JP2013014688A - High damping composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel high damping composition that contains an S-IB diblock copolymer and an S-IB-S triblock copolymer together as a base polymer, and can form a high damping member that has a high damping performance and a large fracture elongation enough for being used as a vibration control damper of a building etc.SOLUTION: A calcium carbonate is combined into the S-IB diblock copolymer and the S-IB-S triblock copolymer as a filler. A tackifier may be combined as well. As the tackifier, a hydrogenated petroleum resin is preferable which has a softening point of lower than 125°C.

Description

  The present invention relates to a highly damped composition that is a source of a highly damped member that relaxes or absorbs transmission of vibration energy.

For example, high-attenuation members are used in a wide range of fields such as buildings such as buildings and bridges, industrial machines, airplanes, automobiles, railway vehicles, computers and peripheral equipment, household electrical equipment, and automobile tires. By using the high damping member, transmission of vibration energy can be relaxed or absorbed, that is, seismic isolation, vibration control, vibration control, vibration isolation, etc. can be performed.
The high damping member is formed by a high damping composition including various base polymers.

For example, a block copolymer (isobutylene block copolymer) of a polymer block (S) having an aromatic vinyl compound as a constituent monomer and a polymer block (IB) having isobutylene as a constituent monomer is Since it is expected that the structure can form a high damping member having excellent damping performance, practical application of the high damping composition as a base polymer has been studied.
In particular, the S-IB diblock copolymer having a structure in which the polymer block (S) and the polymer block (IB) are connected one block at a time is excellent in damping performance. However, when the S-IB diblock copolymer is used alone as a base polymer, there is a problem that the molding processability of the high attenuation composition is low.

In addition, the high attenuation member formed using the high attenuation composition has a small amount of elongation until cutting when a tensile stress is applied, that is, the elongation at the time of cutting is small, so that it is greatly deformed particularly when an earthquake or the like occurs. There is also a problem that it is not suitable as a damping damper for which vibration control is required.
Therefore, another polymer excellent in molding processability, having a large elongation at break and having excellent compatibility with the S-IB diblock copolymer, together with the S-IB diblock copolymer, has a high damping composition. Use as a base polymer of a product has been studied (see, for example, Patent Documents 1 to 3).

  Examples of the other polymer include an S-IB-S triblock copolymer [having a structure in which one polymer block (IB) is sandwiched between two polymer blocks (S)]. The S-IB-S triblock copolymer is not as high in damping performance as the S-IB diblock copolymer, but has excellent moldability than the S-IB diblock copolymer and has an elongation at break. Since it is large and is constituted by the same polymer block (S) (IB), it is excellent in compatibility with the S-IB diblock copolymer.

WO 01/74964 A1 JP-A-11-263896 JP 2000-119478 A

In the combined system of the S-IB diblock copolymer and the S-IB-S triblock copolymer, the balance of damping performance, molding processability, and elongation at cutting can be achieved by adjusting the blending ratio of the two. It is possible to take.
However, by simply adjusting the blending ratio by using both in combination, it is not possible to provide the high damping member with a high damping performance and a large elongation at the time of cutting that can be sufficiently used, for example, as a vibration damper for a building.

  The object of the present invention is to use S-IB diblock copolymer and S-IB-S triblock copolymer together as a base polymer, and it is high enough to be used as a damping damper for buildings. It is an object of the present invention to provide a novel high damping composition capable of forming a high damping member having damping performance and large elongation at break.

In order to solve the above-mentioned problems, the inventor studied to add a filler to the combined system of the two types of block copolymers. The blending of the filler has already been described in Patent Documents 1-3. However, the inventor examined the various fillers in more detail.
As a result, in the combined system of the two types of block copolymers, when a filler other than calcium carbonate is blended, the elongation at break tends to be small, whereas calcium carbonate is used as the filler. When blended, it was found that the damping performance of the high damping member can be specifically and greatly improved compared to the case where no filler is blended at all while preventing the elongation at break from being reduced. It came to be completed.

That is, the present invention provides a base polymer
(1) an S-IB diblock copolymer of a polymer block (S) containing an aromatic vinyl compound as a constituent monomer and a polymer block (IB) containing isobutylene as a constituent monomer; and
(2) S-IB-S triblock copolymer of the polymer block (S) and the polymer block (IB),
A high-damping composition using the two types of block copolymers together, and further comprising calcium carbonate.

