-20, manufactured by Hirono Chemical Co., Ltd.) and an isocyanate (Kratite T-200, manufactured by Hirono Chemical Co., Ltd.) so that the weight ratio was the former: the latter = 3: 1. Made. In addition, the hydroxyl value of a polyol (same) is 50 KOHmg / g, The composition is 30 mass% of o-dichlorobenzene, 15 mass% of toluene, 25 mass% of ethyl acetate, and 30 mass% of polyester polyol.
-Sample 2-
Sample 2 was prepared by adding 2 parts by mass of colloidal silica (MEK-ST, manufactured by Nissan Chemical Co., Ltd.) to 100 parts by mass of the isocyanate-based urethane resin of Sample 1. That is, Sample 2 was obtained by adding 3.75 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 1. The composition of colloidal silica (same as above) is 70% by mass of methyl ethyl ketone and 30% by mass of silica.
-Sample 3-
Sample 3 was prepared by adding 5 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 1. That is, Sample 3 was prepared by adding 7.5 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 1.
-Sample 4-
Sample 4 was prepared by adding 10 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 1. That is, Sample 4 was prepared by adding 15 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 1.
-Sample 5-
Sample 5 was prepared by adding 20 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 1. That is, Sample 5 was prepared by adding 30 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 1.
-Sample 6
A sample (6) was prepared by mixing a polyol (Klatite D, manufactured by Hirono Chemical Co., Ltd.) and an isocyanate (same) so that the weight ratio was the former: the latter = 3: 1.6. In addition, the hydroxyl value of the polyol (same as above) is 80 KOH mg / g, and its composition is substantially the same as the polyol of Sample 1.
-Sample 7-
Sample 2 was obtained by adding 2 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 6. That is, Sample 7 was prepared by adding 3 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 6.
-Sample 8-
Sample 8 was obtained by adding 4 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of sample 6. That is, Sample 8 was obtained by adding 6.5 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 6.
-Sample 9-
Sample 9 was prepared by adding 7 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 6. That is, Sample 9 was obtained by adding 13 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 6.
-Sample 10-
Sample 10 was prepared by adding 15 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 6. That is, Sample 10 was obtained by adding 26 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 6.
-Sample 11-
Polyol (Klatite K-35, manufactured by Hirono Chemical Co., Ltd.) and isocyanate (same as above) were mixed so that the weight ratio was the former: latter = 3: 2.4 to prepare Sample 11. The hydroxyl value of the polyol (same as above) is 110 KOH mg / g, and its composition is substantially the same as the polyol of Sample 1.
-Sample 12-
Sample 12 was prepared by adding 1 part by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 11. That is, Sample 12 was obtained by adding 3 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 11.
-Sample 13-
Sample 13 was prepared by adding 3 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 11. That is, Sample 13 was obtained by adding 5.5 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 11.
-Sample 14-
Sample 12 was prepared by adding 5 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 11. That is, Sample 14 was obtained by adding 11 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 11.
-Sample 15-
Sample 15 was obtained by adding 10 parts by mass of colloidal silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of Sample 11. That is, Sample 15 was obtained by adding 22 g (including solvent) of colloidal silica (same as above) to 100 g of Sample 11.
-Comparative sample 1-
Comparative sample 1 was obtained by adding 2 parts by mass of hydrophobic silica (HDK H18, manufactured by Nissan Chemical Co., Ltd.) to 100 parts by mass of the isocyanate-based urethane resin of sample 6. That is, Comparative Sample 1 was prepared by adding 1 g of hydrophobic silica (same as above) (including solvent) to 100 g of Sample 6.
-Comparative sample 2-
Comparative sample 2 was obtained by adding 4 parts by mass of hydrophobic silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of sample 6. That is, Comparative Sample 2 was obtained by adding 2 g of hydrophobic silica (same as above) (including solvent) to 100 g of Sample 6.
-Comparative sample 3-
Comparative sample 3 was obtained by adding 7 parts by mass of hydrophobic silica (same as above) to 100 parts by mass of the isocyanate-based urethane resin of sample 6. That is, Comparative Sample 3 was prepared by adding 4 g (including solvent) of hydrophobic silica (same as above) to 100 g of Sample 6.
2. 90 degree peeling test method Each of the above samples 1 to 15 and comparative samples 1 to 3 was subjected to a 90 degree peeling test in accordance with JIS K6854-1. Specifically, a test piece in which an iron base material and an elastic member are bonded to each other through a sample 1 is attached to a predetermined position of a 90 degree peeling test apparatus (Autograph Tester, manufactured by Shimadzu Corporation), and the elastic member is made of iron. The elastic member was pulled out of the base material. Thereafter, the fracture surface of the iron substrate was visually observed, and the ratio of the fracture surface being an elastic member was determined as the fracture rate. With respect to the fracture rate, if the fracture rate is 100%, it means dissociation due to fracture in the elastic member.

