JP2010285560A - Carbon black, rubber composition for high-damping laminate, and the high-damping laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-damping laminate which is high in damping performance and excellent in shearing modulus as well, to provide a rubber composition for the high-damping laminate, capable of obtaining the laminate and excellent in processability, and to provide carbon black to be used in the rubber composition. <P>SOLUTION: There is provided the carbon black having the following characteristics: the nitrogen adsorption specific surface area is 150-250 m<SP>2</SP>/g; the difference between the nitrogen adsorption specific surface area and CTAB adsorption ratio surface area is ≤25 m<SP>2</SP>/g; and the ratio of the half-width (D50) of the aggregate distribution to Stokes diameter(Dst):[(D50)/(Dst)] is ≤0.62. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to carbon black, a rubber composition for a high attenuation laminate, and a high attenuation laminate.

  In recent years, anti-vibration devices, vibration isolation devices, seismic isolation devices, and the like are rapidly spreading as vibration energy absorbing devices. In such an apparatus, a rubber composition having vibration energy damping performance is used.

  For example, laminated rubber for seismic isolation used in bridge bearings and building seismic isolation devices has high damping (attenuates vibration energy by converting vibration into more heat) and the desired shear elasticity The rate is required to develop.

As a rubber composition used for such a seismic isolation laminated rubber, the present applicant has disclosed in Patent Document 1 “100 parts by mass of a diene rubber, a nitrogen adsorption specific surface area of 150 to 300 m ² / g, and DBP absorption. amount 115cm ^3/100 g or less, and the nitrogen adsorption specific difference 5~34m ² / g and a carbon black from 50 to 90 parts by weight of high damping support for a rubber composition containing the surface area to CTAB adsorption specific surface area. ".

JP 2007-246655 A

However, the present inventor examined the type and blending amount of carbon black to achieve further improvement in the high damping bearing rubber composition described in Patent Document 1, and improved the damping. Even if it can be done, it has become clear that the viscosity during unvulcanization increases and the processability is inferior, or the shear modulus after vulcanization may decrease.
Accordingly, the present invention provides a highly damped laminate having high damping properties and excellent shear modulus, a rubber composition for a highly damped laminate excellent in processability capable of realizing the laminate, and the rubber composition. The purpose is to provide carbon black to be used.

As a result of intensive studies to solve the above problems, the present inventor has found that the ratio between the nitrogen adsorption specific surface area, the difference between the nitrogen adsorption specific surface area and the CTAB adsorption specific surface area, and the half-value width of the aggregate distribution and the Stokes diameter are predetermined. By using carbon black in the range, a highly damped laminate having high damping properties and excellent shear modulus, and a rubber composition for a highly damped laminate having excellent processability capable of realizing this laminate can be obtained. As a result, the present invention has been completed.
That is, the present invention provides the following (1) to (5).

(1) a nitrogen adsorption specific surface area of 150 to 250 ² / g, the difference between the nitrogen adsorption specific surface area and CTAB adsorption specific surface area of not more than 25 m ² / g, and a half width of aggregate distribution (D50) Carbon black having a ratio [(D50) / (Dst)] to Stokes diameter (Dst) of 0.62 or less.

  (2) A rubber composition for a high-damping laminate comprising 100 parts by mass of a diene rubber and 50 to 90 parts by mass of the carbon black described in (1) above.

  (3) The rubber composition for a high attenuation laminate according to (2), further containing a petroleum resin.

  (4) The rubber composition for a high attenuation laminate according to (3), wherein the content of the petroleum resin is 5 to 45 parts by mass with respect to 100 parts by mass of the diene rubber.

  (5) A high attenuation laminate obtained by alternately laminating the rubber composition for a high attenuation laminate according to any one of (2) to (4) and a hard plate.

  As will be described below, according to the present invention, a highly damped laminate having high damping properties and excellent shear modulus, and a rubber composition for a highly damped laminate having excellent processability capable of realizing this laminate. And carbon black used in the rubber composition can be provided.

FIG. 1 is a schematic cross-sectional view of a high attenuation laminate showing an example of an embodiment of the high attenuation laminate of the present invention. FIG. 2 is a schematic side view of a sample for a lap shear type shear test. FIG. 3 is a graph showing an example of a hysteresis curve obtained by a lap shear type shear test.