  In the high attenuation composition of the present invention, the attenuation performance of the high attenuation member can be improved as the blending ratio of calcium carbonate is increased. However, as the blending ratio of calcium carbonate is increased, the elongation at cutting of the high attenuation member tends to be reduced. In addition, the damping performance of the high damping member varies greatly depending on the environmental temperature, that is, the temperature dependence of the damping performance tends to increase.

  As a result of further studies, the inventors have found that it is preferable to further add a tackifier to the high attenuation composition of the present invention. That is, by blending a tackifier, the effect of blending calcium carbonate can be assisted and the damping performance of the high damping member can be further improved. In addition, the temperature dependence of the damping performance can be reduced, and the elongation at the time of cutting of the high damping member can be increased.

  The tackifier has excellent dispersibility with respect to the two block copolymers as a base polymer, and is finely dispersed in the base polymer. It is preferable to use a hydrogenated petroleum resin having a softening point of less than 125 ° C., which is excellent in the effect of reducing the temperature dependency of the performance or the effect of increasing the elongation at the time of cutting of the high damping member.

  The high attenuation composition of the present invention can be used as a material for forming the various high attenuation members exemplified above. In particular, when a building damping damper for a building as a high damping member is formed, the high damping member is excellent in damping performance, so the number of the damping damper incorporated in one building can be reduced. it can. In addition, particularly when a damping damper is formed using a high damping composition containing a tackifier, the temperature dependence of the damping performance of the damping damper is small, for example, a large temperature difference. The damping damper can also be installed near the outer wall of the building.

  According to the present invention, an S-IB diblock copolymer and an S-IB-S triblock copolymer are used in combination as a base polymer, and the base polymer is sufficiently high enough to be used as a damping damper for buildings. It is possible to provide a novel high damping composition capable of forming a high damping member having a damping performance and a large elongation at break.

FIG. 4 is an exploded perspective view showing a test body as a model of the high attenuation member, which is produced in order to evaluate the attenuation performance of the high attenuation member made of the high attenuation composition of each sample prepared in each comparative test of the present invention. It is. FIGS. 4A and 4B are diagrams for explaining the outline of a testing machine for displacing the test body and obtaining the relationship between the displacement and the load. It is a graph which shows an example of the hysteresis loop which shows the relationship between the displacement amount and a load calculated | required by displacing a test body using the said testing machine.

<< High damping composition >>
The present invention provides a base polymer
(1) an S-IB diblock copolymer of a polymer block (S) containing an aromatic vinyl compound as a constituent monomer and a polymer block (IB) containing isobutylene as a constituent monomer; and
(2) S-IB-S triblock copolymer of the polymer block (S) and the polymer block (IB),
A high-damping composition using the two types of block copolymers together, and further comprising calcium carbonate.

<Base polymer>
As the base polymer, two types of block copolymers of S-IB diblock copolymer and S-IB-S triblock copolymer are used in combination as described above.
The blending ratio of both block copolymers is 10 parts by mass or more, particularly 20 parts by mass or more in terms of parts by mass of the S-IB-S triblock copolymer per 100 parts by mass of the total amount of both block copolymers. It is preferably 65 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less.

When the S-IB-S triblock copolymer is less than the above range, the combined use of the S-IB-S triblock copolymer has the effect of imparting good moldability to the high attenuation composition. In addition, the effect of increasing the elongation at the time of cutting of the high damping member may not be sufficiently obtained.
On the other hand, when the S-IB-S triblock copolymer is more than the above range, the amount of the S-IB diblock copolymer is relatively small, and the S-IB diblock copolymer is There is a possibility that the effect of imparting good damping performance to the high damping member cannot be obtained sufficiently.

  In the both block copolymers, examples of the aromatic vinyl compound used as the basis of the polymer block (S) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl- o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4 -Dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene , P-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro -O-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2, 4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, o- Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-butyl Examples thereof include one or more of lomomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, a styrene derivative substituted with a silyl group, indene, and vinylnaphthalene.

The polymer block (S) may contain a monomer other than the aromatic vinyl compound, or may not contain the other monomer.
Examples of such other monomers include one or more of isobutylene, aliphatic olefins, dienes, vinyl ethers, β-pinene, and the like.
When the polymer block (S) contains another monomer, the proportion of the aromatic vinyl compound in the total amount of all monomers constituting the polymer block (S) is 60% by mass or more, particularly It is preferable that it is 80 mass% or more.

