JP2009154443A - Gel/rubber laminate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gel/rubber laminate which is adhesively formed of a pliable gel member and a rubber member in one piece, and a manufacturing method of this gel/rubber laminate. <P>SOLUTION: This gel/rubber laminate is composed of a gel member formed of a thermoplastic gel containing a thermoplastic elastomer and a softening agent, with not more than 30 type E durometer hardness, a rubber member formed of a crosslinked rubber, and an adhesive layer which is sandwiched between the gel member and the rubber member and made up of a supermolecular weight polyethylene. For example, in a first heating process, an adhesive member consisting of the supermolecular weight polyethylene, is arranged on the surface of the rubber member composed of an uncrosslinked rubber composition. Further, the uncrosslinked rubber composition is crosslinked by heat and at the same time, the adhesive member is fused to the rubber member. Also, in a second heating process, the gel member is arranged on the surface to which the adhesive member of the rubber member is fused, and the adhesive member is fused to the gel member by heat. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a gel / rubber laminate in which a gel member and a rubber member having different hardnesses are bonded, and a method for manufacturing the same.

Rubber materials are widely used as protective members, impact absorbing members and the like. In order to improve the functionality of members, various types of laminates in which the same or different types of rubbers are joined together or laminates in which a thermoplastic elastomer and rubber are joined have been developed. In such a laminate, each material is bonded by an adhesive force between the materials or using an adhesive or the like. For example, as a method of joining a thermoplastic elastomer and rubber, Patent Document 1 describes a method of injection-molding a thermoplastic elastomer with respect to rubber to which a thermoplastic resin powder is adhered. Patent Document 2 describes a method in which an ultrahigh molecular weight polyethylene sheet is interposed between a thermoplastic elastomer and an unvulcanized rubber and vulcanized and bonded.
JP-A-6-47816 JP-A-6-184327

  In order to improve the impact resistance and durability of the rubber member, the present inventor tried to stack and integrate a gel member on the rubber member. The gel member is made of a thermoplastic gel in which a large amount of oil (softening agent) is blended with a thermoplastic elastomer, and has a large elongation and is very flexible as compared with a rubber member. According to the laminated body of the rubber member and the gel member, the input impact can be buffered by the gel member, and the stress can be dispersed. For this reason, impact resistance and durability can be improved as compared with the rubber member alone.

  However, the adhesive force of the gel member to the rubber member is poor, and it is easily peeled off simply by laminating them. Moreover, since the gel member is very flexible, it is easily deformed. Therefore, even if an adhesive or a pressure-sensitive adhesive tape is used, it is impossible to follow the deformation of the gel member and a sufficient adhesive force cannot be obtained.

  This invention is made | formed in view of such a situation, and makes it a subject to provide the gel / rubber laminated body with which the flexible gel member and the rubber member were integrated by adhesion | attachment. Another object of the present invention is to provide a production method capable of easily producing the gel / rubber laminate.

  (1) In order to solve the above problems, the gel / rubber laminate of the present invention comprises a gel member made of a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less, and a crosslinked rubber. And a bonding layer made of ultrahigh molecular weight polyethylene interposed between the gel member and the rubber member (corresponding to claim 1).

  The gel / rubber laminate of the present invention is formed by laminating a gel member and a rubber member via an adhesive layer. The gel member is made of a thermoplastic gel, and the gel member has a type E durometer hardness of 30 or less. That is, the gel member is very flexible compared to the rubber member. Here, “type E durometer hardness” is hardness measured by a type E durometer defined in JIS K 6253 “Vulcanized Rubber and Thermoplastic Rubber—How to Obtain Hardness”. Since the gel member is flexible, it has excellent cushioning properties. Therefore, the input impact is buffered by the gel member, and the stress is dispersed. For this reason, the gel / rubber laminate of the present invention is more excellent in impact resistance and durability than the rubber member alone. Moreover, since a gel member is flexible, even if it contacts with the other party member which has an uneven surface, followability is high. Moreover, since the adhesiveness to the other member is high, the sealing property is excellent.