The present invention is described in detail below.
Carbon black of the present invention, the nitrogen adsorption specific surface area of 150 to 250 ² / g, the difference between the nitrogen adsorption specific surface area and CTAB adsorption specific surface area of not more than 25 m ² / g, and a half width of aggregate distribution Carbon black having a ratio [(D50) / (Dst)] of (D50) to the Stokes diameter (Dst) of 0.62 or less.

(Nitrogen adsorption specific surface area)
The nitrogen adsorption specific surface area refers to the specific surface area obtained by the nitrogen adsorption method. Usually, the larger this value, the smaller the particle size of the carbon black.
The nitrogen adsorption specific surface area is a value measured by “nitrogen adsorption method—single point method” described in JIS K6217-2: 2001.

In the present invention, the nitrogen adsorption specific surface area is 150 to 250 ² / g, preferably from ^{175~225m 2 / g, 185~215m 2 /} g is more preferable.
When the nitrogen adsorption specific surface area is within this range, the balance between the processability of the rubber composition for a high attenuation laminate of the present invention described later and the attenuation of the high attenuation laminate of the present invention described later becomes good.

(Difference between nitrogen adsorption specific surface area and CTAB adsorption specific surface area)
The difference between the nitrogen adsorption specific surface area and the CTAB adsorption specific surface area represents the degree of unevenness on the surface of the carbon black, and it can be said that the smaller the value, the less the unevenness of the carbon black.
The difference between the nitrogen adsorption specific surface area and the CTAB adsorption specific surface area is a value obtained by subtracting the CTAB adsorption specific surface area from the nitrogen adsorption specific surface area, that is, a value obtained by (nitrogen adsorption specific surface area) − (CTAB adsorption specific surface area). is there.
Here, as the CTAB adsorption specific surface area, a value measured by “How to obtain a specific surface area—CTAB adsorption method” described in JIS K6217-3: 2001 is used.

In the present invention, the difference between the nitrogen adsorption specific surface area and CTAB adsorption specific surface area is at 25 m ² / g or less, preferably from 21~24m ² / g.
If the difference between the nitrogen adsorption specific surface area and the CTAB adsorption specific surface area is in this range, carbon black with relatively little unevenness is used, and the carbon black is not subject to excessive restriction by the diene rubber described later. It is considered that the dispersibility of carbon black is increased. Therefore, it is possible to suppress a decrease in shear modulus accompanying a decrease in dispersibility of carbon black, and a desired shear modulus can be obtained.

(Ratio between half-value width of aggregate distribution and Stokes diameter)
The ratio [(D50) / (Dst)] of the half-value width (D50) of the aggregate distribution and the Stokes diameter (Dst) represents the degree of distribution of the carbon black to be produced. Become sharp.
Here, the Stokes diameter (Dst) is the Stokes equivalent diameter of the maximum frequency in the distribution curve of the Stokes equivalent diameter of the aggregate obtained by centrifugal sedimentation of carbon black.
The half width (D50) refers to the width of the distribution curve at a position where 50% of the maximum Stokes equivalent diameter maximum frequency is obtained.
In this invention, it measured as follows. First, carbon black was added to water to adjust the carbon black concentration to 0.05% by mass, and then a sample solution sufficiently dispersed by ultrasonic waves was prepared. Next, 10 mL of spin solution (distilled water) was added to a rotating disk (rotation speed: 8000 rpm), and then 0.2 mL of the sample solution was injected to start centrifugal sedimentation, and the absorbance was measured by a photoelectric precipitation method. From the results, an aggregate distribution curve was prepared, and the half width (D1 / 2) and Stokes diameter (Dst) of the aggregate distribution were calculated. In addition, a disk centrifugal photo sidiometer (manufactured by Joye Loebl) was used for measuring the absorbance.