Further, the polymer block (IB) may contain a monomer other than isobutylene or may not contain the other monomer.
Examples of such other monomers include one or more of the above aromatic vinyl compounds, aliphatic olefins, dienes, vinyl ethers, β-pinene, and the like.
When the polymer block (IB) contains other monomers, the proportion of isobutylene in the total amount of all monomers constituting the polymer block (IB) is 60% by mass or more, particularly 80% by mass or more. Is preferred.

Examples of the aliphatic olefins include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexane, and octene. , And one or more of norbornene and the like.
Examples of the dienes include one or more of butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, ethylidene norbornene, and the like.

  Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, methyl propenyl ether, and ethyl propenyl ether. Or 2 or more types are mentioned.

(S-IB diblock copolymer)
The S-IB diblock copolymer has a structure in which the polymer block (S) and the polymer block (IB) are connected one block at a time.
The copolymer ratio of both polymer blocks (S) and (IB) in the S-IB diblock copolymer is that of the polymer block (S) in the total amount of both polymer blocks (S) and (IB). Expressed as a ratio, it is preferably 2% by mass or more, particularly preferably 5% by mass or more, particularly preferably 15% by mass or more, and more preferably 80% by mass or less, particularly preferably 60% by mass or less, particularly preferably 40% by mass or less.

By setting the ratio of the polymer block (S) within the above range, the chain lengths of both polymer blocks (S) and (IB) are balanced, and the S-IB diblock copolymer can be used as a high attenuation member. The effect of imparting good damping performance can be exhibited well.
The molecular weight of the S-IB diblock copolymer is 3,000 or more, particularly 30,000 or more, particularly 50,000 or more, preferably 1,000,000 or less, especially 500, in terms of number average molecular weight. 000 or less, and particularly preferably 400,000 or less.

If the number average molecular weight is less than the above range, physical properties such as mechanical strength as a polymer may not be sufficiently exhibited. Moreover, when it exceeds the said range, there exists a possibility that the molding workability of a high attenuation | damping composition may fall.
The S-IB diblock copolymer can be produced by, for example, the synthesis methods described in Patent Documents 1 and 2.

(S-IB-S triblock copolymer)
The S-IB-S triblock copolymer has a structure in which one polymer block (IB) is sandwiched between two polymer blocks (S).
In the S-IB-S triblock copolymer, the copolymer ratio of both polymer blocks (S) (IB) is the polymer block (S) in the total amount of both polymer blocks (S) (IB). ), It is preferably 2% by mass or more, especially 5% by mass or more, particularly preferably 15% by mass or more, more preferably 80% by mass or less, particularly preferably 60% by mass or less, and particularly preferably 40% by mass or less.

  By adjusting the ratio of the polymer block (S) within the above range, the chain lengths of both polymer blocks (S) and (IB) are balanced, and high attenuation as an S-IB-S triblock copolymer is achieved. While giving favorable molding processability to a composition, all can show the effect which enlarges the elongation at the time of a high attenuation | damping member large. Also, good compatibility with the S-IB diblock copolymer can be imparted.

The molecular weight of the S-IB-S triblock copolymer is 3,000 or more, particularly 30,000 or more, particularly 50,000 or more, preferably 1,000,000 or less, among the number average molecular weight. It is preferably 500,000 or less, particularly 400,000 or less.
If the number average molecular weight is less than the above range, physical properties such as mechanical strength as a polymer may not be sufficiently exhibited. Moreover, when it exceeds the said range, there exists a possibility that the molding workability of a high attenuation | damping composition may fall.

The S-IB-S triblock copolymer can also be produced by, for example, the synthesis methods described in Patent Documents 1 and 2.
<Calcium carbonate>
Examples of calcium carbonate include synthetic calcium carbonate, heavy calcium carbonate having various particle sizes classified according to the production method, or surfaces thereof such as fatty acids, quaternary ammonium salts, rosin acid, and lignin. One type or two or more types such as surface-treated calcium carbonate surface-treated with seeds or two or more types may be mentioned.

The blending ratio of the calcium carbonate is preferably 10 parts by mass or more, particularly preferably 50 parts by mass or more, particularly 120 parts by mass or less, particularly 100 parts by mass of the total amount of the base polymer, that is, the two types of block copolymers. The amount is preferably 100 parts by mass or less.
If the blending ratio is less than the above range, the effect of improving the damping performance of the high damping member by blending calcium carbonate as a filler may not be sufficiently obtained.