The same 90-degree peel test was also performed on a test piece in which the chemically formed iron base material and the elastic member were bonded, and a test piece in which the aluminum base material and the elastic member were bonded.
3. Results and Discussion Table 1 shows the test results.

  First, based on the test results of Sample 1, Sample 6, and Sample 11, optimization of the chemical species of the polyol will be considered.

  As shown in Table 1, when Kratite T-20 was used as the polyol, the fracture rate was 0 to 5%. When Kratite D and Kratite K-35 were used as the polyol, the fracture rate was May be 100%. Therefore, it is preferable to use Kratite D and Kratite K-35 as the polyol, and it is preferable to use a polyol having a hydroxyl value of 80 KOHmg / g or more.

  Next, optimization of the chemical species of silica will be considered based on the test results of Samples 7 to 9 and the test results of Comparative Samples 1 to 3.

  As shown in Table 1, for example, when the test result of the sample 7 and the test result of the comparative sample 1 were compared, the sample 7 showed a larger destruction rate. Similarly, when the test result of Sample 8 and the test result of Comparative Sample 2 were compared, the same result was obtained when the test result of Sample 9 and the test result of Comparative Sample 3 were compared. Therefore, as silica, it is preferable not to contain hydrophobic silica but to contain colloidal silica.

  Subsequently, based on the test results of Samples 6 to 10 and based on the test results of Samples 11 to 15, the relationship between the colloidal silica content and the adhesive strength will be considered.

  As shown in Table 1, in Samples 6 to 10, the fracture rate increased as the colloidal silica content increased, and Sample 10 showed 100% regardless of the material of the test piece. In Samples 11 to 15, the fracture rate increased as the colloidal silica content increased, and Sample 13 showed 100% regardless of the material of the test piece. Therefore, the adhesive strength increased as the content of colloidal silica was increased.

As described above, in this example, it is preferable to use a polyol having a hydroxyl value of 80 KOHmg / g or more as the polyol, and it is preferable to use colloidal silica as the silica, and the content of colloidal silica is larger. Was found to be preferable.
<Example 2—Test at room temperature (part 2)>
In Example 2, the amount of colloidal silica added was optimized. As a comparative sample, a material in which hydrophilic silica and hydrophobic silica were added instead of colloidal silica was used. The compositions of Samples 16 to 20 and Comparative Samples 4 and 5 are also described in Table 2 described later.
1. Preparation Method of Sample and Comparative Sample -Sample 16-
First, a polyol (Kratite D, manufactured by Hirono Chemical Industry Co., Ltd.) and an isocyanate (Kratite T-200, manufactured by Hirono Chemical Industry Co., Ltd.) are mixed so that the weight ratio is the former: latter = 3: 1.6. Isocyanate urethane resin was made.