In the present invention, the ratio [(D50) / (Dst)] between the half-value width (D50) of the aggregate distribution and the Stokes diameter (Dst) is 0.62 or less, and is 0.62 to 0.55. Is preferable, and it is more preferable that it is 0.60-0.57.
When the ratio [(D50) / (Dst)] of the half-value width (D50) of the aggregate distribution and the Stokes diameter (Dst) is within this range, the aggregate distribution is sharpened, and the dispersibility of the carbon black is thereby improved. The rubber composition for a highly attenuated laminate according to the present invention, which will be described later, also has good processability.

Carbon black of the present invention, for reasons that can suppress a decrease in shear modulus of the high damping laminate of the present invention to be described later, DBP absorption amount, but preferably not more than ^{115cm 3 / 100g, 95~113cm 3 /} 100g Is more preferable, and 100-110 cm < ³ > / 100g is still more preferable.
Here, the DBP absorption is a measure of the ability of carbon black to absorb dibutyl phthalate (DBP), and the smaller this value, the smaller the structure of carbon black.
Further, the DBP absorption amount uses a value measured according to “Obtaining oil absorption amount” described in JIS K6217-4: 2008.

  The method for producing the carbon black of the present invention is not particularly limited, and can be produced by appropriately controlling combustion conditions, high-temperature combustion gas flow rate, feedstock introduction conditions, reaction stop time, and the like. Specifically, for example, in a reaction zone where raw material hydrocarbons are converted to carbon black, a method in which the calcination gas is made uniform and subjected to a thermal decomposition reaction at a high temperature (1600 ° C. or higher) and in a short time (within 100 msec), etc. It is done.

The rubber composition for highly attenuated laminates of the present invention (hereinafter also referred to as “the composition of the present invention”) contains 100 parts by mass of a diene rubber and 50 to 90 parts by mass of the above-described carbon black of the present invention. This is a rubber composition for a high attenuation laminate.
Hereinafter, each component used for the composition of this invention is demonstrated.

<Diene rubber>
The diene rubber used in the composition of the present invention is not particularly limited. Specifically, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber. (SBR), acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR), chloroprene rubber (CR) and the like.
The average molecular weight, monomer composition molar ratio, halogenation rate, and the like of these diene rubbers are not particularly limited, and can be arbitrarily set depending on the intended use.

Among these, natural rubber (NR) is preferable because the processability of the composition of the present invention is good and the high attenuation laminate of the present invention is also good.
In addition, butadiene rubber (BR) is preferred because the temperature dependency of the damping property and shear modulus of the high damping laminate of the present invention can be reduced.

In the present invention, each of the diene rubbers may be used alone or in combination of two or more.
As a suitable combination of the above diene rubbers when two or more kinds are used in combination, the rubber components are excellent in compatibility, processability, green strength and vulcanized physical properties. For example, natural rubber (NR) and butadiene rubber (BR) combined use system, isoprene rubber (IR) and butadiene rubber (BR) combined use system, natural rubber (NR) ), Isoprene rubber (IR) and butadiene rubber (BR). Among these, a combination system of natural rubber (NR) and butadiene rubber (BR) is more preferable in that this characteristic is more excellent. These mixing ratios are not particularly limited.

<Carbon black>
The carbon black used in the composition of the present invention is the carbon black of the present invention described above.
Content of the said carbon black is 50-90 mass parts with respect to 100 mass parts of said diene rubbers, It is preferable that it is 60-80 mass parts, and it is more preferable that it is 65-75 mass parts.
When the content of the carbon black is within this range, the effects described in the above-described carbon black of the present invention, that is, the processability of the composition of the present invention is improved, and the high-attenuation laminate of the present invention described later is used. The damping property is high and the shear modulus is also good.

<Petroleum resin>
The composition of the present invention preferably further contains a petroleum resin.
As the petroleum resin, conventionally known ones can be used, for example, C5 aliphatic unsaturated hydrocarbon polymer, C9 aromatic unsaturated hydrocarbon polymer, C5 aliphatic. Copolymers of unsaturated hydrocarbons and C9 aromatic unsaturated hydrocarbons can be used.
By containing such a petroleum resin, physical properties such as tensile strength after vulcanization and elongation at break are improved, and the damping property of the high damping laminate of the present invention described later is further enhanced.
Such a petroleum resin can stably exhibit high damping properties and excellent shear modulus when used in combination with an aggregate of quartz and kaolinite described later.