On the other hand, when exceeding the said range, there exists a possibility that elongation at the time of a cutting | disconnection of a high attenuation | damping member may become small. In addition, the damping performance of the high damping member may vary greatly depending on the environmental temperature, that is, the temperature dependence of the damping performance may increase.
<Tackifier>
As described above, a tackifier can be further blended in the highly attenuating composition of the present invention as necessary. By mix | blending a tackifier, the effect by having mix | blended calcium carbonate can be assisted, and the attenuation | damping performance of a high attenuation | damping member can further be improved. In addition, the temperature dependence of the damping performance can be reduced, and the elongation at the time of cutting of the high damping member can be increased.

  Examples of the tackifier include one or more of petroleum resin, hydrogenated petroleum resin, rosin derivative and the like. In particular, a hydrogenated petroleum resin having a softening point of less than 125 ° C. is preferable. The hydrogenated petroleum resin having the above softening point is excellent in dispersibility with respect to the two block copolymers as the base polymer, and can be dispersed in the base polymer with a dispersed particle size as small as possible. Specifically, since it can be dispersed in a fine state with an average particle size of 20 μm or less, the effect of improving the damping performance of the high damping member, the effect of reducing the temperature dependence of the damping performance, or the high damping Excellent in increasing the elongation at the time of cutting of the member.

The softening point is represented by a value measured by a softening point measurement method (ring ball method) described in Japanese Industrial Standard JIS K2207-1996 “Petroleum Asphalt”.
The average particle diameter also using microscopic FTIR imaging apparatus, and depicts the relative intensities of the peaks of the polymer components (isobutylene, 1230 cm ^-1) to the internal standard peak (total _CH 2, 1450 cm ^-1), derived from the polymer component It will be expressed by the average value of the domain size of the weak part.

As the hydrogenated petroleum resins, P-90 (softening point: 90 ± 5 ° C.) and P-100 (softening point: 100 ± 5 ° C.) of the Alcon (registered trademark) series manufactured by Arakawa Chemical Industries, Ltd. ) And P-115 (softening point 115 ± 5 ° C.) and the like.
The blending ratio of the tackifier is preferably 5 parts by mass or more and preferably 150 parts by mass or less with respect to 100 parts by mass of the total amount of the base polymer, that is, the two kinds of block copolymers.

The blending ratio of the tackifier can be arbitrarily adjusted within the above range according to the damping performance required for the high damping member.
For example, in order to impart an attenuation performance having an equivalent attenuation constant Heq of 0.38 or more and less than 0.80 to the high attenuation member, which is obtained by an attenuation performance evaluation described later, the blending ratio of the tackifier is within the above range. However, it is preferably 10 parts by mass or more, particularly 20 parts by mass or more, and less than 80 parts by mass, especially 50 parts by mass or less, particularly 40 parts by mass or less.

In consideration of making the temperature dependence of the damping performance as small as possible, the blending ratio of the tackifier is 10 parts by mass or more and less than 80 parts by mass, particularly 30 parts by mass or less. Is preferred.
Furthermore, it is also possible to impart extremely high attenuation performance such that the equivalent attenuation constant Heq is 0.80 or more to a high attenuation member. In that case, the blending ratio of the tackifier is preferably 80 parts by mass or more, particularly preferably 100 parts by mass or more, and preferably 120 parts by mass or less, even within the above range.

The highly attenuating composition of the present invention basically adheres to the three components of the S-IB diblock copolymer, S-IB-S triblock copolymer, and calcium carbonate, or the three components. In order to simplify the structure, it is preferable that the composition is composed of four kinds of ingredients to which an imparting agent is added, and other ingredients such as paraffinic oil are not included.
<Evaluation of temperature dependence of damping performance>
In order to make the temperature dependence of the damping performance as small as possible while maintaining an appropriate damping performance, the high damping composition was measured in the following (I) (I) ( It is preferable that all the characteristics of II) are satisfied.

(I) The ratio G ′ ₀ / G ′ ₄₀ between the shear storage modulus G ′ ₀ (MPa) at ₀ ° C. and the shear storage modulus G ′ ₄₀ (MPa) at 40 ° C. is 10.0 or less.
(II) The loss tangent tan δ is 0.4 or more in the range of 0 to 40 ° C.
If the condition (I) is not satisfied, the temperature dependence of the damping performance tends to increase, and if the condition (II) is not satisfied, the damping performance may be lowered.

