JP4718895B2 - Rubber composition for rubber body and composite using the same - Google Patents

Description

  The present invention relates to a rubber composition for obtaining a rubber body excellent in adhesion to an adherend surface with an adhesive, and a composite using the same.

In general, vulcanized rubbers, especially vulcanizates of rubbers with low polarity and surface activity such as natural rubber (NR), ethylene-propylene-diene copolymer rubber (EPDM), and metal materials such as steel, stainless steel, aluminum, It is difficult to obtain a sufficient adhesion strength when the concrete structure is bonded using an adhesive.
For example, when the adherend is a metal material, since the polarity of the adherend becomes high, an adhesive having a high polarity is usually used. Such an adhesive is vulcanized rubber, especially, The affinity for the above-mentioned low-polar rubber (or low-surface active rubber) is low, resulting in a problem that the adhesive strength between the rubber and the metal material is low.

  Conventionally, as a means for improving the adhesion between a highly polar adherend such as a metal material and vulcanized rubber, for example, the surface of a highly polar adherend is subjected to an isocyanate treatment to make it hydrophobic. The method of making it known is known. Patent Document 1 discloses that a highly polar adherend surface has a thermosetting resin such as an epoxy resin, a filler such as clay powder, talc powder, silica powder, and hard rubber powder, a solvent, and a curing agent. And a metal surface primer is formed, and if necessary, a chlorinated rubber primer is formed on the surface of the metal surface primer. A method for adhering rubber and metal, characterized in that vulcanized rubber is adhered to the surface using a rubber-based adhesive, is described.

On the other hand, for example, when the adherend is a concrete structure, it is formed on the surface of the concrete structure in consideration of fine irregularities (so-called unevenness) on the surface of the concrete structure and the porosity of the concrete. It is required to increase the thickness of the adhesive layer to be formed.
By the way, in recent years, silica has been widely used as a reinforcing agent to be blended in a rubber composition, instead of carbon black. For example, the rigidity composed of a rubber-like elastic layer and a steel plate described in Patent Document 2 is used. In a seismic isolation structure including laminated portions in which layers are alternately laminated in the vertical direction, a rubber-like elastic layer is formed using a rubber composition containing silica.
JP 2001-354912 A JP 2000-320594 A

However, the hydrophobic treatment such as isocyanate treatment on the surface of the highly polar adherend takes time for the treatment itself, and the effect of improving the adhesiveness is not sufficient. Further, in the bonding method described in Patent Document 1, since a primer coating process and an adhesive coating process are required, the bonding process takes time and cost.
In addition, it is difficult to form an adhesive layer having a large thickness from the viewpoint of the viscosity of the adhesive or the like with an isocyanate-based adhesive or the like used as an adhesive for low-polar rubber (low surface active rubber). In addition, when moisture is contained between the rubber-concrete structure, it is difficult to provide sufficient adhesive strength between the rubber-concrete structure.

  Conventionally, silica particles used as a rubber reinforcing agent have many OH groups derived from silanol groups on the particle surface and are a highly cohesive substance. Therefore, they are blended in a rubber composition. As a result, the degree of hydrophilicity and polarity of the rubber composition may be increased, and further, the processability of the rubber composition may be reduced by being incorporated in a large amount in the rubber composition. Therefore, in the invention described in Patent Document 2, the amount of silica particles blended in the rubber composition is limited, and further, the adsorption amount of dibutylamine (DBA) per kg of silica particles is 100 mmol / kg. It is said that it is preferable.

  An object of the present invention is to provide a rubber composition for obtaining a rubber body that can be bonded to an adherend with high adhesion strength by a simple treatment, and a composite using the same.

In order to achieve the above object, the present invention provides:
(1) It contains rubber and silica particles, the dibutylamine adsorption amount of the silica particles is 180 to 450 mmol / kg, the content of the silica particles with respect to 100 parts by weight of the rubber is 160 parts by weight or less, and , the content of the silica particles to the rubber 100 parts by weight (parts by weight), the integrated value of the dibutylamine adsorption amount of the silica particles (mmol / kg) is 10,000 to 40,000 der is, through an adhesive layer A rubber composition for a rubber body, wherein the rubber composition is used for a rubber body bonded to an adherend .
(2) the content of the silane compound of the rubber body rubber composition, characterized in that relative to the content of the silica particles of the rubber body rubber composition is 30 wt% or less, A rubber composition for a rubber body according to (1),
(3) The rubber composition for a rubber body according to (1) or (2), wherein the rubber is a low polarity rubber,
(4) The rubber body comprising the rubber composition for a rubber body according to any one of (1) to (3) and an adherend are bonded via an adhesive layer. , Complex,
(5) The composite according to (4), wherein the rubber body is a rubber sheet vulcanized before adhesion to the adherend,
Is to provide.

  In the present invention, the dibutylamine (DBA) adsorption amount of silica particles is the DBA adsorption amount (mmol) per kg of silica particles, and is an index indicating the degree of hydrophilicity of silica particles. The greater the amount of silanol groups on the surface of the silica particles, the greater the amount of DBA adsorbed, indicating a greater degree of hydrophilicity on the surface of the silica particles. This DBA adsorption amount is determined by R.I. Meyer, Kautschuk und Gummi Kunststoffe, 7 (8), pp. 180-182 (1954).

  In the present invention, the integrated value of the content (parts by weight) of silica particles with respect to 100 parts by weight of rubber and the DBA adsorption amount (mmol / kg) of silica particles (hereinafter simply referred to as “DBA × silica amount”). Is an index indicating the total amount of silanol groups contained in the rubber composition. This “DBA × silica amount” is the content of silica particles (amount expressed in “parts by weight”) with respect to 100 parts by weight of rubber in the rubber composition, and the DBA adsorption amount (“mmol / kg”) for the silica particles. It is a dimensionless number consisting of the product of the quantity represented by

According to the present invention, in the rubber composition for rubber bodies, silica particles having a dibutylamine adsorption amount in a predetermined range are blended, and the total amount of silanol groups contained in the rubber composition for rubber bodies is in a predetermined range. Therefore, polarity (or surface activity) can be imparted to the rubber composition for a rubber body and a rubber body (rubber molded body) obtained using the rubber composition.
As a result, for example, the affinity between the rubber body of the present invention (for example, a rubber sheet) and the adhesive can be improved, and the adherend to which the rubber body is bonded is, for example, a metal material or the like. The adhesion strength between the rubber and the adherend is high even when the polarity is high, or when the surface has fine irregularities or is porous, such as a concrete structure. It is possible to form a composite excellent in the above.