Specific examples of the C5 aliphatic unsaturated hydrocarbon include, for example, 1-pentene, 2-pentene, 2-methyl-1-butene contained in a C5 fraction obtained by thermal decomposition of naphtha, Olefinic hydrocarbons such as 3-methyl-1-butene and 2-methyl-2-butene; 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, 3-methyl-1 , 2-olefin hydrocarbons such as 2-butadiene;
These can be polymerized or copolymerized in the presence of a suitable catalyst. Here, the C5 aliphatic unsaturated hydrocarbon polymer is a co-polymer of a single C5 aliphatic unsaturated hydrocarbon homopolymer and two or more C5 aliphatic unsaturated hydrocarbons. It refers to any polymer.

Specific examples of the C9 aromatic unsaturated hydrocarbon include, for example, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p contained in a C9 fraction obtained by thermal decomposition of naphtha. -Vinyl-substituted aromatic hydrocarbons such as vinyltoluene.
These can be polymerized or copolymerized in the presence of a suitable catalyst. Here, the C9 aromatic unsaturated hydrocarbon polymer is a co-polymer of a single C9 aromatic unsaturated hydrocarbon homopolymer and two or more C9 aromatic unsaturated hydrocarbons. It refers to any polymer.

In addition, a copolymer of a C5 aliphatic unsaturated hydrocarbon and a C9 aromatic unsaturated hydrocarbon is a C9 aromatic unsaturated hydrocarbon in that the softening point of the copolymer is high. What a unit is 60 mol% or more is preferable, and what is 90 mol% or more is more preferable.
A copolymer of a C5 aliphatic unsaturated hydrocarbon and a C9 aromatic unsaturated hydrocarbon can be copolymerized in the presence of a suitable catalyst.

  In the present invention, the petroleum resin preferably has a softening point (JIS K2207) of 100 ° C. or higher because the molecular weight and the reactivity of the double bond affect the physical properties of the diene rubber. The above is more preferable.

Moreover, in this invention, it is preferable that it is 5-45 mass parts with respect to 100 mass parts of said diene rubbers, and, as for content of the said petroleum resin, it is more preferable that it is 10-45 mass parts.
When the content of the petroleum resin is within this range, a balanced highly-damped laminate is obtained that maintains high damping properties but has low temperature dependence and does not deteriorate stability against long-term repeated shear deformation. be able to.

Furthermore, in this invention, the mass ratio (inorganic filler / petroleum resin) of the inorganic filler mentioned later and the said petroleum resin is 1 / 0.2-1 / 3.5 in the range of the said mass part. Is more preferable, 1/1 to 1 / 3.0 is more preferable, and 1/1 to 1 / 2.5 is still more preferable.
When the mass ratio is within this range, it is possible to obtain a highly attenuated laminate having high attenuation and excellent stability against repeated shear deformation.

<Silica>
It is one of the preferred embodiments that the composition of the present invention further contains silica.
As the silica, conventionally known ones can be used, and specific examples thereof include fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, colloidal silica, etc., and these can be used alone. Or two or more of them may be used in combination.
Silica preferably has an average aggregate particle diameter of 5 to 50 μm, more preferably 5 to 30 μm.

In the present invention, the content of the silica is preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the diene rubber.
When the silica content is within this range, a highly attenuated laminate having excellent damping properties and shear modulus can be obtained.

<Inorganic filler>
It is one of the preferred embodiments that the composition of the present invention further contains an inorganic filler.
The inorganic filler does not include the above-described carbon black and silica.
Examples of the inorganic filler used include soft clays such as T-clay, kaolin clay, wax stone clay, sericite clay, and calcined clay; diatomaceous earth; heavy calcium carbonate, magnesium carbonate, aluminum hydroxide, sulfuric acid And agglomerates of barium, talc, quartz and kaolinite.
Among these, the high damping laminate of the present invention, which will be described later, can maintain particularly high damping properties and stability of physical properties against repeated shear deformation, so that the coagulation of T-clay, kaolin clay, quartz and kaolinite. Aggregation is preferred.