Next, 1 part by mass of colloidal silica (MEK-ST organosilica sol, manufactured by Nissan Chemical Co., Ltd.) was added to 100 parts by mass of the isocyanate-based urethane resin to prepare Sample 16. That is, Sample 16 was prepared by adding 1.8 g of colloidal silica (including the solvent) to 100 g of the isocyanate-based urethane resin.
-Sample 17-
A sample having the same configuration as the sample 16 was used as a sample 17 except that 5 parts by mass of colloidal silica (same) was added to 100 parts by mass of the isocyanate-based urethane resin. That is, 9 g (including a solvent) of colloidal silica (same as above) was added to 100 g of the above isocyanate-based urethane resin to prepare Sample 17.
-Sample 18-
A sample having the same configuration as Sample 16 was designated as Sample 18, except that 10 parts by mass of colloidal silica (same) was added to 100 parts by mass of the isocyanate-based urethane resin. That is, 18 g (including a solvent) of colloidal silica (same as above) was added to 100 g of the above isocyanate-based urethane resin to prepare Sample 18.
-Sample 19-
A sample having the same configuration as the sample 16 was used as a sample 19 except that 20 parts by mass of colloidal silica (same) was added to 100 parts by mass of the isocyanate-based urethane resin. That is, the sample 19 was prepared by adding 36 g (including a solvent) of colloidal silica (same as above) to 100 g of the isocyanate-based urethane resin.
-Sample 20-
A sample having the same configuration as the sample 16 was used as a sample 20 except that 40 parts by mass of colloidal silica (same) was added to 100 parts by mass of the isocyanate-based urethane resin. That is, 72 g (including a solvent) of colloidal silica (same as above) was added to 100 g of the isocyanate-based urethane resin to prepare Sample 20.
-Comparative sample 4-
A sample having the same configuration as Sample 16 was used as Comparative Sample 4 except that 10 parts by mass of hydrophobic silica (HDK H18, manufactured by Nissan Chemical Industries, Ltd.) was added to 100 parts by mass of the isocyanate-based urethane resin. That is, Comparative Sample 4 was prepared by adding 5.4 g of hydrophobic silica (same as above) (including solvent) to 100 g of the isocyanate-based urethane resin.
-Comparative sample 5-
A sample having the same configuration as that of Sample 16 was used as Comparative Sample 5 except that 10 parts by mass of hydrophilic silica (HDK V15, manufactured by Nissan Chemical Industries, Ltd.) was added to 100 parts by mass of the isocyanate-based urethane resin. That is, Comparative Sample 5 was prepared by adding 5.4 g of hydrophilic silica (same as above) (including solvent) to 100 g of the above isocyanate-based urethane resin.
2. Adhesive strength measurement method The adhesive strength of the adhesive was measured for each of Samples 16 to 20 and Comparative Samples 4 and 5 in accordance with JIS K6849. Specifically, it is attached to a predetermined position of an adhesive force measuring apparatus (autograph tester, manufactured by Shimadzu Corporation) in which two iron substrates are bonded through a sample 16, and one iron substrate is made of the other iron. One of the iron substrates was pulled so as to be detached from the substrate, and the tensile force when the substrate was detached was read.
3. Results and Discussion Table 2 shows the test results.

  When the test results of Samples 16 to 20 were compared, the adhesive strength of Sample 17 was the largest, and the adhesive strength was smaller than that of Sample 17 whether the amount of colloidal silica added was increased or decreased. Thereby, it is most preferable to add 5 parts by mass of colloidal silica to 100 parts by mass of the isocyanate-based urethane resin.

Moreover, when the test result of the sample 18 and the test results of the comparative samples 4 and 5 were compared, the adhesive force of the sample 18 was the greatest. Thereby, like the test result in Example 1 above, it is preferable to add colloidal silica to the isocyanate-based urethane resin instead of adding hydrophobic silica or hydrophilic silica.
<Example 3-Test at high temperature (previous test)>
In Example 3, a pre-test for developing an adhesive having a large adhesive force at a high temperature was performed. Specifically, Comparative Samples 6 to 10 were used to optimize the hydroxyl value of the polyol and the isocyanate content in the isocyanate-based urethane resin. The compositions of Comparative Samples 6 to 10 are also described in Table 3 described later.
a) Optimization of hydroxyl number of polyol Preparation method of comparative sample-Comparative sample 6-
Sample 1 in Example 1 was used as comparative sample 6. That is, a polyol (Kratite T-20, manufactured by Hirono Chemical Co., Ltd.) and an isocyanate (Kratite T-200, manufactured by Hirono Chemical Co., Ltd.) were mixed so that the weight ratio was the former: the latter = 3: 1. Comparative sample 6 was made.
-Comparative sample 7-
Sample 6 in Example 1 was used as comparative sample 7. That is, a comparative sample 7 was prepared by mixing a polyol (Klatite D, manufactured by Hirono Chemical Co., Ltd.) and an isocyanate (same) so that the weight ratio was the former: the latter = 3: 1.6.
-Comparative sample 8-
Sample 11 in Example 1 was used as comparative sample 8. That is, a comparative sample 8 was prepared by mixing a polyol (Klatite K-35, manufactured by Hirono Chemical Co., Ltd.) and an isocyanate (same) so that the weight ratio was the former: the latter = 3: 2.4.
2. Method for Measuring Adhesive Strength at High Temperature With respect to the above comparative samples 6 to 8, the adhesive strength of the adhesive at 150 ° C. was measured according to JIS K6849. Specifically, first, it was attached to a predetermined position of an adhesive force measuring apparatus (autograph tester, manufactured by Shimadzu Corporation) in which two iron base materials were bonded via the comparative sample 6. At this time, the adhesive force measuring device was placed in an atmosphere of 150 ° C. And one iron base material was pulled so that one iron base material might remove | deviate from the other iron base material, and the tensile force when it removed was read.
3. Results and Discussion Table 3 shows the test results.