  The shear storage modulus G ′ (MPa) and the loss tangent tan δ were 40% shear deformation using an ARES (Advanced Rheometric Expansion System) -G2 rheometer manufactured by TA Instruments. , And the values obtained under the conditions of frequency 0.1 Hz, temperature 0 ° C., 20 ° C., and 40 ° C.

《High damping member》
As a high damping member that can be formed using the high damping composition of the present invention, for example, a damper for seismic isolation incorporated in the foundation of a building such as a building, or for vibration control (vibration suppression) incorporated in the structure of a building Dampers for cables, suspension members for cables such as suspension bridges and cable-stayed bridges, anti-vibration members for industrial machines, aircraft, automobiles, railway vehicles, etc., anti-vibration members for computers and peripheral devices, or household electrical equipment, Furthermore, treads for automobile tires and the like can be mentioned.

According to the present invention, the types and combinations of the S-IB diblock copolymer, the S-IB-S triblock copolymer, calcium carbonate, and the tackifier, and the blending ratio thereof are adjusted within the above range. Thus, it is possible to obtain a high damping member having excellent damping performance suitable for each application.
In particular, when a damping damper incorporated into a structure of a building is formed using the high damping composition of the present invention, the high damping member is excellent in damping performance, so that the damping incorporated into one building is used. The quantity of seismic dampers can be reduced. In addition, particularly when a damping damper is formed using a high damping composition containing a tackifier, the temperature dependence of the damping performance of the damping damper is small, for example, a large temperature difference. The damping damper can also be installed near the outer wall of the building.

Preparation and measurement of the highly attenuated composition in each of the following comparative tests were carried out in an environment at a temperature of 20 ° C. unless otherwise specified.
<< Comparison Test 1 >>
<Sample 1-1>
As base polymer, 80 parts by mass of S-IB diblock copolymer [trade name Shibstar 042D manufactured by Kaneka Co., Ltd.] and S-IB-S triblock copolymer [trade name Shibster 062T manufactured by Kaneka Co., Ltd. ] 20 parts by mass, with respect to 100 parts by mass of the total amount of both, surface-treated calcium carbonate [Shiraishi Hana (registered trademark) DD manufactured by Shiroishi Calcium Co., Ltd., synthetic calcium carbonate surface-treated with rosin acid , Primary particle diameter 50 nm] 100 parts by mass were blended and kneaded using a closed kneader to prepare a highly attenuated composition.

<Sample 1-2>
A highly attenuating composition was prepared in the same manner as in Sample 1-1 except that the amount of S-IB diblock copolymer was 60 parts by mass and the amount of S-IB-S triblock copolymer was 40 parts by mass. Prepared.
<Sample 1-3>
A highly attenuating composition was prepared in the same manner as Sample 1-1 except that the amount of S-IB diblock copolymer was 40 parts by mass and the amount of S-IB-S triblock copolymer was 60 parts by mass. Prepared.

<Sample 1-4>
A highly attenuating composition was prepared in the same manner as Sample 1-1 except that 40 parts by mass of silica (Nippil (registered trademark) ER manufactured by Tosoh Silica Co., Ltd.) was used instead of the surface-treated calcium carbonate.
<Sample 1-5>
A highly attenuated composition was prepared in the same manner as Sample 1-1 except that the surface-treated calcium carbonate was not blended.

<Sample 1-6>
Only the S-IB diblock copolymer alone was used as a highly attenuated composition.
<Sample 1-7>
Only the S-IB-S triblock copolymer alone was used as a highly attenuated composition.
The following evaluation was performed on the highly attenuated composition prepared in each sample, and the characteristics were evaluated.

<Attenuation performance evaluation>
(Preparation of test specimen)
The high attenuation composition prepared in each sample was extruded into a sheet and then punched to produce a disk 1 (thickness 5 mm × diameter 25 mm) as shown in FIG. Each of the circular plates 1 is bonded to the two steel plates 2 by stacking and pressing the rectangular flat plate-shaped steel plates 2 having a thickness of 6 mm × length 44 mm × width 44 mm through a cyanoacrylate adhesive, respectively, A specimen 3 for evaluating damping performance as a model of a high damping member was produced.