  The gel member and the rubber member are bonded by an adhesive layer made of ultra high molecular weight polyethylene. The ultrahigh molecular weight polyethylene is bonded to each of the gel member and the rubber member by melting by heating. The melted ultra high molecular weight polyethylene is easily compatible with the gel member, and is dispersed in the gel member in the vicinity of the interface between the adhesive layer and the gel member. Thus, the gel member is firmly adhered. In particular, when the adhesive layer is formed of powdery ultra-high molecular weight polyethylene, the melted ultra-high molecular weight polyethylene powder enters the fine irregularities on the surface of the rubber member, and firmly adheres the rubber member by the anchor effect. . Thus, according to the gel / rubber laminate of the present invention, the gel member and the rubber member having different hardness are firmly bonded, and the characteristics of each member are sufficiently exhibited.

  (2) The first method for producing the gel / rubber laminate of the present invention (hereinafter referred to as “first production method” as appropriate) is that ultrahigh molecular weight polyethylene is applied to the surface of a rubber member comprising an uncrosslinked rubber composition. A first heating step of disposing the adhesive member comprising: cross-linking the uncrosslinked rubber composition by heating and fusing the adhesive member to the rubber member; and the adhesive member of the rubber member being fused. A gel member made of a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less is disposed on the surface, and the adhesive member is fused to the gel member by heating. And a heating step (corresponding to claim 5). Further, the second method for producing the gel / rubber laminate of the present invention (hereinafter referred to as “second production method” as appropriate) includes a rubber member comprising a crosslinked rubber, and a heat containing a thermoplastic elastomer and a softening agent. An adhesive member made of ultrahigh molecular weight polyethylene is arranged on the surface of any one of the members of a gel member made of a plastic gel and having a type E durometer hardness of 30 or less, and the adhesive member is heated by heating the one member. And a second heating step in which the other member is disposed on the surface of the one member on which the adhesive member is fused, and the adhesive member is fused to the other member by heating. And a heating step (corresponding to claim 6).

  That is, the first and second manufacturing methods of the present invention have two heating steps for performing fusion bonding of the adhesive member and the like. By dividing the fusion bonding of the adhesive member into two steps, the rubber member and the gel member can be heated at an optimum temperature to fuse the adhesive member. In the first production method of the present invention, an uncrosslinked rubber composition is used as the rubber member, and the adhesive member is fused to the rubber member in the first heating step, and at the same time, the uncrosslinked rubber composition is crosslinked. For this reason, it is not necessary to crosslink the uncrosslinked rubber composition in advance. Thus, according to the first or second production method of the present invention, the gel / rubber laminate of the present invention can be easily produced.

  (3) The third method for producing the gel / rubber laminate of the present invention (hereinafter referred to as “third production method” as appropriate) comprises a rubber member comprising an uncrosslinked rubber composition, a thermoplastic elastomer and a softening agent. A laminated member forming step of forming a laminated member by disposing an adhesive member made of ultra-high molecular weight polyethylene between a gel member made of a thermoplastic gel containing and a type E durometer hardness of 30 or less; And heating the laminated member to cross-link the uncrosslinked rubber composition and to fuse the adhesive member to the rubber member and the gel member (corresponding to claim 7). ). The fourth method for producing the gel / rubber laminate of the present invention (hereinafter referred to as “fourth production method” as appropriate) is a heat containing a rubber member made of a crosslinked rubber, a thermoplastic elastomer and a softening agent. A laminated member forming step for forming a laminated member by placing an adhesive member made of ultra high molecular weight polyethylene between a gel member made of a plastic gel and having a type E durometer hardness of 30 or less, and heating the laminated member And a heating step of fusing the adhesive member to the rubber member and the gel member (corresponding to claim 8).

  That is, the third and fourth manufacturing methods of the present invention form a laminated member in which an adhesive member is interposed between the rubber member and the gel member in the laminated member forming step, and the adhesive member is formed in the heating step. The rubber member and the gel member are fused. Since the adhesive member is fused at a time, it is efficient. In the third production method of the present invention, an uncrosslinked rubber composition is used as the rubber member, and the adhesive member is fused in the heating step, and at the same time, the uncrosslinked rubber composition is crosslinked. For this reason, it is not necessary to crosslink the uncrosslinked rubber composition in advance. Thus, according to the third or fourth production method of the present invention, the gel / rubber laminate of the present invention can be produced simply and efficiently.

  Hereinafter, the gel / rubber laminate of the present invention and the production method thereof will be described in detail.