The rubber composition of the present invention contains rubber and silica particles having a DBA adsorption amount of 180 to 450 mmol / kg.
The rubber is not particularly limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (IIR), acrylonitrile-butadiene rubber (NBR; acrylonitrile) Rubber-like copolymer of butadiene), rubber-like copolymer of acrylonitrile, butadiene and isoprene (NBIR), rubber-like copolymer of acrylonitrile and isoprene (NIR), styrene-butadiene rubber (SBR; styrene and butadiene) Rubbery copolymer), α-methylstyrene and butadiene rubbery copolymer (MSBR), styrene, isoprene and butadiene rubbery copolymer (SIBR), brominated butyl rubber (BIIR; brominated) Rubber-like copolymer of isobutene and isoprene), salt Rubbers having unsaturated carbon bonds in the main chain (rubbers belonging to the R group classified according to JIS K 6397) such as butylated rubber (CIIR; rubbery copolymer of chlorinated isobutene and isoprene); for example, acrylic Rubber (ACM), rubber-like copolymer of acrylic acid ester and ethylene (AEM), ethylene-propylene-diene copolymer rubber (EPDM; rubber-like copolymer of ethylene, propylene and diene), ethylene-propylene Copolymer rubber (EPM; rubbery copolymer of ethylene and propylene), fluoro rubber (FKM; rubbery copolymer having fluoro and perfluoroalkyl or perfluoroalkoxy groups in the side chain), polymethylene type Rubber having a saturated main chain (rubber belonging to M group classified according to JIS K 6397); Rubbers with carbon and oxygen in the main chain (rubbers belonging to group O according to JIS K 6397), such as chlorohydrin rubber (CO); for example, silicone rubber (VMQ; methyl and vinyl substituents in the polymer chain Rubbers having silicon and oxygen in the main chain (rubbers belonging to the Q group classified according to JIS K 6397); for example, polyester urethane (AU) rubbers (belonging to the U group classified according to JIS K 6397) And various rubbers such as rubber).

The rubbers exemplified above can be used alone or in combination of two or more.
The effect of the present invention in combination with the above silica particles that the rubber composition is imparted with polarity (or surface activity) is a low polarity (or surface activity) rubber among the rubbers exemplified above. When used, it appears particularly prominent. Examples of such low polar rubber (or low surface active rubber) include NR, IR, IIR, EPDM and the like.

The rubber used in the rubber composition is not limited to the low-polar rubber (low-surface active rubber). For example, rubber having a relatively high polarity (or surface activity), specifically NBR or the like. Even if it exists, the effect of this invention that the adhesive strength with a to-be-adhered body improves can be acquired with mix | blending the said silica particle.
The silica particles used in the rubber composition have a DBA adsorption amount of 180 to 450 mmol / kg, preferably 200 to 430 mmol / kg, and more preferably 250 to 350 mmol / kg. If the DBA adsorption amount of the silica particles is less than the above range, the number of silanol groups per unit particle of silica is reduced, so that the effect of imparting polarity to the rubber composition becomes insufficient or sufficient for the rubber composition. The amount of silica particles necessary for imparting a high polarity (or surface activity) becomes too large, and the processability of the rubber composition is lowered. On the other hand, if the DBA adsorption amount of the silica particles exceeds the above range, the cohesiveness of the silica particles becomes too strong and the processability of the rubber composition is lowered.

  The average particle diameter of the silica particles is not particularly limited, but is preferably 2.0 to 30 μm, more preferably 10 to 20 μm. Here, the average particle diameter refers to the crystallite diameter (cristat diameter) measured by the X-ray diffraction method or the average value of primary particles obtained by morphological observation with a transmission electron microscope. In addition, for example, since the particle diameter obtained by a sedimentation method such as laser diffraction shows a large value due to aggregation of primary particles, such a particle diameter is excluded. When the average particle diameter of the silica particles is below the above range, the cohesiveness of the silica particles becomes strong and the processability of the rubber composition may be reduced. Further, if the average particle diameter of the silica particles exceeds the above range, the number of silanol groups per unit particle of silica tends to decrease, and the effect of imparting polarity (or surface activity) to the rubber composition may be insufficient. In addition, a large amount of silica particles may be required to impart sufficient polarity (or surface activity) to the rubber composition.

Moreover, the specific surface area of a silica particle is although it does not specifically limit, Preferably, it is 100-350 m < ² > / g, More preferably, it is 150-280 m < ² > / g.
The silica particles used in the rubber composition are not limited based on the production method, and for example, silica particles produced by various production methods such as a precipitation method, a gel method, and a dry method can be used. In general, the amount of silanol groups present on the surface of the silica particles is about 8 particles / nm ^{2 for} precipitated silica (about 10 ²¹ particles / g for silica with a specific surface area of 200 m ² / g) and about silica / gel method silica. 5 pieces / nm ² , and about 3.5 pieces / nm ² with dry process silica.

  The compounding amount of the silica particles affects “DBA × silica amount” described later, and needs to be set according to the DBA adsorption amount of the silica particles. Therefore, the lower limit of the amount of silica particles is not particularly limited, but the upper limit is limited to a predetermined range from the viewpoint of processability of the rubber composition. Specifically, the compounding amount of the silica particles is 160 parts by weight or less, preferably 140 parts by weight or less, more preferably 120 parts by weight or less with respect to 100 parts by weight of rubber in the rubber composition. When the compounding amount of the silica particles exceeds the above range with respect to 100 parts by weight of the rubber in the rubber composition, the processability of the rubber composition is lowered. Although not limited to this, from the viewpoint of the effect of imparting polarity (or surface activity) to the rubber composition, the compounding amount of the silica particles is preferably 40 with respect to 100 parts by weight of the rubber in the rubber composition. Part by weight or more, more preferably 60 parts by weight or more.