(Displacement test)
As shown in FIG. 2 (a), two test bodies 3 are prepared, and the two test bodies 3 are fixed to one central fixing jig 4 with bolts via one steel plate 2. One left and right fixing jig 5 was fixed to the other steel plate 2 of each test body 3 with bolts. The center fixing jig 4 is fixed to the upper fixing arm 6 of the testing machine (not shown) with a bolt via a joint 7, and the two left and right fixing jigs 5 are connected to the lower movable platen of the testing machine. 8 was fixed with bolts through a joint 9.

  Next, in this state, the movable platen 8 is displaced so as to be pushed up in the direction of the fixed arm 6 as indicated by the white arrow in the figure, and the disk 1 of the test body 3 is moved to the position shown in FIG. As shown in the figure, the test body 3 is strained and deformed in a direction orthogonal to the stacking direction, and from this state, the movable platen 8 is moved in a direction opposite to the direction of the fixed arm 6 as indicated by a white arrow in the figure. The operation of the test body 3 when the disk 1 of the test body 3 is repeatedly distorted or deformed, that is, vibrated, with the operation of displacing it down and returning to the state shown in FIG. A hysteresis loop H (see FIG. 3) indicating the relationship between the displacement (mm) of the disk 1 in the direction perpendicular to the stacking direction and the load (N) was obtained.

For the measurement, the above operation was performed for 3 cycles, and the third value was obtained. The maximum amount of displacement was set so that the amount of deviation of the two steel plates 2 sandwiching the disc 1 in the direction perpendicular to the stacking direction was 100% of the thickness of the disc 1.
Then, connecting the maximum displacement point and the minimum displacement point of the hysteresis loop H shown in FIG. 3 obtained by the measurement, determine the slope Keq (N / mm) of the straight line L ₁ shown by a thick solid line in the figure, the From the inclination Keq (N / mm), the thickness T (mm) of the disc 1, and the cross-sectional area A (mm ² ) of the disc 1, the formula (1):

The equivalent shear modulus Geq (N / mm ² ) was determined by
Also, the absorbed energy amount ΔW represented by the total surface area of the hysteresis loop H shown with diagonal lines in FIG. 3, the straight line L ₁ shown with a mesh line in the figure, and the horizontal axis, and a straight line L ₁ and the hysteresis loop H elastic strain energy W represented by the surface area of the region surrounded by the perpendicular L ₂ grated on the horizontal axis from the intersection of the formula (2):

Thus, an equivalent damping constant Heq was obtained.
It can be determined that the higher the equivalent attenuation constant Heq, the better the high attenuation member (test body 3) formed using the high attenuation composition of the corresponding sample. In Comparative Test 1, a sample having an equivalent attenuation constant Heq of 0.38 or more was evaluated as good.
<Tensile property evaluation>
A dumbbell-shaped No. 1 test piece defined in Japanese Industrial Standard JIS K6251 _{: 2010} “Vulcanized rubber and thermoplastic rubber—How to determine tensile properties” was prepared using the highly attenuated composition prepared in each sample. Using the test piece, a tensile test was carried out at a test speed of 300 mm / min in accordance with the test method defined in the same standard to obtain the elongation at break E _b (%).

As described above, the elongation _Eb at the time of cutting is preferably as large as possible. In Comparative Test 1, a sample having an elongation at break _Eb of 200% or more was evaluated as good.
The above results are shown in Tables 1 and 2.

From the results of Samples 1-6 and 1-7 in Table 2, the elongation at break _Eb is small for the S-IB diblock copolymer alone, and the elongation at break E is small for the S-IB-S triblock copolymer alone. _{Although b} was large, it was found that sufficient attenuation performance could not be obtained.
In addition, from the results of Sample 1-5, it was found that when both the block copolymers are used in combination, the elongation _Eb at the time of cutting can be increased while securing a certain level of damping performance, but the damping performance is still insufficient. It was.

Further, from the results of Sample 1-4, it was found that, when silica was added as a filler to the both block copolymers, the damping performance was improved, but the elongation at break _Eb was reduced.
On the other hand, from the results of Samples 1-1 to 1-3 in Table 1, by adding calcium carbonate as a filler to both block copolymers, the elongation at break _Eb is prevented from being reduced. It was found that the damping performance can be greatly improved.