<Gel / Rubber laminate>
The gel / rubber laminate of the present invention includes a gel member, a rubber member, and an adhesive layer. The gel member is made of a thermoplastic gel. The thermoplastic gel includes a thermoplastic elastomer and a softening agent. As the thermoplastic elastomer, for example, a styrene block copolymer is preferable in that it can be used at a relatively high temperature (about 100 ° C.). Examples of the styrene block copolymer include styrene- (ethylene / butylene) -styrene block copolymer (SEBS), styrene- (ethylene / propylene) -styrene block copolymer (SEPS), and styrene-butadiene-styrene. Examples thereof include a block copolymer (SBS) and a styrene-isoprene-styrene block copolymer (SIS). Further, it is desirable to use mineral oil as the softening agent. Of these, paraffinic mineral oil is desirable because it is well-suited to the thermoplastic elastomer and difficult to bleed.

  The thermoplastic gel may contain various additives in addition to the thermoplastic elastomer and the softening agent. Examples of the additive include processing aids, anti-aging agents, colorants and the like. The thermoplastic gel can be prepared by blending a thermoplastic elastomer with a softening agent and, if necessary, an additive, and heat-kneading with a kneader or the like. The blending ratio of the thermoplastic elastomer in the thermoplastic gel may be appropriately determined according to the use. For example, in consideration of hardness and the like to be described later, 20% by weight or less when the whole is 100% by weight, and further 10% by weight. % Or less.

  The hardness of the gel member made of such a thermoplastic gel is 30 or less in type E durometer hardness. When it exceeds 30, flexibility will fall and it will become difficult to express gel characteristics, such as cushioning properties. On the other hand, when the gel member is too soft, since the thermoplastic elastomer content in the thermoplastic gel is small, the adhesive force with the adhesive layer is reduced. Accordingly, it is desirable that the gel member has a type E durometer hardness of 5 or more.

  The rubber member is made of a crosslinked rubber. The type of the crosslinked rubber is not particularly limited and may be appropriately selected depending on the application. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), styrene-butadiene copolymer rubber (SBR), ethylene-propylene copolymer rubber [ethylene-propylene Copolymer (EPM), ethylene-propylene-diene terpolymer (EPDM), etc.], butyl rubber (IIR), halogenated butyl rubber (Cl-IIR, Br-IIR, etc.), hydrogenated nitrile rubber (H-NBR) ), Chloroprene rubber (CR), acrylic rubber (AR), chlorosulfonated polyethylene rubber (CSM), hydrin rubber, silicone rubber, fluorine rubber, urethane rubber and the like. The hardness of the crosslinked rubber, that is, the rubber member, may be 30 or more in the type A durometer hardness defined in JIS K 6253 “Vulcanized rubber and thermoplastic rubber—How to obtain hardness”.

  The adhesive layer interposed between the gel member and the rubber member is made of ultra high molecular weight polyethylene. The average molecular weight of the ultra high molecular weight polyethylene is desirably 1 million or more. Further, the thickness of the adhesive layer is desirably 10 μm or more. If it is less than 10 μm, sufficient adhesion cannot be obtained. On the other hand, the thickness of the adhesive layer is desirably 200 μm or less. If it exceeds 200 μm, the properties of the adhesive layer become dominant, which may affect the properties of the rubber member and the gel member. 50 μm or less, more preferably 30 μm or less is more preferable.

  The form of ultra high molecular weight polyethylene for forming the adhesive layer is not particularly limited, such as a sheet form or a powder form. For example, in addition to being able to bond regardless of the shape of the gel member and the rubber member, ultra high molecular weight polyethylene powder may be used from the viewpoint of easily forming a thin and uniform adhesive layer. In this case, the average particle diameter of the ultrahigh molecular weight polyethylene powder is desirably 10 μm or more and 50 μm or less. In order to further reduce the thickness of the adhesive layer, 30 μm or less is preferable. Here, the average particle diameter is a particle diameter (D50) at which the cumulative weight is 50% in the cumulative particle size curve.