The integrated value (DBA × silica amount) of the content (parts by weight) of silica particles with respect to 100 parts by weight of rubber and the DBA adsorption amount (mmol / kg) of silica particles is 10,000 to 40000, preferably 15000. It is 35000, More preferably, it is 20000-30000.
When “DBA × silica amount” is below the above range, even if both the DBA adsorption amount of silica particles and the compounding amount of silica particles satisfy the above range, the rubber composition is polar (or surface The effect of imparting (activity) becomes insufficient. As a result, in the case where a rubber body made of the rubber composition (for example, a rubber molded body such as a rubber sheet) and an adherend are bonded via an adhesive layer, between the rubber body and the adherend Sufficient adhesive strength cannot be obtained.

On the contrary, if “DBA × silica amount” exceeds the above range, even if both the DBA adsorption amount of the silica particles and the compounding amount of the silica particles satisfy the above range, the processing of the rubber composition It becomes difficult to process a rubber sheet or the like.
Although the content rate of the silica particle which occupies for the said whole rubber composition is not specifically limited, Preferably, it is 30 to 60 weight%, More preferably, it is 35 to 55 weight%. If the content ratio of the silica particles in the entire rubber composition is less than the above range, the effect of imparting polarity (or surface activity) to the rubber composition may be poor. On the contrary, when the content ratio of the silica particles in the entire rubber composition exceeds the above range, the processability of the rubber composition may be lowered.

Other components other than the rubber and the silica particles can be blended in the rubber composition. Other components may be appropriately selected from various additives depending on, for example, the use of the rubber body made of the rubber composition and the physical properties required for the rubber body.
Examples of such additives include vulcanizing agents, vulcanization accelerators, vulcanization acceleration aids, fillers, plasticizers, anti-aging agents, pigments, silane compounds, and the like.

Examples of the vulcanizing agent include sulfur and organic sulfur-containing compounds such as trimethylthiourea and N, N′-diethylthiourea. These can be used individually or in mixture of 2 or more types. The blending amount of the vulcanizing agent is not particularly limited.
Examples of vulcanization accelerators include thiazoles such as 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS) and zinc salt of 2-mercaptobenzothiazole (ZnMBT); N-cyclohexyl-2-benzothia Sulfenamides such as zolylsulfenamide; thiurams such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TETD); zinc dimethyldithiocarbamate (ZnMDC), zinc diethyldithiocarbamate Dithiocarbamates such as (ZnEDC), zinc dibutyldithiocarbamate (ZnBDC), zinc N-ethyl-N-phenyldithiocarbamate (ZnEPDC); trimethylthiourine (TMU) thiourea and the like; 1,3-diphenylguanidine (DPG), vulcanization accelerators such as guanidine-based, such as di -o- tolyl guanidine (DOTG) and the like. These can be used individually or in mixture of 2 or more types.

Examples of the vulcanization acceleration aid include fatty acids such as stearic acid, oleic acid, and cottonseed fatty acid, and metal oxides such as zinc white. These can be used individually or in mixture of 2 or more types.
Examples of the filler include kaolin clay, hard clay, calcium carbonate, barium sulfate, and diatomaceous earth. The blending amount of the filler is not particularly limited, and is set according to the mechanical strength required for the rubber body made of the rubber composition.

Examples of the plasticizer include paraffinic oil, ester oil, and olefin oil. The compounding amount of the plasticizer is set according to the processability of the rubber composition, the rubber hardness required for the rubber body made of the rubber composition, etc. while preventing the occurrence of bleeding, It is not particularly limited.
Examples of the antioxidant include imidazoles such as 2-mercaptobenzimidazole; phenyl-α-naphthylamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p. -Amines such as phenylenediamine; phenols such as di-tert-butyl-p-cresol and styrenated phenol.

In the rubber composition, the silane compound is blended in the rubber composition for the purpose of preventing the processability of the rubber composition from being lowered with the blending of the silica particles.
Although not limited to this as a silane type compound, For example, the various silane type compounds currently supplied as a silane coupling agent, a silylating agent, etc. are mentioned. Specifically, for example, chlorosilanes such as methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, trifluoropropyltrichlorosilane; tetramethoxysilane, methyltrimethoxysilane, dimethyl Dimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane , 3-chloropropylmethyldimethoxysilane, trifluoropropyltrimethoxysilane, 3-isocyanate Alkoxysilanes such as propyltriethoxysilane; silazanes such as hexamethyldisilazane; vinyl group-containing silanes such as vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) Epoxy group-containing silanes such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane Styryl group-containing silane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane Any methacryloxy group-containing silane; acryloxy group-containing silanes such as 3-acryloxypropyltrimethoxysilane; N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 -Dimethylbutylidene) amino group-containing silane such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane; ureido group-containing silane such as 3-ureidopropyltriethoxysilane; 3-mercaptopropylmethyldimethoxysilane, 3- Mercaptopropyltri Examples include mercapto group-containing silanes such as methoxysilane; bis (triethoxysilylpropyl) tetrasulfide.

  Since the silane compound chemically reacts with the silanol group on the surface of the silica particles, when the compounding ratio of the silane compound increases, the rubber composition is given polarity (or surface activity) as the silica particles are compounded. There is a risk that the effect of performing may be impaired. Therefore, the blending ratio of the silane compound is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less with respect to the content of the silica particles in the rubber composition. It is set in the range.