Here, conventionally known aggregates of quartz and kaolinite can be used. Especially, it is preferable that it is a natural coupling | bonding material of block quartz and plate-shaped kaolinite.
Specific examples of commercially available products include siritin (Siritin Z86, Siritin V85, Siritin N82, Siritin 85, Siritin N87 (all manufactured by Hoffman Mineral Co., Ltd.)). In addition, what has the same structure manufactured artificially can also be used.
As described above, when the composition of the present invention contains an aggregate of quartz and kaolinite, it is particularly excellent in the effect of improving the stability of damping property and shear modulus, and when used in combination with the petroleum resin, Damping and shear modulus can be exhibited more stably.

  Further, the mass ratio of quartz and kaolinite constituting the aggregate of quartz and kaolinite (quartz / kaolinite) is not particularly limited, but even if the high attenuation laminate of the present invention described later is repeatedly shear-deformed, The mass ratio of quartz and kaolinite is preferably 12/1 to 1/1, because higher damping properties and higher shear modulus can be stably exhibited, and 9/1 to 2/1. It is more preferable that

  Further, the aggregate of quartz and kaolinite can contain, for example, iron oxide, phosphorus component, and sulfur component in addition to quartz and kaolinite. Such an aggregate may be used independently and may use 2 or more types together.

In the present invention, the content of the inorganic filler is preferably 5 to 55 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 15 to 40 parts by mass with respect to 100 parts by mass of the diene rubber. .
When the content of the inorganic filler is within this range, it is possible to obtain a highly-damped laminate having a stable damping property and shear modulus for a long-term repeated shear deformation while maintaining a high damping property.

In the present invention, the total amount of the silica and the inorganic filler is preferably 20 to 75 parts by mass, more preferably 30 to 65 parts by mass with respect to 100 parts by mass of the diene rubber. .
When the total amount of silica and inorganic filler is in such a range, the damping is higher, the damping against long-term repeated shear deformation and the shear modulus are more stable, and the balance is high. A damping laminate is obtained.

  Furthermore, in the present invention, the mass ratio of the silica to the inorganic filler is preferably 1/1 to 1 / 2.5, and more preferably 1/1 to 1 / 2.0. When the mass ratio of silica to the inorganic filler is within this range, the processability of the composition of the present invention becomes better.

<Additives>
The composition of the present invention can contain other additives as necessary within a range not impairing the object of the present invention.
Examples of the additive include a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a plasticizer, a softening agent, a vulcanization aid, a flame retardant, a weathering agent, and a heat resistance agent.
Specific examples of the vulcanizing agent include sulfur; organic sulfur-containing compounds such as TMTD; organic peroxides such as dicumyl peroxide; and the like.
Specific examples of the vulcanization accelerator include sulfenamides such as N-cyclohexyl-2-benzothiazole sulfenamide (CBS); thiazoles such as mercaptobenzothiazole; tetramethylthiuram monosulfide and the like. Thiurams; stearic acid; and the like.
Specific examples of the antiaging agent include ketone / amine condensates such as TMDQ; amines such as DNPD; monophenols such as styrenated phenol; and the like.
Specific examples of the plasticizer include phthalic acid derivatives (for example, DBP, DOP and the like), sebacic acid derivatives (for example, DBS and the like) monoesters, and the like.
Specific examples of the softening agent include paraffinic oil (process oil).

  Although the manufacturing method of the composition of this invention is not specifically limited, For example, a well-known method and apparatus (for example, a Banbury mixer, a kneader, a roll, etc.) are used for the unvulcanized rubber composition which mix | blended each component mentioned above. And can be prepared by kneading.

  The high attenuation laminate of the present invention is a high attenuation laminate obtained by alternately laminating the above-described composition of the present invention and a hard plate, and is a structure used for bridge support, building base isolation, etc. It is.

  In FIG. 1, the cross-sectional schematic of the high attenuation | damping laminated body showing an example of the embodiment of the high attenuation | damping laminated body of this invention is shown. In FIG. 1, the code | symbol 1 represents a high attenuation | damping laminated body (seismic isolation laminated body), the code | symbol 2 represents a hard board, and the code | symbol 3 represents the rubber composition for high attenuation | damping laminated bodies of this invention.