  In the gel / rubber laminate of the present invention, a gel member, an adhesive layer, and a rubber member may be laminated one by one, or a plurality of gel members and rubber members may be laminated via an adhesive layer. In the latter case, the material, hardness and thickness of each member, the thickness of the adhesive layer, and the like may be the same or different. Hereafter, the suitable manufacturing method of the gel / rubber laminated body of this invention is demonstrated. In each of the production methods of the present invention, it is desirable to employ a preferred embodiment of the gel / rubber laminate of the present invention.

<Method for producing gel / rubber laminate>
(1) 1st manufacturing method The 1st manufacturing method of this invention has a 1st heating process and a 2nd heating process. Hereinafter, each process is demonstrated in order.

(A) First heating step In this step, an adhesive member made of ultrahigh molecular weight polyethylene is placed on the surface of a rubber member made of an uncrosslinked rubber composition, and the uncrosslinked rubber composition is crosslinked by heating, This is a step of fusing the adhesive member to the rubber member. The rubber member in this step is made of an uncrosslinked rubber composition. The uncrosslinked rubber composition may be a composition that can form a desired crosslinked rubber, and may contain various additives in addition to the polymer and the crosslinking agent. Examples of the additive include a vulcanization accelerator, a processing aid, a vulcanization aid, an antiaging agent, a plasticizer, a softening agent, and a colorant. An uncrosslinked rubber composition can be prepared by adding a crosslinking agent and, if necessary, an additive to the polymer and kneading. The prepared uncrosslinked rubber composition may be molded into a predetermined shape to form a rubber member.

As the adhesive member, an ultrahigh molecular weight polyethylene sheet or powder may be used. As described above, the average molecular weight of the ultra high molecular weight polyethylene is desirably 1 million or more. For example, when an ultrahigh molecular weight polyethylene sheet is used, the thickness of the sheet is preferably 10 μm or more and 200 μm or less in consideration of the thickness of the adhesive layer to be formed. Moreover, when using ultra high molecular weight polyethylene powder, it is good to make the average particle diameter of powder into 10 micrometers or more and 50 micrometers or less. Here, the amount of the ultrahigh molecular weight polyethylene powder applied to the rubber member is preferably 0.1 g / 100 cm ² or more and 1.0 g / 100 cm ² or less in consideration of the thickness of the adhesive layer to be formed. In the case of less than 0.1 g / 100 cm ² , the thickness of the adhesive layer becomes too thin and sufficient adhesive force cannot be obtained. If it exceeds 1.0 g / 100 cm ² , the rigidity of the adhesive layer increases, which may affect the properties of the rubber member or gel member to be bonded. It is desirable to use ultrahigh molecular weight polyethylene powder in that it can be bonded regardless of the shape of the gel member or rubber member, and the adhesive layer can be easily formed thinly and uniformly.

  The heating temperature in this step may be a temperature at which the uncrosslinked rubber composition can be crosslinked and the adhesive member melts. For example, what is necessary is just to heat for about 20 minutes at the temperature of 120 degreeC or more which is more than melting | fusing point of ultra high molecular weight polyethylene. In consideration of thermal decomposition of ultra high molecular weight polyethylene, the heating temperature is desirably 300 ° C. or lower. The heating may be performed while pressurizing the rubber member and the adhesive member.

(B) Second heating step This step is a gel composed of a thermoplastic gel containing a thermoplastic elastomer and a softening agent on the surface where the adhesive member of the rubber member is fused, and having a type E durometer hardness of 30 or less. This is a step of disposing a member and fusing the adhesive member to the gel member by heating.

  The thermoplastic gel is as described in the gel / rubber laminate of the present invention. What is necessary is just to shape | mold the thermoplastic gel prepared by heat-kneading a thermoplastic elastomer, a softening agent, etc. in a predetermined shape, and let it be a gel member. Moreover, the heating temperature in this process should just be a temperature which an adhesive member fuse | melts similarly to the 1st heating process of said (a). For example, what is necessary is just to heat about 5 minutes at the temperature of 120 degreeC or more which is more than melting | fusing point of ultra high molecular weight polyethylene. In consideration of thermal decomposition of ultrahigh molecular weight polyethylene, melting of the gel member, etc., the heating temperature is desirably 300 ° C. or lower.