The composite of the present invention is obtained by bonding a rubber body made of the rubber composition of the present invention and an adherend through an adhesive layer.
In the composite, the rubber body bonded to the adherend via the adhesive layer may be vulcanized at the time of bonding or may be in an unvulcanized state. Since the rubber body has a high affinity with the adhesive, even if it has been molded into a rubber sheet and vulcanized in advance, that is, vulcanization adhesion is performed upon adhesion to the adherend. Even if it is not, sufficient adhesive strength can be obtained. Therefore, even when it is difficult to perform the vulcanization adhesion operation, sufficient adhesion between the rubber and the adherend can be realized. When the rubber body is in an unvulcanized state, the adhesion strength between the rubber body and the adherend can be further improved by vulcanizing the rubber body after bonding.

The vulcanization treatment of the rubber body is not particularly limited, and may be vulcanized according to a conventional method.
As described above, since the predetermined silica particles are blended in the rubber composition at a predetermined ratio, even if the rubber in the rubber composition is a low-polar rubber, the entire rubber composition As a rubber body obtained using the same, it has polarity (surface activity) and has excellent affinity with an adhesive.

Accordingly, the adherend is not particularly limited as long as it has an affinity with an adhesive and excellent adhesive strength, and examples thereof include metal materials such as steel, stainless steel, and aluminum; concrete, cement cured products, Examples include inorganic materials such as stone, ceramics, and glass; organic materials such as plastic and rubber; and wood.
Further, the adherend is not limited to this, but the adhesive force (peeling force) with the adhesive layer exceeds the adhesive force (peeling force) between the rubber body and the adhesive layer. Is preferred.

  When the adherend is a metal material such as steel, stainless steel, and aluminum, the surface of the adherend (the adherend surface) is not limited to this. It is preferable to perform a roughening process such as a shot blasting process. In addition, when the adherend is concrete, hardened cement, stone, ceramics, glass or the like, it is not limited to this, but the adherend surface of the adherend is subjected to a degreasing treatment or the like in advance. It is preferable.

The adhesive that forms the adhesive layer is not particularly limited, and examples thereof include various adhesives such as epoxy, urethane, vinyl acetate, cyanoacrylate, polyester, and acrylic-modified silicone resin. .
The adhesive may be appropriately selected according to the material of the adherend, and is not particularly limited. Among them, an epoxy-based or acrylic-modified silicone resin-based adhesive is preferable. Epoxy adhesives include one-part curable type and two-part curable type, and any of them may be used.

  Epoxy and acrylic-modified silicone resin adhesives generally have low adhesion to low-polarity (low surface active) rubber, and therefore are not commercially available for epoxy or acrylic-modified silicone resin adhesives. In general, it has been shown that it is not suitable for bonding low polarity (low surface activity) rubber (eg, NR, IR, IIR, EPDM, etc.). However, in the above composite, when the rubber composition forming the rubber body is given sufficient polarity (or surface activity), an epoxy-based or acrylic-modified silicone resin-based adhesive is used. Even so, a rubber body made of low-polarity (low surface activity) rubber can be adhered to the adherend with high adhesive strength.

1 to 4 are all schematic cross-sectional views showing an embodiment of the composite of the present invention.
In FIG. 1, the composite 10 includes a rubber sheet (rubber body) 11 and an adherend 12, and the rubber sheet 11 and the adherend 12 are bonded via an adhesive layer 13. Yes.
Examples of the rubber composition that forms the rubber sheet 11 include the above-described rubber composition of the present invention.

Examples of the adherend 12 include the adherend described above. For example, when the adherend 12 is a steel plate, a rubber-steel plate composite is formed, and when the adherend 12 is a concrete structure, a rubber-concrete composite is formed.
Examples of the adhesive forming the adhesive layer 13 include the adhesives described above.
According to the composite 10 shown in FIG. 1, since the rubber sheet 11 as the adherend to be attached to the surface of the adherend 12 is made of the rubber composition of the present invention described above, the rubber sheet 11 and a composite with high adhesive strength between the adherend 12 can be obtained. The adhesive strength between the rubber sheet 11 and the adherend 12 is such that even if the adherend 12 is a highly polar adherend such as a metal material or a concrete structure, Even if the rubber used in the rubber composition forming the rubber sheet 11 is a low polarity (low surface activity) rubber, a high value can be obtained.

Further, according to the composite 10 shown in FIG. 1, even when the rubber used in the rubber composition forming the rubber sheet 11 is a low polarity (low surface activity) rubber, an epoxy-based or acrylic-modified silicone resin is used. High adhesive strength can be obtained by using an adhesive of the system.
In FIG. 2, the composite 15 includes a rubber sheet 11, a sheet (other sheet) 16 made of a rubber composition or a resin composition different from the rubber composition forming the rubber sheet 11, an adherend 12 The rubber sheet 11, the other sheet 16, and the adherend 12 are bonded through an adhesive layer 13.

The rubber sheet 11, the adherend 12 and the adhesive layer 13 are the same as described above.
Although it does not specifically limit as a rubber composition or resin composition which forms the other sheet | seat 16, From the viewpoint of the adhesiveness of the rubber sheet 11 and the other sheet | seat 16, the rubber | gum which comprises the said rubber composition, and the said resin composition The resin constituting the material is preferably a material that is easily vulcanized and bonded to the rubber sheet 11 when the rubber sheet 11 is vulcanized, for example.

  According to the composite 15 shown in FIG. 2, a composite having a high adhesive strength between the rubber sheet 11 and the adherend 12 can be obtained as in the case of the composite 10 shown in FIG. 1. Therefore, a composite in which the other sheet 16 and the adherend 12 are firmly bonded by combining the rubber sheet 11 and the other sheet 16 with a high adhesive strength by, for example, vulcanization bonding. You can get a body.

In FIG. 3, the composite 20 includes a total of two rubber sheets 11 and an adherend 12, and the two rubber sheets 11 are respectively attached to the adherend 12 via an adhesive layer 13. It is glued to.
The rubber sheet 11, the adherend 12 and the adhesive layer 13 are the same as described above.
According to the composite 20 shown in FIG. 3, a composite having high adhesive strength between the rubber sheet 11 and the adherend 12 can be obtained as in the case of the composite 10 shown in FIG. 1. The number of layers of the rubber sheet 11 and the adherend 12 is not limited to the number of layers shown in FIG. 3 and can be set as appropriate.