Moreover, from the results of Samples 1-1 to 1-3, the mass part of the S-IB-S triblock copolymer is 10 parts by mass or more, particularly 20 parts by mass or more per 100 parts by mass of both block copolymers. It was found that it was preferably 65 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less.
<< Comparison Test 2 >>
<Sample 2-1>
As base polymer, 80 parts by mass of S-IB diblock copolymer [trade name Shibstar 042D manufactured by Kaneka Co., Ltd.] and S-IB-S triblock copolymer [trade name Shibster 062T manufactured by Kaneka Co., Ltd. ] 20 parts by mass, with respect to 100 parts by mass of the total amount of both, surface-treated calcium carbonate [Shiraishi Hana (registered trademark) DD manufactured by Shiroishi Calcium Co., Ltd., synthetic calcium carbonate surface-treated with rosin acid , Primary particle diameter 50 nm] and 100 parts by mass of hydrogenated petroleum resin as a tackifier [Arcon (registered trademark) P-100 manufactured by Arakawa Chemical Industries, softening point: 100 ± 5 ° C.] A highly attenuated composition was prepared by blending and kneading using a closed kneader.

<Sample 2-2>
A highly attenuated composition was prepared in the same manner as Sample 2-1, except that the amount of hydrogenated petroleum resin was 40 parts by mass.
<Sample 2-3>
A highly attenuating composition was prepared in the same manner as Sample 2-1, except that calcium carbonate was not blended and the amount of hydrogenated petroleum resin was 40 parts by mass.

About the high attenuation | damping composition prepared with the said each sample, the said attenuation | damping performance evaluation and tensile property evaluation were implemented, and the characteristic was evaluated. In Comparative Test 2, a sample having an equivalent attenuation constant Heq of 0.38 or more was evaluated as good. Moreover, the thing whose elongation _Eb at the time of a cutting | disconnection is 400% or more was evaluated as favorable.
The results are shown in Table 3 together with the results of the previous sample 1-1.

From the results of Sample 2-3 in Table 3, when only hydrogenated petroleum resin as a tackifier is blended without blending calcium carbonate, the damping performance is improved as compared to Sample 1-1. In addition, it was found that although the elongation _Eb at the time of cutting can be increased, the improvement effect is not yet sufficient.
On the other hand, from the results of Samples 2-1 and 2-2, by adding both calcium carbonate and hydrogenated petroleum resin, it is possible to further improve the damping performance and further increase the elongation at break _Eb. I understood.

From the results of Samples 2-1 and 2-2, the blending ratio of the hydrogenated petroleum resin as a tackifier is 10 parts by mass or more, particularly 20 parts by mass or more per 100 parts by mass of the total amount of both block copolymers. It was found that the amount is preferably less than 80 parts by mass, more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less.
<< Comparison Test 3 >>
<Sample 3-1>
As base polymer, 80 parts by mass of S-IB diblock copolymer [trade name Shibstar 042D manufactured by Kaneka Co., Ltd.] and S-IB-S triblock copolymer [trade name Shibster 062T manufactured by Kaneka Co., Ltd. ] 20 parts by mass, with respect to 100 parts by mass of the total amount of both, surface-treated calcium carbonate [Shiraishi Hana (registered trademark) DD manufactured by Shiroishi Calcium Co., Ltd., synthetic calcium carbonate surface-treated with rosin acid 50 parts by mass of primary particle diameter] and 10 parts by mass of hydrogenated petroleum resin [Arukawa Chemical Industries, Ltd. Alcon (registered trademark) P-90, softening point: 90 ± 5 ° C.] as a tackifier. A highly attenuated composition was prepared by blending and kneading using a closed kneader.

<Sample 3-2>
A highly attenuated composition was prepared in the same manner as Sample 3-1, except that the amount of hydrogenated petroleum resin was 20 parts by mass.
<Sample 3-3>
A highly attenuated composition was prepared in the same manner as Sample 3-1, except that the amount of the hydrogenated petroleum resin was 30 parts by mass.

<Sample 3-4>
A highly attenuated composition was prepared in the same manner as Sample 3-1, except that the amount of hydrogenated petroleum resin was 40 parts by mass.
<Sample 3-5>
A hydrogenated petroleum resin having a softening point of 115 ± 5 ° C. [Alcon (registered trademark) P-115 manufactured by Arakawa Chemical Industries, softening point: 115 ± 5 ° C.] was blended in the same amount. A highly attenuated composition was prepared in the same manner as Sample 3-2.