(2) Second manufacturing method The second manufacturing method of the present invention includes a first heating step and a second heating step. The first heating step is performed on the surface of any one of a rubber member made of a crosslinked rubber and a gel member made of a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less. In this step, an adhesive member made of ultra high molecular weight polyethylene is disposed and the adhesive member is fused to the one member by heating. The second heating step is a step in which the other member is disposed on the surface of the one member on which the adhesive member is fused, and the adhesive member is fused to the other member by heating. The difference from the first production method is that a crosslinked rubber is used instead of an uncrosslinked rubber composition as the rubber member, and that the member on which the adhesive member is first arranged may be either a rubber member or a gel member. Here, matters relating to the differences will be described, and the other points are the same as in the first manufacturing method, and thus the description thereof will be omitted.

  The rubber member in this step is made of a crosslinked rubber. The crosslinked rubber is as described in the gel / rubber laminate of the present invention. For example, an uncrosslinked rubber composition capable of forming a desired crosslinked rubber can be formed into a predetermined shape and crosslinked by heating to obtain a rubber member.

  In the first heating step, an adhesive member is disposed on the surface of one of the rubber member and the gel member, and the adhesive member is fused to the one member by heating. In the subsequent second heating step, the other member is disposed on the surface of the one member to which the adhesive member has been fused, and the adhesive member is fused to the other member by heating. In any heating step, the heating temperature may be determined in consideration of melting of the adhesive member, thermal decomposition of the adhesive member, progress of crosslinking of the rubber member, melting of the gel member, and the like.

(3) Third Manufacturing Method The third manufacturing method of the present invention includes a laminated member forming step and a heating step. Hereinafter, each process is demonstrated in order.

(A) Laminated member forming step This step comprises a rubber member comprising an uncrosslinked rubber composition, a gel member comprising a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less, It is the process of arrange | positioning the adhesive member which consists of ultra high molecular weight polyethylene between these, and forming a laminated member.

  The rubber member, gel member, and adhesive member made of the uncrosslinked rubber composition are the same as in the first manufacturing method. These members are arranged so as to be a rubber member / adhesive member / gel member to form a laminated member. For example, when ultra high molecular weight polyethylene powder is used as the adhesive member, the powder may be attached to one or both of the rubber member and the gel member.

(B) Heating step This step is a step of heating the formed laminated member to crosslink the uncrosslinked rubber composition and fusing the adhesive member to the rubber member and the gel member. The heating temperature may be a temperature at which the uncrosslinked rubber composition can be crosslinked and the adhesive member melts. For example, what is necessary is just to heat at the temperature of 120 degreeC or more which is more than melting | fusing point of ultra high molecular weight polyethylene. In consideration of thermal decomposition of ultrahigh molecular weight polyethylene, melting of the gel member, etc., the heating temperature is desirably 300 ° C. or lower. For example, it may be heated at a temperature of 150 ° C. or higher and 180 ° C. or lower for about 5 to 20 minutes. Moreover, you may perform a heating, pressing a laminated member.

(4) Fourth Manufacturing Method The fourth manufacturing method of the present invention includes a laminated member forming step and a heating step. The laminated member forming step is performed from ultrahigh molecular weight polyethylene between a rubber member made of a crosslinked rubber and a gel member made of a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less. This is a step of disposing an adhesive member to form a laminated member. The heating step is a step of heating the laminated member to fuse the adhesive member to the rubber member and the gel member.

  The difference from the third production method is that a crosslinked rubber is used instead of an uncrosslinked rubber composition as the rubber member. Except for this, it may be performed in the same manner as the third manufacturing method. The crosslinked rubber is as described in the gel / rubber laminate of the present invention. For example, an uncrosslinked rubber composition capable of forming a desired crosslinked rubber can be formed into a predetermined shape and crosslinked by heating to obtain a rubber member. In the heating step, it is not necessary to consider the crosslinking temperature of the uncrosslinked rubber composition. Therefore, the heating temperature may be determined in consideration of melting of the adhesive member, thermal decomposition of the adhesive member, progress of crosslinking of the rubber member, melting of the gel member, and the like.

  A gel / rubber laminate was manufactured by laminating gel members and rubber members having different hardnesses. And the adhesiveness and cushioning property of the manufactured gel / rubber laminate were evaluated. Hereinafter, it demonstrates in order.