For example, the composite 20 obtained using a metal plate such as a steel plate as the adherend 12 is suitable for use as a seismic isolation structure, for example.
In FIG. 4, the composite body 25 includes a rubber sheet 11 and two types of adherends 12 a and 12 b, and the two types of adherends 12 a and 12 b are respectively interposed through the adhesive layer 13. Bonded to the rubber sheet 11.

The rubber sheet 11 and the adhesive layer 13 are the same as described above.
Examples of the two types of adherends 12a and 12b include the same ones as the above-described adherend 12.
According to the composite body 25 shown in FIG. 4, a composite body in which the two adherends 12a and 12b are bonded with high adhesive strength can be obtained. Therefore, for example, the two kinds of adherends 12a and 12b are poorly compatible with each other, and the two kinds of adherends 12a and 12b can be directly bonded using the above-described adhesive. Even if it is difficult, the two types of adherends 12a and 12b can be firmly bonded to each other by interposing the rubber sheet 11 and the adhesive layer 13 between the two types of adherends 12a and 12b. it can.

  As the two types of adherends 12a and 12b, for example, a sheet shape obtained by using two rubber sheets having different polarities (specifically, a sheet made of NBR and a sheet made of NR, EPDM, etc.). The composite body 25 can highly suppress the separation between the adherends 12a and 12b while making the rubber material different on one side and the other side of the sheet.

Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example.
<Manufacture of rubber composition>
One of the following four types was used for the silica particles.
“Nipsil RS-150”: DBA adsorption amount 154 mmol / kg, manufactured by Tosoh Silica Co., Ltd. “Nipsil VN3”: DBA adsorption amount 280 mmol / kg, manufactured by Tosoh Silica Co., Ltd. “Nipsil KQ” : DBA adsorption amount 340 mmol / kg, manufactured by Tosoh Silica Co., Ltd. “Nipsil AZ-200”: DBA adsorption amount 420 mmol / kg, manufactured by Tosoh Silica Co., Ltd. Example 1
100 parts by weight of natural rubber (raw rubber), 40 parts by weight of “Nipseal VN3”, 4 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1.5 parts by weight of sulfur and a vulcanization accelerator (sulfenamide vulcanization accelerator BBS A rubber composition was obtained by blending 1 part by weight of a trade name “Noxeller NS” (manufactured by Ouchi Shinsei Chemical Co., Ltd.) and kneading with a closed kneader.

  The content ratio of silica particles in the whole rubber composition was about 26.9% by weight, and the rubber composition did not contain a silane compound. Further, the integrated value (hereinafter referred to as “DBA ×”) of the content (parts by weight) of silica particles (Nipseal VN3) with respect to 100 parts by weight of rubber (NR) and the DBA adsorption amount (mmol / kg) of the silica particles (Nipseal VN3). Was sometimes referred to as “silica amount”).

Example 2
A rubber composition was obtained in the same manner as in Example 1 except that the blending amount of “Nipsea VN3” was 80 parts by weight. The content ratio of the silica particles in the whole rubber composition obtained was about 26.9% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 22400.

Comparative Example 1
A rubber composition was obtained in the same manner as in Example 1 except that “Nipsea VN3” was not blended. The obtained rubber composition contained neither silica particles nor a silane compound, and “DBA × silica amount” was zero.
Comparative Example 2
The same procedure as in Example 1 was performed except that “Nipseal RS-150” was used instead of “Nipseal VN3”, and the blending amount of “Nipseal RS-150” was 60 parts by weight with respect to 100 parts by weight of NR. Thus, a rubber composition was obtained. The content ratio of silica particles in the whole rubber composition was about 35.6% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 9240.

Comparative Example 3
A rubber composition was obtained in the same manner as in Comparative Example 2 except that the blending amount of “Nipsea RS-150” was 80 parts by weight with respect to 100 parts by weight of NR. The content ratio of silica particles in the whole rubber composition was about 42.4% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 12320.

Example 3
100 parts by weight of natural rubber (raw rubber), 80 parts by weight of “Nipsea VN3”, 12 parts by weight of silane compound (phenyltriethoxysilane, trade name “KBE103”, manufactured by Shin-Etsu Chemical Co., Ltd.), 4 parts by weight of zinc oxide A rubber composition was prepared by blending 2 parts by weight of stearic acid, 1.5 parts by weight of sulfur and 1 part by weight of a vulcanization accelerator (BBS, the above-mentioned trade name “Noxeller NS”) and kneading in a closed kneader. I got a thing.

The content ratio of the silica particles in the whole rubber composition is about 39.9%, and the rubber composition contains the silane compound at a ratio of 15.0% by weight with respect to the amount of silica particles. It was. Further, “DBA × silica amount” was 22400.
Example 4
100 parts by weight of natural rubber (raw rubber), 120 parts by weight of “Nipsea VN3”, 20 parts by weight of silane compound (phenyltriethoxysilane, the above-mentioned trade name “KBE103”), process oil (aromatic process oil, trade name) “Diana Process AH-16” (manufactured by Idemitsu Kosan Co., Ltd.) 30 parts by weight, zinc oxide quadruple parts, stearic acid 2 parts by weight, sulfur 1.5 parts by weight and vulcanization accelerator (BBS, the above-mentioned product) A rubber composition was obtained by blending 1 part by weight of “Noxeller NS”) and kneading with a closed kneader.

The content ratio of the silica particles in the whole rubber composition is about 43.1%, and the rubber composition contains the silane compound at a ratio of 16.7% by weight with respect to the amount of silica particles. It was. Further, “DBA × silica amount” was 33600.
Example 5
A rubber composition was obtained in the same manner as in Example 4 except that the compounding amount of “Nipsea VN3” was 135 parts by weight. The content ratio of silica particles in the obtained rubber composition is about 46.0% by weight, and the rubber composition contains a silane compound in a ratio of 14.8% by weight with respect to the amount of silica particles. Contained. Further, “DBA × silica amount” was 37800.