As shown in FIG. 1 as an example, the high attenuation laminate 1 of the present invention includes a rubber composition 3 for a high attenuation laminate of the present invention and a hard plate 2 (for example, a general structural steel plate, a cold rolled steel plate, etc.). Are alternately stacked.
The high attenuation laminate 1 may be configured by providing an adhesive layer between the rubber composition 3 for the high attenuation laminate of the present invention and the hard plate 2, or directly without providing the adhesive layer. It may be configured by vulcanization.

In FIG. 1, the high attenuation laminate 1 of the present invention is shown in a state where the rubber composition 3 for the high attenuation laminate of the present invention and the hard plate 2 are alternately laminated. The body rubber composition 3 may have a structure in which two or more layers are laminated.
Moreover, in FIG. 1, although the example of a total of 13 layers of 6 layers about the rubber composition 3 for high attenuation laminated bodies of this invention and 7 layers about the hard board 2 is shown, the high attenuation laminated body 1 of this invention is shown. The number of laminated layers of the rubber composition 3 for a highly attenuated laminate of the present invention and the hard plate 2 is not limited to this, and can be arbitrarily set according to the intended use, required characteristics, and the like.
Furthermore, the size of the high attenuation structure 1 of the present invention, the overall thickness, the layer thickness of the rubber composition 3 for the high attenuation laminate of the present invention, the thickness of the hard plate, etc. It can be set arbitrarily according to the required characteristics.

  In order to produce the highly attenuated laminate of the present invention, the rubber composition for the highly attenuated laminate of the present invention is molded into a sheet and then vulcanized to obtain a sheet-like rubber composition, and then the adhesive is used. It may be laminated alternately with a hard plate by providing a layer, or after the rubber composition for a highly damped laminate of the present invention which has not been vulcanized in advance is formed into a sheet shape and alternately laminated with a hard plate The vulcanization and adhesion may be performed simultaneously by heating.

Since the highly attenuated laminate of the present invention uses the above-described composition of the present invention, it has an effect of high attenuation and excellent shear modulus.
Specifically, an equivalent damping constant (Heq) that is an index of damping performance measured by a lap shear shear test described later is 0.18 or more, and a shear elasticity modulus (Geq) that is similarly measured is 0.84 or more. .

The equivalent damping constant (Heq) and shear modulus (Geq) are measured by a lap shear shear test.
FIG. 2 is a schematic side view of a sample for a lap shear type shear test. In FIG. 2, the code | symbol 4 represents the sample for a lap shear type shear test, the code | symbol 5 represents the rolled unvulcanized rubber composition, and the code | symbol 6 represents a steel plate.
The unvulcanized rubber composition 5 is an unvulcanized rubber composition of the composition of the present invention that has been rolled to a size of 25 mm wide × 25 mm long × 5 mm thick. The steel plate 6 is a steel plate (width 25 mm × length 100 mm × thickness 20 mm) having a surface sandblasted and coated with a metal adhesive.
The sample 4 for lap shear type shear test is obtained by placing (stacking) the unvulcanized rubber composition 5 and the steel plate 6 as shown in FIG. 2 and then press vulcanizing at 130 ° C. for 120 minutes.

The lap shear shear test is performed under the following conditions using a vibrator (manufactured by Saginomiya), an input signal oscillator, and an output signal processor.
Using the lap shear type shear test sample prepared as described above, each time when a 175% strain was applied 10 times at a deformation frequency of 0.5 Hz by a biaxial shear tester at a measurement temperature of 23 ° C. Obtain the average shear characteristic value.
Specifically, using the Xmax and Qmax indicated by the hysteresis curve obtained in the lap shear type shear test, the equivalent damping constant (Heq) and shear modulus (Geq) are determined according to the following formulas (1) and (2). calculate. FIG. 3 shows an example of a hysteresis curve obtained by a lap shear type shear test.

In equation (1), ΔW is the area of the hysteresis loop (the shaded area in FIG. 3).
In the formula (2), Keq is represented by the following formula (3), H represents the total thickness of the rubber layer laminated in the high attenuation laminate, and A is the cross-sectional area of the rubber layer.