<Manufacture of gel / rubber laminate>
First, two types of gel members having different hardnesses were manufactured. 100 parts by weight of styrene- (ethylene / butylene) -styrene block copolymer (SEBS) (“Clayton (registered trademark) G1651” manufactured by Clayton Polymer Japan) and paraffinic mineral oil (“Diana (registered trademark) manufactured by Idemitsu Kosan Co., Ltd.) ) Process oil PW90 ") 600 parts by weight, 25 parts by weight of processing aid ethylene resin (" Sun Wax (registered trademark) 151P "manufactured by Sanyo Chemical Industries), and polyphenol anti-aging agent (Ouchi Shinsei Chemical Industry) A thermoplastic gel was prepared by heating and kneading 1 part by weight of “NOCRACK (registered trademark) NS-7” manufactured by the company. The prepared thermoplastic gel was formed into a strip shape having a length of 50 mm, a width of 25 mm, and a thickness of 1 mm to form a first gel member. The type E durometer hardness of the manufactured first gel member was 10. Moreover, in manufacture of a 1st gel member, the compounding quantity of paraffinic mineral oil was changed into 400 weight part, and the 2nd gel member was manufactured. The type E durometer hardness of the second gel member was 30.

  Next, the composition before cross-linking of ethylene-propylene-diene terpolymer (EPDM) was molded into a strip of 50 mm length × 25 mm width × 2 mm thickness to obtain a rubber member. Two types of rubber members having a type A durometer hardness of 30 and 60 were manufactured. The surface of the rubber member is coated with ultra high molecular weight polyethylene powder (“Miperon (registered trademark)” manufactured by Mitsui Chemicals, average particle diameter of 25 μm) as an adhesive member, and heated under pressure at a temperature of 150 ° C. for 20 minutes for crosslinking. The pre-composition (rubber member) was cross-linked and the ultra high molecular weight polyethylene powder was fused. Subsequently, the manufactured first or second gel member was placed on the fusion surface of the ultrahigh molecular weight polyethylene powder, and the ultrahigh molecular weight polyethylene powder was fused to the gel member by heating at 160 ° C. for 10 minutes. . In this way, five types of gel / rubber laminates in which the gel member and the rubber member were laminated via the adhesive layer were produced (Examples 1 to 5).

On the other hand, for comparison, a gel / rubber laminate was manufactured by stacking a gel member and a rubber member without using an adhesive member (ultra high molecular weight polyethylene powder) (Comparative Example). Table 1 below summarizes the gel member, the hardness of the rubber member, the coating amount of the ultra-high molecular weight polyethylene powder, and the thickness of the formed adhesive layer for each gel / rubber laminate.

<Evaluation of gel / rubber laminate>
(1) First, a peel test was performed in order to evaluate the adhesion between the gel member and the rubber member. The peel test was performed according to JIS K 6854-2 (1999). FIG. 1 schematically shows the state of the peel test. In addition, what is shown in FIG. 1 is the mode of the peeling test with respect to the gel / rubber laminated body of an Example. As shown in FIG. 1, the gel / rubber laminate 1 includes a gel member 10, a rubber member 11, and an adhesive layer 12 that bonds both members. One end of the gel member 10 is sandwiched by the gripping tool 13a in a state of being peeled from the adhesive layer 12, and is peeled at an angle of about 180 ° with respect to the adhesive surface (indicated by an upward white arrow in the figure). ) Is bent. One end of the gel / rubber laminate 1 where the gel member 10 is not bonded is sandwiched and fixed by a gripping tool 13b. One end of the gel member 10 was pulled in the peeling direction by the gripping tool 13a, and the adhesiveness at the other end of the gel / rubber laminate 1, that is, the bonded portion between the gel member 10 and the rubber member 11 was evaluated. In addition, this test was performed under 23 degreeC (room temperature), and the moving speed of the holding | gripping tool 13a was 50 mm / min.

  (2) Next, in order to evaluate the cushioning property of the gel / rubber laminate, a penetration test was performed. The penetration test is a test for measuring how much the needle enters the sample when the needle is dropped perpendicular to the sample, and conforms to the penetration test method of JIS K 2207 (1996). went. In this test, the manufactured gel / rubber laminate was placed with the gel member facing up, and the needle was dropped from above the gel member.