Comparative Example 4
A rubber composition was used in the same manner as in Example 1 except that “Nipsil KQ” was used instead of “Nipsil VN3”, and the blending amount of “Nipsil KQ” was 20 parts by weight with respect to 100 parts by weight of NR. I got a thing. The content ratio of the silica particles in the whole rubber composition was about 15.6% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 6800.

Example 6
A rubber composition was obtained in the same manner as in Comparative Example 4 except that the amount of “Nipseal KQ” was 65 parts by weight with respect to 100 parts by weight of NR. The content ratio of the silica particles in the whole rubber composition obtained was about 37.5% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 22100.

Example 7
A rubber composition was obtained in the same manner as in Comparative Example 4 except that the amount of “Nipseal KQ” was 80 parts by weight with respect to 100 parts by weight of NR. The content ratio of silica particles in the whole rubber composition was about 42.4% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 30400.

Comparative Example 5
The same procedure as in Example 1 was performed except that “Nipseal AZ-200” was used instead of “Nipseer VN3”, and the blending amount of “Nipseer AZ-200” was 100 parts by weight with respect to 100 parts by weight of NR. Thus, a rubber composition was obtained. The content ratio of the silica particles in the whole rubber composition was about 48.0% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 42,000.

Example 8
A rubber composition was obtained in the same manner as in Comparative Example 5, except that the amount of “Nipseal AZ-200” was 53 parts by weight with respect to 100 parts by weight of NR. The content ratio of the silica particles in the whole rubber composition was about 32.8% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 22260.

<Manufacture of rubber-steel plate composite>
Each of the rubber compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 was charged into a mold and vulcanized at 150 ° C. to obtain a vulcanized rubber sheet having a thickness of 2 mm. . Next, from the obtained vulcanized rubber sheet, a rubber piece having a width of 25 mm, a length of 125 mm, and a thickness of 2 mm was cut out, and the surface of the obtained rubber piece was wiped off with a cloth soaked in toluene, and degreased. And then dried.

Next, the surface of a steel plate having a width of 25 mm, a length of 60 mm, and a thickness of 1.5 mm was roughened by shot blasting (grinding material: steelmaking slag, dry air blasting), and then washed with acetone.
About 1.5 g of two-component curing type epoxy adhesive (main agent: trade name “GB301”, hardener: trade name “GB101”, manufactured by SRI Hybrid Co., Ltd.) is applied to the blasted surface of the obtained steel sheet. After the rubber pieces were stacked, the steel plate and the rubber pieces were fixed with clips and left at room temperature for 96 hours or longer to bond the steel plates and the rubber pieces to obtain a rubber-steel plate composite.

Incidentally, the rubber - steel complexes in accordance with the test piece in the "90 ° peel test of a steel sheet and vulcanized rubber" of JIS K 6256 _-1999 "adhesion test method of vulcanized rubber and thermoplastic rubber" Preparation did. The layer structure of this rubber-steel plate composite is as shown in FIG.
<Evaluation of physical properties of rubber composition and rubber-steel plate composite>
(A) Processability of rubber composition For the rubber compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5, the degree of processability when producing a vulcanized rubber sheet from the rubber composition, respectively. The evaluation was based on the following criteria.
A: Workability was good.
B: Although workability was slightly inferior, there was no problem in practical use.
C: Workability was inferior, and practical problems such as the inability to produce a vulcanized rubber sheet occurred.

(B) Peel strength of vulcanized rubber sheet in rubber-steel plate composite For the rubber-steel plate composites obtained in Examples 1-8 and Comparative Examples 1-5, the peel strength of the vulcanized rubber sheet, respectively. (N / 25 mm) was measured based on the "90 ° peel test of a steel sheet and vulcanized rubber" described in JIS K 6256 _-1999 "adhesion test method of vulcanized rubber and thermoplastic rubber." A tensile / compression tester (manufactured by Shimadzu Corporation) was used for the measurement.

  The result of the said physical-property evaluation is shown to Tables 1-3 with the composition of a rubber composition, etc.

  In Tables 1 to 3, “DBA × silica amount” is an integrated value of the DBA adsorption amount (mmol) of silica particles and the compounding amount (parts by weight) of silica particles with respect to 100 parts by weight of rubber. “Silica particles” in the “content ratio” column indicates the content ratio (% by weight) of silica particles in the entire rubber composition, and “silane compound” indicates a silane compound relative to the content of silica particles in the rubber composition. The content ratio (% by weight) of each is shown. “Epoxy” in the “Adhesive Type” column indicates a curable epoxy adhesive. In addition, “other compounding agents” in the “composition of rubber composition” column includes zinc oxide, stearic acid, sulfur and a vulcanization accelerator.

FIG. 6 is a graph showing the relationship between the DBA adsorption amount (mmol) of silica particles and the compounding amount (parts by weight) of silica particles with respect to 100 parts by weight of rubber for the examples and comparative examples.
As shown in Tables 1 to 3, silica particles having a dibutylamine adsorption amount in the range of 180 to 450 mmol / kg were used, and the silica particles were blended at a ratio of 160 parts by weight or less with respect to 100 parts by weight of rubber (NR). Thus, according to the rubber compositions of Examples 1 to 8 in which “DBA × silica amount” was set in the range of 10,000 to 40,000, the bond strength with the steel sheet was remarkably maintained while maintaining the processability of the rubber composition. I was able to improve.

<Manufacture of rubber composition>
Example 9
100 parts by weight of ethylene-propylene-diene copolymer rubber (EPDM), 80 parts by weight of “Nipseal VN3”, 30 parts by weight of process oil (aromatic process oil, the above-mentioned trade name “Diana Process AH-16”), oxidation 4 parts by weight of zinc, 2 parts by weight of stearic acid, 2 parts by weight of sulfur, 1 part by weight of sulfenamide vulcanization accelerator BBS (the above-mentioned trade name “Noxeller NS”), and thiuram vulcanization accelerator TETD (product) A rubber composition was obtained by blending 1 part by weight of “Noxeller TET” (manufactured by Ouchi Shinsei Chemical Co., Ltd.) and kneading with a closed kneader.