As shown in Table 3, the adhesive strength of Comparative Sample 8 was the maximum. Therefore, in the following, it was decided to use polyol (Kuratite K-35, manufactured by Hirono Chemical Co., Ltd.).
b) Optimization of isocyanate content Test Method-Comparative Sample 9-
Comparative sample 9 was the same as Comparative sample 6 except that the weight ratio of polyol (Klatite K-35, manufactured by Hirono Chemical Co., Ltd.) and isocyanate (same as above) was 3: 4.8. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
-Comparative sample 10-
Comparative sample 10 had the same configuration as comparative sample 6 except that the weight ratio of polyol (Klatite K-35, manufactured by Hirono Chemical Co., Ltd.) and isocyanate (same) was 3: 9.6. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
2. Test results and discussion The test results are shown in Table 3 above.

As shown in Table 3, in Comparative Samples 8 to 10, the adhesive strength of Comparative Sample 9 was the maximum. From the above, in this test, polyol (Kratite K-35, manufactured by Hirono Chemical Co., Ltd.) and isocyanate (Kuratite T-200, manufactured by Hirono Chemical Co., Ltd.) are in the weight ratio of the former: the latter = 3: 4.8. The isocyanate-based urethane resin adhesive A contained in is used.
<Example 4-Test at high temperature (main test)>
In Example 4, by using the isocyanate-based urethane resin A, an optimum compound as a silane coupling agent was specified and the addition amount of the silane coupling agent with respect to the urethane resin A was optimized. The compositions of samples 21 to 28 described later are also described in Table 4 described later.
a) Identification of the most suitable compound as a silane coupling agent Test Method-Sample 21-
5 parts by mass of colloidal silica (MEK-ST, manufactured by Nissan Chemical Co., Ltd.) is added to 100 parts by mass of the isocyanate-based urethane resin A, and 3-glycidoxypropyltrimethoxysilane (Z-6040, Dow) A sample 21 was prepared by adding 0.1 part by mass of “Epoxysilane” in Table 4 manufactured by Corning Toray. That is, to 100 g of isocyanate-based urethane resin A, 12 g of colloidal silica (same as above) and 0.07 g of 3-glycidoxypropyltrimethoxysilane (same as above) (including solvent) are added. Sample 21 was made. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
-Sample 22-
For 100 parts by mass of the isocyanate-based urethane resin A, not 3-glycidoxypropyltrimethoxysilane (same) but 3-mercaptopropyltrimethoxysilane (Z-6062, manufactured by Dow Corning Toray, Table 4 Sample 22 was the same configuration as Sample 21 except that 0.1 part by mass of “mercaptosilane” was added. That is, the addition amount of 3-mercaptopropyltrimethoxysilane (same as above) was 0.07 g (including solvent) with respect to 100 g of the isocyanate-based urethane resin A. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
-Sample 23-
For 100 parts by mass of the isocyanate-based urethane resin A, not 3-glycidoxypropyltrimethoxysilane (same) but 3-aminopropyltriethoxysilane (Z-6011, manufactured by Dow Corning Toray, Table 4 Sample 23 had the same configuration as Sample 21 except that 0.1 part by mass of “aminosilane” was added. That is, the addition amount of 3-aminopropyltriethoxysilane (same as above) was 0.07 g (including solvent) with respect to 100 g of isocyanate urethane resin A. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
2. Test results and discussion The test results are shown in Table 4.

As shown in Table 4, the adhesive force of Sample 23 was the maximum. Therefore, in the following, the optimum addition amount of 3-aminopropyltriethoxysilane (same as above) to the isocyanate-based urethane resin A was examined.
b) Optimization of addition amount of silane coupling agent to isocyanate-based urethane resin A Test Method-Sample 24-
The addition amount of 3-aminopropyltriethoxysilane (same as above) is 0.2 parts by mass with respect to 100 parts by mass of the isocyanate-based urethane resin A (0.14 g (including solvent) with respect to 100 g of the isocyanate-based urethane resin). Except for this, the sample 24 has the same configuration as the sample 23 described above. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
-Sample 25-
The addition amount of 3-aminopropyltriethoxysilane (same as above) is 0.5 parts by mass with respect to 100 parts by mass of the isocyanate-based urethane resin A (0.35 g (including solvent) with respect to 100 g of the isocyanate-based urethane resin). Except for this, the sample 25 has the same configuration as the sample 23 described above. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
-Sample 26-
The addition amount of 3-aminopropyltriethoxysilane (same as above) is 0.7 parts by mass with respect to 100 parts by mass of the isocyanate-based urethane resin A (0.5 g (including solvent) with respect to 100 g of the isocyanate-based urethane resin). Except for this, the sample 26 has the same configuration as the sample 23 described above. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
-Sample 27-
The addition amount of 3-aminopropyltriethoxysilane (same as above) is 1 part by mass with respect to 100 parts by mass of the isocyanate-based urethane resin A (0.7 g (including solvent) with respect to 100 g of the isocyanate-based urethane resin). Except for, sample 27 was the same as the sample 23 described above. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
-Sample 28-
The addition amount of 3-aminopropyltriethoxysilane (same as above) is 3 parts by mass with respect to 100 parts by mass of the isocyanate-based urethane resin A (2.1 g (including solvent) with respect to 100 g of the isocyanate-based urethane resin). Except for, sample 28 had the same configuration as sample 23 described above. Thereafter, the adhesive strength at high temperature was measured in the same manner as in Comparative Sample 6.
2. Test results and discussion The test results are shown in Table 4 above.