<Sample 3-6>
A hydrogenated petroleum resin having a softening point of 125 ± 5 ° C. [Alcon (registered trademark) P-125, softening point: 125 ± 5 ° C., manufactured by Arakawa Chemical Industries, Ltd.] is blended in the same amount. A highly attenuated composition was prepared in the same manner as Sample 3-2.
<Evaluation of temperature dependence of damping performance>
Using an ARES (Advanced Rheometric Expansion System) -G2 rheometer manufactured by TA Instruments, Inc., shear deformation rate 40%, frequency 0.1 Hz, temperature 0 ° C., 20 ° C., and Shear storage elastic modulus G ′ (MPa) and loss tangent tan δ were measured at 40 ° C. Further, a ratio G ′ ₀ / G ′ ₄₀ between the shear storage modulus G ′ ₀ (MPa) at ₀ ° C. and the shear storage modulus G ′ ₄₀ (MPa) at 40 ° C. was determined.

As described above, the ratio G ′ ₀ / G ′ ₄₀ is 10.0 or less and the loss tangent tan δ is 0.4 or more at any measurement temperature. It was evaluated.
The results are shown in Tables 4 and 5.

From the results of Samples 3-1 to 3-4 in Tables 4 and 5, hydrogenation as a tackifier is considered in consideration of improving the damping performance of the high damping member as much as possible and making its temperature dependence as small as possible. It has been found that the blending ratio of the petroleum resin is preferably 10 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the total amount of both block copolymers.
From the results of Samples 3-2, 3-5, and 3-6, it was found that it is preferable to use a hydrogenated petroleum resin having a softening point of less than 125 ° C.

<< Comparison Test 4 >>
<Sample 4-1>
As base polymer, 80 parts by mass of S-IB diblock copolymer [trade name Shibstar 042D manufactured by Kaneka Co., Ltd.] and S-IB-S triblock copolymer [trade name Shibster 062T manufactured by Kaneka Co., Ltd. ] 20 parts by mass, with respect to 100 parts by mass of the total amount of both, surface-treated calcium carbonate [Shiraishi Hana (registered trademark) DD manufactured by Shiroishi Calcium Co., Ltd., synthetic calcium carbonate surface-treated with rosin acid 100 parts by mass of primary particle diameter 50 nm] and 100 parts by mass of hydrogenated petroleum resin [Arcon (registered trademark) P-100 made by Arakawa Chemical Industries, softening point: 100 ± 5 ° C.] as a tackifier. A highly attenuated composition was prepared by blending and kneading using a closed kneader.

<Sample 4-2>
A highly attenuated composition was prepared in the same manner as Sample 4-1, except that the amount of hydrogenated petroleum resin was 120 parts by mass.
About the high attenuation | damping composition prepared with the said both samples, the said attenuation | damping performance evaluation and tensile property evaluation were implemented, and the characteristic was evaluated. In Comparative Test 4, a sample having an equivalent attenuation constant Heq of 0.80 or more was evaluated as good. Moreover, the thing whose elongation _Eb at the time of a cutting | disconnection is 400% or more was evaluated as favorable.

  The results are shown in Table 6 together with the results of the previous samples 2-1 and 2-2.

  From the results of samples 4-1 and 4-2 in Table 6, the blending ratio of the hydrogenated petroleum resin as a tackifier is 80 parts by mass or more, particularly 100 parts by mass or more per 100 parts by mass of the total amount of both block copolymers. And it turned out that a high attenuation | damping performance can be provided to a high attenuation | damping member by setting it as 120 mass parts or less.

DESCRIPTION OF SYMBOLS 1 Disc 2 Steel plate 3 Test body 4 Center fixing jig 5 Left and right fixing jig 6 Fixed arm 7 Joint 8 Movable platen 9 Joint

Claims (4)

As a base polymer,
(1) an S-IB diblock copolymer of a polymer block (S) containing an aromatic vinyl compound as a constituent monomer and a polymer block (IB) containing isobutylene as a constituent monomer; and
(2) S-IB-S triblock copolymer of the polymer block (S) and the polymer block (IB),
A highly attenuating composition comprising a combination of the above two block copolymers, further comprising calcium carbonate.   The highly attenuating composition according to claim 1, further comprising a tackifier.   The high-damping composition according to claim 1 or 2, wherein the tackifier is a hydrogenated petroleum resin having a softening point of less than 125 ° C.   The high-damping composition according to any one of claims 1 to 3, which is used as a material for forming a damper for vibration control of a building.

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