The content ratio of the silica particles in the whole rubber composition was about 36.4% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 22400.
Comparative Example 6
A rubber composition was obtained in the same manner as in Example 9 except that “Nipsea VN3” was not blended. The obtained rubber composition contained neither silica particles nor a silane compound, and “DBA × silica amount” was zero.

<Manufacture of rubber-steel plate composite>
A rubber piece having a width of 25 mm, a length of 125 mm, and a thickness of 2 mm was produced in the same manner as described above except that the rubber composition obtained in Example 9 and Comparative Example 6 was used. Similarly, it was degreased and dried.
Next, on the blasted surface of a steel plate (width 25 mm, length 60 mm, thickness 1.5 mm) blasted in the same manner as described above, a two-component curable epoxy adhesive (main agent: trade name “GB301”), Curing agent: Product name “GB101” (manufactured by SRI Hybrid Co., Ltd.) of about 1.5 g is applied, and after the rubber pieces are stacked, the steel plate and the rubber pieces are fixed with clips and left at room temperature for 96 hours. Thus, the steel plate and the rubber piece were bonded to obtain a rubber-steel plate composite.

Incidentally, the rubber - steel complexes in accordance with the test piece in the "90 ° peel test of a steel sheet and vulcanized rubber" of JIS K 6256 _-1999 "adhesion test method of vulcanized rubber and thermoplastic rubber" Preparation did. The layer structure of this rubber-steel plate composite is as shown in FIG.
In addition, as an adhesive, instead of a two-part curable epoxy adhesive, an adhesive mainly composed of an acrylic-modified silicone resin (trade name “Cemedine (registered trademark) Super X No. 8008”, manufactured by Cemedine Co., Ltd.) A rubber-steel plate composite was obtained in the same manner as above except that was used.

  In addition, it was set as Example 10 about the rubber-steel plate composite which adhere | attached the rubber piece produced from the same rubber composition as Example 9 by "Cemedine (trademark) super X No.8008." Further, Comparative Example 7 was used for a rubber-steel plate composite in which a rubber piece produced from the same rubber composition as Comparative Example 6 was bonded with “Cemedine (registered trademark) Super X No. 8008”.

<Evaluation of physical properties of rubber composition and rubber-steel plate composite>
(A) Processability of rubber composition For the rubber compositions obtained in Example 9 and Comparative Example 6, the degree of processability when producing a vulcanized rubber sheet from the rubber composition was described above. Was evaluated according to the same criteria.
(B) Peel strength of vulcanized rubber sheet in rubber-steel plate composite For the rubber-steel plate composites obtained in Examples 9-10 and Comparative Examples 6-7, the peel strength of the vulcanized rubber sheet, respectively. (N / 25 mm) was measured on the basis of the "90 ° peel test of a steel sheet and vulcanized rubber" described in JIS K 6256 _-1999 "adhesion test method of vulcanized rubber and thermoplastic rubber". A tensile / compression tester (manufactured by Shimadzu Corporation) was used for the measurement.

  The results of the above physical property evaluation are shown in Table 4 together with the composition of the rubber composition.

  In Table 4, “DBA × silica amount” is an integrated value of the DBA adsorption amount (mmol) of silica particles and the compounding amount (parts by weight) of silica particles with respect to 100 parts by weight of rubber. “Silica particles” in the “content ratio” column indicates the content ratio (% by weight) of silica particles in the entire rubber composition, and “silane compound” indicates a silane compound relative to the content of silica particles in the rubber composition. The content ratio (% by weight) of each is shown. In the “Adhesive Type” column, “epoxy” indicates a curable epoxy adhesive, and “silicone” indicates an adhesive mainly composed of an acrylic-modified silicone resin.

FIG. 6 is a graph showing the relationship between the DBA adsorption amount (mmol) of silica particles and the compounding amount (parts by weight) of silica particles with respect to 100 parts by weight of rubber for the examples and comparative examples.
As shown in Table 4, silica particles having a dibutylamine adsorption amount in the range of 180 to 450 mmol / kg are used, and the silica particles are blended at a ratio of 160 parts by weight or less with respect to 100 parts by weight of rubber (EPDM). According to the rubber compositions of Examples 9 and 10 in which “DBA × silica amount” is set in the range of 10,000 to 40,000, the bond strength with the steel sheet is remarkably improved while maintaining the workability of the rubber composition. I was able to.

<Manufacture of rubber composition>
Example 11
100 parts by weight of acrylonitrile-butadiene rubber (NBR), 80 parts by weight of “Nipsea VN3”, 4 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of sulfur, sulfenamide vulcanization accelerator BBS 1 part by weight of “Noxeller NS”) and 1 part by weight of thiuram vulcanization accelerator TETD (the above-mentioned “Noxeller TET”) are mixed and kneaded in a closed kneader to obtain a rubber composition. Got.

The content ratio of the silica particles in the whole rubber composition was about 42.1% by weight, and the rubber composition did not contain a silane compound. Further, “DBA × silica amount” was 22400.
Comparative Example 8
A rubber composition was obtained in the same manner as in Example 11 except that “Nipseal VN3” was not blended. The obtained rubber composition contained neither silica particles nor a silane compound, and “DBA × silica amount” was zero.