  The use, application conditions, and the like of the high attenuation laminate are not particularly limited as long as the high attenuation laminate is used as a vibration energy absorber. Among these, since it has the above-described excellent characteristics, it is preferably used as a vibration energy absorption device for buildings. For example, various vibration energy absorption devices for vibration isolation, vibration isolation, vibration isolation, etc. Is suitably used for, for example, support of road bridges, bridges, building base isolation, and detached base isolation applications).

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely according to an Example, this invention is not limited to the following Example.

(Production of carbon blacks 1 to 4)
Using a carbon black production plant, the conditions such as the amount of raw material oil (kg / h), the amount of fuel oil (kg / h) and the total amount of air (Nm ³ / h) shown in Table 1 below are adjusted. Table nitrogen adsorption specific surface area shown ^{(NSA) [m 2 / g} ], CTAB adsorption specific surface area ^{(CTAB) [m 2 / g} ], DBP absorption [cm ³ / 100g], the nitrogen adsorption specific surface area and CTAB adsorption specific surface area And carbon so that the difference [m ² / g] and the ratio of the half-value width (D50) [mm] of the aggregate distribution to the Stokes diameter (Dst) [mm] [(D50) / (Dst)] Blacks 1 to 4 were produced.
Carbon blacks 1, 3 and 4 can be obtained by requesting production from Shin Nikka Carbon Co., Ltd., and carbon black 2 is referred to as “Niteron # 415UD” manufactured by Nippon Nikkei Carbon Co., Ltd. Available under the trade name.

(Examples 1-3, Comparative Examples 1-5: Preparation of samples for lap shear type shear test)
First, each compound was blended and kneaded in a B-type Banbury mixer for 5 minutes so as to have the composition shown in Table 2 below (unit is part by mass) to prepare an unvulcanized rubber composition.
Next, the prepared unvulcanized rubber composition was rolled into a size of width 25 mm × length 25 mm × thickness 5 mm.
An unvulcanized rubber composition after rolling (5 in FIG. 2) and a steel plate (25 mm wide × 100 mm long × 20 mm thick, 6 in FIG. 2) coated with a metal adhesive by sandblasting the surface. 2 was placed (laminated) as shown in the side view of the lap shear type shear test sample 4 in FIG. 2, and then press vulcanized at 130 ° C. for 120 minutes to prepare a lap shear type shear test sample.

<Mooney viscosity>
About the obtained unvulcanized rubber composition, Mooney viscosity was measured according to JIS K6300-1: 2001 using an L-shaped rotor under the conditions of a preheating time of 1 minute and a test temperature of 125 ° C. The results are shown in Table 2.
Here, if the Mooney viscosity at 125 ° C. is 100 or less, it can be determined that the processability is excellent, but it is preferably 90 or less from the viewpoint of processability during mass production.

<Tensile properties>
The obtained unvulcanized rubber composition was vulcanized for 45 minutes under a pressure of 3.0 MPa using a press molding machine at 148 ° C. to prepare a vulcanized sheet having a thickness of 2 mm. A JIS No. 3 dumbbell-shaped test piece was punched from this sheet, and a tensile test at a tensile speed of 500 mm / min was conducted in accordance with JIS K6251-2004. Tensile strength (T _B ) [MPa], elongation at break (E _B ) [%], 100% modulus (M ₁₀₀ ) [MPa] and 300% modulus (M ₃₀₀ ) [MPa] were measured at room temperature. The results are shown in Table 2.

<Lap shear test>
A lap shear shear test was performed on the lap shear type shear test sample using a vibrator (manufactured by Saginomiya), an input signal oscillator, and an output signal processor. The number of lap shear type shear test samples used in each example was ten.
Specifically, the shear characteristics of each time when 175% strain was applied 10 times at a deformation frequency of 0.5 Hz by a biaxial shear tester and a measurement temperature of 23 ° C. with respect to the lap shear type shear test sample. The average of the values was obtained.
Using Xmax and Qmax indicated by the hysteresis curve obtained by this lap shear shear test, average shear characteristic values (Geq, Heq) were determined according to the above formulas (1) and (2). The results are shown in Table 2.
Here, the shear modulus (Geq) is desirably a high value, but is preferably 0.84 or more, and more preferably 0.90 or more.
The equivalent attenuation constant (Heq) is desirably a high value, but is preferably 0.18 or more, and more preferably 0.19 or more.