  (3) The above two test results are also shown in Table 1 above. In the evaluation of Table 1, those satisfying both adhesiveness and cushioning properties are indicated by ◯ marks. First, the results of the peel test will be described. In each of the gel / rubber laminates of Examples 1 to 5, the gel member was cut while the gel member was being pulled. At this time, no peeling of the gel member was observed at the other end of the gel / rubber laminate. This shows that the adhesive force between the gel member and the rubber member is superior to the tensile strength of the gel member. That is, it can be seen that the gel member and the rubber member are firmly bonded by the adhesive layer. On the other hand, in the gel / rubber laminate of the comparative example, when the gel member was pulled, the gel member was peeled off from the rubber member.

  Next, the results of the penetration test will be described. In each of the gel / rubber laminates of Examples 1 to 5, the rubber member was not damaged. That is, the gel member became a buffer material, and the needle did not reach the rubber member. In contrast, in the gel / rubber laminate of the comparative example, the needle reached the rubber member, and the rubber member was damaged. In the gel / rubber laminate of the comparative example, since the adhesive force between the gel member and the rubber member is small, it is considered that the gel member peeled off due to the impact of the needle entering and the needle reached the rubber member.

  As described above, according to the gel / rubber laminate of the present invention, it was confirmed that the flexible gel member and the rubber member were firmly bonded and integrated by the adhesive layer. Moreover, the cushioning property which is a characteristic of the gel member was sufficiently exhibited, and it was confirmed that the gel / rubber laminate of the present invention was excellent in impact resistance and durability.

  The gel / rubber laminate of the present invention can be widely used for protective members, shock absorbing members and the like that require cushioning properties. For example, it is suitable for tires, bearing dampers, in-vehicle CD player dampers, building damping dampers and floor dampers, shock absorbers for display panels of electronic devices, developing rolls and charging rolls in electrophotographic apparatuses.

It is a schematic diagram which shows the mode of the peeling test in an Example.

Explanation of symbols

1: Rubber laminate 10: Gel member 11: Rubber member 12: Adhesive layer 13a, 13b: Grip

Claims (8)

A gel member comprising a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less;
A rubber member made of a crosslinked rubber;
An adhesive layer interposed between the gel member and the rubber member and made of ultrahigh molecular weight polyethylene;
A gel / rubber laminate comprising:   The gel / rubber laminate according to claim 1, wherein the thermoplastic elastomer is at least one selected from styrene block copolymers.   The gel / rubber laminate according to claim 1 or 2, wherein the adhesive layer has a thickness of 10 µm or more and 200 µm or less.   The gel / rubber laminate according to any one of claims 1 to 3, wherein the adhesive layer is formed of ultra high molecular weight polyethylene powder. An adhesive member made of ultrahigh molecular weight polyethylene is disposed on the surface of a rubber member made of an uncrosslinked rubber composition, and the uncrosslinked rubber composition is crosslinked by heating and the adhesive member is fused to the rubber member. A first heating step;
A gel member made of a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less is disposed on the surface of the rubber member where the adhesive member is fused, and the adhesion is achieved by heating. A second heating step of fusing the member to the gel member;
A method for producing a gel / rubber laminate comprising: On the surface of any one of a rubber member made of a crosslinked rubber and a gel member made of a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less, an ultra high molecular weight polyethylene A first heating step in which an adhesive member is disposed and the adhesive member is fused to the one member by heating;
A second heating step in which the other member is disposed on the surface of the one member on which the adhesive member is fused, and the adhesive member is fused to the other member by heating;
A method for producing a gel / rubber laminate comprising: An adhesive member made of ultrahigh molecular weight polyethylene between a rubber member made of an uncrosslinked rubber composition and a gel member made of a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less And a laminated member forming step of forming a laminated member,
Heating the laminated member to crosslink the uncrosslinked rubber composition and fusing the adhesive member to the rubber member and the gel member;
A method for producing a gel / rubber laminate comprising: An adhesive member made of ultrahigh molecular weight polyethylene is placed between a rubber member made of a crosslinked rubber and a gel member made of a thermoplastic gel containing a thermoplastic elastomer and a softening agent and having a type E durometer hardness of 30 or less. A laminated member forming step of forming a laminated member;
Heating the laminated member to fuse the adhesive member to the rubber member and the gel member;
A method for producing a gel / rubber laminate comprising:

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