<Manufacture of rubber-steel plate composite>
A rubber piece having a width of 25 mm, a length of 125 mm, and a thickness of 2 mm was produced in the same manner as described above except that the rubber composition obtained in Example 11 and Comparative Example 8 was used. Similarly, it was degreased and dried.
Next, on the blasted surface of a steel plate (width 25 mm, length 60 mm, thickness 1.5 mm) blasted in the same manner as described above, a two-component curable epoxy adhesive (main agent: trade name “GB301”), Curing agent: Product name “GB101” (manufactured by SRI Hybrid Co., Ltd.) of about 1.5 g is applied, and after the rubber pieces are stacked, the steel plate and the rubber pieces are fixed with clips and left at room temperature for 96 hours. Thus, the steel plate and the rubber piece were bonded to obtain a rubber-steel plate composite.

Incidentally, the rubber - steel complexes in accordance with the test piece in the "90 ° peel test of a steel sheet and vulcanized rubber" of JIS K 6256 _-1999 "adhesion test method of vulcanized rubber and thermoplastic rubber" Preparation did. The layer structure of this rubber-steel plate composite is as shown in FIG.
<Evaluation of physical properties of rubber composition and rubber-steel plate composite>
(A) Processability of rubber composition For the rubber compositions obtained in Example 11 and Comparative Example 8, the degree of processability when producing a vulcanized rubber sheet from the rubber composition was described above. Was evaluated according to the same criteria.

(B) Peel strength of vulcanized rubber sheet in rubber-steel plate composite For the rubber-steel plate composite obtained in Example 11 and Comparative Example 8, the peel strength (N / 25 mm) of the vulcanized rubber sheet, respectively. ) was measured on the basis of the "90 ° peel test of a steel sheet and vulcanized rubber" described in JIS K 6256 _-1999 "adhesion test method of vulcanized rubber and thermoplastic rubber". A tensile / compression tester (manufactured by Shimadzu Corporation) was used for the measurement.

  The results of the physical property evaluation are shown in Table 5 together with the composition of the rubber composition.

  In Table 5, “DBA × silica amount” is an integrated value of the DBA adsorption amount (mmol) of silica particles and the compounding amount (parts by weight) of silica particles with respect to 100 parts by weight of rubber. “Silica particles” in the “content ratio” column indicates the content ratio (% by weight) of silica particles in the entire rubber composition, and “silane compound” indicates a silane compound relative to the content of silica particles in the rubber composition. The content ratio (% by weight) of each is shown. “Epoxy” in the “Adhesive Type” column indicates a curable epoxy adhesive.

FIG. 6 is a graph showing the relationship between the DBA adsorption amount (mmol) of silica particles and the compounding amount (parts by weight) of silica particles with respect to 100 parts by weight of rubber for the examples and comparative examples.
As shown in Table 5, silica particles having a dibutylamine adsorption amount in the range of 180 to 450 mmol / kg are used, and the silica particles are blended at a ratio of 160 parts by weight or less with respect to 100 parts by weight of rubber (EPDM). According to the rubber compositions of Examples 9 and 10 in which “DBA × silica amount” is set in the range of 10,000 to 40,000, the bond strength with the steel sheet is remarkably improved while maintaining the workability of the rubber composition. I was able to.

  FIG. 6 is a graph showing the relationship between the DBA adsorption amount (mmol) of silica particles and the compounding amount (parts by weight) of silica particles with respect to 100 parts by weight of rubber for the above Examples and Comparative Examples, as described above. is there. According to the graph shown in FIG. 6 and the results shown in Tables 1 to 5 above, (i) the range of the dibutylamine adsorption amount is 180 to 450 mmol / kg for the silica particles blended in the rubber composition, and (ii) this When the blending amount of silica particles with respect to 100 parts by weight of rubber is 160 parts by weight or less and (iii) the range of “DBA × silica amount” is 10,000 to 40,000, while maintaining the processability of the rubber composition, It can be seen that the adhesive strength with the steel sheet can be remarkably improved as compared with the case where at least one of the numerical ranges shown in the above (i) to (iii) is out of the above range.

The present invention is not limited to the above description, and various design changes can be made within the scope of the matters described in the claims.
In addition, examples of application of the rubber composition of the present invention and a rubber body using the rubber composition include a waterproof sheet to be bonded to concrete, a lining material for a concrete structure, and the like. Moreover, the composite body of a rubber body and a steel plate (metal material) as described above can be applied to vibration-proof rubber, damping material, and the like. For example, conventional anti-vibration rubber is generally vulcanized and bonded to rubber and attached with anchor bolts. By using the rubber body of the present invention, it is directly attached to steel with adhesive. The cost can be reduced significantly.

It is a schematic sectional drawing which shows one Embodiment of the composite_body | complex of this invention. It is a schematic sectional drawing which shows other embodiment of the composite_body | complex of this invention. It is a schematic sectional drawing which shows other embodiment of the composite_body | complex of this invention. It is a schematic sectional drawing which shows other embodiment of the composite_body | complex of this invention. It is a graph which shows the relationship between the DBA adsorption amount of a silica particle, and the compounding quantity of a silica particle about the Example and comparative example of this invention.

Explanation of symbols

10, 15, 20, 25 Composite 11 Rubber sheet (rubber body)
12, 12a, 12b Substrate 13 Adhesive layer

Claims (5)

Containing rubber and silica particles,
The dibutylamine adsorption amount of the silica particles is 180 to 450 mmol / kg,
The content of the silica particles with respect to 100 parts by weight of the rubber is 160 parts by weight or less, and
The content of the silica particles to the rubber 100 parts by weight (parts by weight), the integrated value of the dibutylamine adsorption amount of the silica particles (mmol / kg) is Ri 10000-40000 der,
A rubber composition for a rubber body , characterized by being used for a rubber body bonded to an adherend through an adhesive layer . The content of the silane compound of the rubber body rubber composition, characterized in that 30% by weight or less relative to the content of the silica particles of the rubber body rubber composition, according to claim 1 The rubber composition for rubber bodies described in 1. The rubber composition for a rubber body according to claim 1, wherein the rubber is a low polarity rubber. A rubber body comprising the rubber composition for a rubber body according to any one of claims 1 to 3 and an adherend are bonded via an adhesive layer.   The composite body according to claim 4, wherein the rubber body is a rubber sheet vulcanized before adhesion to the adherend.

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