As shown in Table 4, the adhesive force of Sample 25 was the maximum. From the above, it is most preferable that 0.5 parts by mass of 3-aminopropyltriethoxysilane (the same) is added to 100 parts by mass of the isocyanate-based urethane resin A.
<Example 5-Temperature dependence of adhesive force>
Using the sample 25 in Example 4 above, the temperature dependence of the adhesive force was examined.
1. Test Method First, in accordance with JIS K6849, the adhesive strength at 0 ° C., 23 ° C. (room temperature), 100 ° C., 120 ° C. and 150 ° C. was determined. At this time, as a test piece, an iron base material (base) not subjected to chemical conversion treatment, an iron base material (chemical conversion film) subjected to chemical conversion treatment, and an aluminum base material were used.

And based on the measurement result of the adhesive strength at each temperature, the temperature dependence of the adhesive strength was determined in accordance with JIS K6831.
2. Test results and discussion The test results are shown in FIG.

  As shown in FIG. 3, when Sample 25 was used as an adhesive, the adhesive strength at 150 ° C. was about ½ of the adhesive strength at room temperature. Therefore, even at a high temperature of about 150 ° C., if the sample 25 was used as an adhesive, the elastic member could be bonded and fixed to the iron base or aluminum base.

  As described above, the present invention is useful for an anti-vibration structure in which an anti-vibration material body made of an elastic material is bonded to a metal substrate or a resin substrate via an adhesive.

FIG. 3 is a cross-sectional view of the vibration-proof structure in Embodiment 1. It is sectional drawing of the vibration proof structure in Embodiment 2. FIG. It is a graph which shows the temperature dependence of the adhesive strength of the adhesive agent in Example 5. FIG.

Explanation of symbols

10, 20 Anti-vibration structure 11, 31, 42 Inner cylinder (metal substrate)
12 Outer cylinder (metal base)
13, 33, 43 Anti-vibration material body 17 Adhesive 41 Resin tube (resin base material)

Claims (8)

An anti-vibration structure in which an anti-vibration material body made of an elastic material is bonded and fixed to at least one of a metal substrate and a resin substrate via an adhesive,
The adhesive contains an isocyanate-based urethane resin that is a reaction product of a polyol and a polyisocyanate, and colloidal silica.
The content of the colloidal silica per 100 parts by weight of the isocyanate-based urethane resin state, and are than 40 parts by weight 1 part by mass or more,
The isocyanate-based urethane resin is produced by reacting 100 parts by mass or more and 1000 parts by mass or less of the polyisocyanate with respect to 100 parts by mass of the polyol, and the colloidal through a physical bond or a chemical bond. An anti-vibration structure characterized by being bonded to a surface of silica . The vibration-proof structure according to claim 1,
The anti-vibration structure according to claim 1, wherein the polyol has a hydroxyl value of 50 KOHmg / g or more and 150 KOHmg / g or less. The vibration-proof structure according to claim 1,
The anti-vibration structure according to claim 1, wherein the adhesive further contains a silane coupling agent. In the vibration-proof structure according to claim 3 ,
Content of the said silane coupling agent is 0.1 mass part or more and 5 mass parts or less with respect to 100 mass parts of the said isocyanate type urethane resin, The vibration-proof structure characterized by the above-mentioned. The vibration-proof structure according to claim 1,
The anti-vibration structure body is made of vulcanized rubber. The vibration-proof structure according to claim 1,
The vibration-proof structure according to claim 1, wherein the metal substrate is made of at least one of iron, aluminum, and an aluminum alloy. The vibration-proof structure according to claim 1,
The vibration-proof structure is characterized in that the resin base material is made of a thermoplastic resin. In the vibration-proof structure according to claim 7 ,
The vibration-proof structure is characterized in that the resin base material is made of at least one of polyamide and glass fiber reinforced polyamide.

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