The components shown in Table 2 other than the carbon blacks 1 to 4 described above were as follows.
・ Natural rubber: STR20, manufactured by SIAM INDO RUBBER ・ Butadiene rubber: NipolBR1220, manufactured by Nippon Zeon ・ Silica: Nipseal AQ, manufactured by Tosoh Silica ・ Clay: SUPREX PLAY, manufactured by Kentucky Tennessee Clay Company ・ Zinc oxide: Zinc No. 3, manufactured by Shodo Chemical Co., Ltd. ・ Stearic acid: beads stearic acid YR, manufactured by NOF Corporation ・ Petroleum resin: High Resin # 120S (softening point 120 ° C., manufactured by Toho Chemical Co., Ltd.)
・ Anti-aging agent: 6C, manufactured by Seiko Chemical Co., Ltd. ・ Wax: Sunnock, manufactured by Ouchi Shinsei Chemical Co., Ltd. ・ Oil: Aroma oil (AO-MIX, manufactured by Sankyo Oil Chemical Co., Ltd.)
・ Sulfur: Sulfur powder, manufactured by Hosoi Chemical Co., Ltd. ・ Vulcanization accelerator: Noxeller CZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.

As apparent from Tables 1 and 2, the difference between the nitrogen adsorption specific surface area and the CTAB adsorption specific surface area, and the ratio between the half-value width (D50) of the aggregate distribution and the Stokes diameter (Dst) are within a predetermined range. When carbon black 2 not used was used, it was found that the Mooney viscosity was high and the processability was poor when the blending amount was increased from the viewpoint of improving the damping property and the shear modulus (see Comparative Examples 1 to 3). .
In addition, the rubber composition (Comparative Example 4) prepared using the carbon black 3 in which the ratio between the half width of the aggregate distribution (D50) and the Stokes diameter (Dst) is not within the predetermined range is excellent in processability. It was found that the damping property was low and the shear modulus was low.
Further, a rubber prepared using carbon black 4 in which the difference between the nitrogen adsorption specific surface area and the CTAB adsorption specific surface area, and the ratio between the half-value width (D50) of the aggregate distribution and the Stokes diameter (Dst) are not within a predetermined range. The composition (Comparative Example 5) was found to have excellent processability but low shear modulus.
In contrast, carbon black in which the nitrogen adsorption specific surface area, the difference between the nitrogen adsorption specific surface area and the CTAB adsorption specific surface area, and the ratio of the half-value width (D50) of the aggregate distribution to the Stokes diameter (Dst) are within a predetermined range. It was found that the rubber compositions (Examples 1 to 3) prepared using No. 1 were excellent in processability, high in damping properties, and excellent in shear modulus.

1 High attenuation laminate (Seismic isolation laminate)
2 Hard plate 3 Rubber composition for high attenuation laminate of the present invention 4 Sample for lap shear type shear test 5 Rolled unvulcanized rubber composition 6 Steel plate

Claims (5)

Nitrogen adsorption specific surface area of 150 to 250 ² / g, the difference between the nitrogen adsorption specific surface area and CTAB adsorption specific surface area of not more than 25 m ² / g, and a half width of aggregate distribution (D50) and the Stokes diameter ( Carbon black whose ratio [(D50) / (Dst)] to Dst) is 0.62 or less.   A rubber composition for a high damping laminate comprising 100 parts by mass of a diene rubber and 50 to 90 parts by mass of the carbon black according to claim 1.   The rubber composition for a high attenuation laminate according to claim 2, further comprising a petroleum resin.   The rubber composition for a high attenuation laminate according to claim 3, wherein the content of the petroleum resin is 5 to 45 parts by mass with respect to 100 parts by mass of the diene rubber.   A high attenuation laminate obtained by alternately laminating the rubber composition for a high attenuation laminate according to any one of claims 2 to 4 and a hard plate.

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