JP2001288329A - Viscoelastic composition and viscoelastic damper made thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a viscoelastic composition having excellent characteristics to improve the damping property at room temperature or thereabout and keep the temperature dependence of rigidity at a low level and provide a viscoelastic damper produced by using the composition. SOLUTION: The viscoelastic composition is composed mainly of an isobutylene block copolymer composed of a polymer block containing isobutylene as main monomer component and a polymer block which does not contain isobutylene as main monomer component. The ratio of G'10 deg.C/G'30 deg.C (G'10 deg.C and G'30 deg.C are storage moduli measured by the dynamic viscoelastic measurement of the composition in shearing mode at 10 deg.C and 30 deg.C, respectively) is <=5 and the loss tangent (tanδ) measured by the above measurement is >=0.4 at 10 deg.C to 30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a viscoelastic composition for absorbing shocking displacement and vibration of a skeletal structure forming material in the field of construction and a viscoelastic damper made of the composition.

[0002]

2. Description of the Related Art In the field of construction, a viscoelastic damper for absorbing a shaking caused by an earthquake, a typhoon or the like and giving a very high vibration damping structure to a building is being developed. For damping materials used for viscoelastic dampers with stable damping properties, high damping properties are required in order to exhibit the effect of absorbing shocking displacement and vibration of the skeletal structure forming material. In addition, it is required that the rigidity around the room temperature has small temperature dependence in consideration of environmental conditions.

[0003] A normal rubber material has a certain damping property at around room temperature. However, if the damping property is further increased, the rigidity is reduced and it is difficult to reduce the size of the viscoelastic damper. Problems arise. It is also difficult to obtain a high damping property that can be used for a viscoelastic damper.

On the other hand, damping rubber generally has a glass transition temperature (Tg) near room temperature. Examples of such a commercially available oil-loaded norbornene rubber, a styrene-isoprene-based block copolymer having a high vinyl content, and a hydrogenated product thereof (trade name: Hibler) are commercially available. Such a material has a high damping property near room temperature, but has a high Tg.
Since the change in the elastic modulus is large in the vicinity, the temperature dependence of the stiffness near room temperature is very large, and it is difficult to use the viscoelastic damper.

As such viscoelastic compositions for viscoelastic dampers in the field of construction, polyurethane compounds and polyurethane / asphalt compositions (JP-A-10-33)
No. 0451) is disclosed. However, all of the materials are required to be further improved with respect to the balance between the damping property near room temperature and the temperature dependence of rigidity.

On the other hand, the fact that a damping material can be obtained from a styrene-isobutylene-based block copolymer is disclosed in WO93 / 1.
No. 4135 and Japanese Patent Application Laid-Open No. 7-137194, each of which only discloses that it can be used as a general vibration damping material, such as a viscoelastic damper in the field of construction. Nothing is described for use in applications where special properties are required.
In addition, the materials disclosed in the examples of both publications have too low attenuating property at around room temperature, so that it is difficult to use them as a damping material for a viscoelastic damper.

[0007]

That is, an object of the present invention is to provide a viscoelastic composition having excellent characteristics of improving the damping property near room temperature and keeping the temperature dependence of rigidity low, and a viscoelastic composition having the same. It is to provide a viscoelastic damper used.

[0008]

That is, the present invention comprises an isobutylene-based block copolymer comprising a polymer block containing isobutylene as a monomer main component and a polymer block containing no isobutylene as a monomer main component. A ratio of the storage elastic modulus (G ′) obtained by dynamic viscoelasticity measurement in a shear mode of the composition at 10 ° C. to 30 ° C. (G ′ ₁₀ ° C./G ′ ₃₀₎ ° C) is 5 or less, and the loss tangent (tan δ) obtained by the measurement is 1
It is a viscoelastic composition that is 0.4 or more at 0 ° C to 30 ° C.

A second aspect of the present invention is a composition comprising, as a main component, an isobutylene-based block copolymer composed of a polymer block containing isobutylene as a monomer main component and a polymer block containing no isobutylene as a monomer main component. Wherein the ratio of the storage elastic modulus (G ′) obtained by dynamic viscoelasticity measurement in shear mode of the composition at 10 ° C. and 30 ° C. (G ′ ₁₀ ° C./G ′ ₃₀ ° C.) 4, and the loss tangent (tan δ) obtained by the measurement is 10 ° C to 30 ° C.
It is a viscoelastic composition which is 0.5 or more at a temperature of ° C.

The above viscoelastic composition comprises a composition obtained by further mixing a tackifier resin with an isobutylene-based block copolymer, and has a peak of loss tangent (tan δ) obtained by dynamic viscoelasticity measurement in a shear mode. Temperature is -15 to 15
It is preferably in the range of ° C.

Further, the viscoelastic composition can be obtained by further mixing a plasticizer with the isobutylene-based block copolymer and the tackifier resin.

On the other hand, the viscoelastic damper of the present invention is a viscoelastic damper obtained by alternately laminating a layer using the above viscoelastic composition and a steel sheet layer, and is more effective than a layer using the composition. And a viscoelastic damper characterized by having more steel layers.

As the above-mentioned lamination form, concentric laminations can also be made. Further, it is preferable that the bonding surface of the layer using the viscoelastic composition and the layer of the steel plate or the steel pipe is bonded via an adhesive.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The viscoelastic composition of the present invention is a composition mainly composed of an isobutylene-based block copolymer composed of a polymer block mainly composed of isobutylene and a polymer block not mainly composed of isobutylene. The ratio of the storage elastic modulus (G ′) at 10 ° C. to the value at 30 ° C. (G ′ ₁₀ ° C./G ′ ₃₀ ° C.) of the storage modulus (G ′) obtained by the dynamic viscoelasticity measurement in the shear mode of the composition is as follows. 5 or less, and the loss tangent (tan δ) obtained by the measurement is 10 ° C to 3 ° C.
A viscoelastic composition that is 0.4 or more at 0 ° C., and (G ′ ₁₀ ° C./G ′ ₃₀ ° C.) is 4 or less and (ta)
nδ) is preferably 0.5 or more at 10 ° C to 30 ° C.

The dynamic viscoelasticity measurement in the above-mentioned shear mode is as follows.
What is necessary is just to carry out according to JIS K-6394 (dynamic property test method of vulcanized rubber and thermoplastic rubber). At this time, the frequency is set to 0.1 to 5 Hz, but in this specification, the value measured at 0.5 Hz is shown. In addition, this frequency corresponds to the frequency of vibration caused by an earthquake or a typhoon received by the building. The storage elastic modulus (G ′) and the loss tangent (tanδ) obtained by performing the dynamic viscoelasticity measurement in the shear mode in this way are equivalent stiffness (Ke) used in the construction field.
q) and the equivalent damping constant (heq), G ′ = Ke
It is known that there is a relationship of q, tan δ = 2 · heq. G ′ represents the rigidity of the viscoelastic composition (damping material), and the larger the value, the higher the rigidity. On the other hand, tan δ
Represents the damping property of the damping material, and the larger the value, the higher the damping property.

As described above, in order to be used as a vibration damper, high damping near room temperature and low temperature dependence of rigidity near room temperature are required. In the present invention, the value of G ′ at ₁₀ ° C. (G ′ ₁₀ ° C.) and the value of G ′ at ₃₀ ° C. (G ′ ₃₀ ° C.)
By setting the ratio (G ′ ₁₀ ° C./G ′ ₃₀ ° C.) to 5 or less, a vibration damper having small temperature dependence of rigidity near room temperature is realized, and G ′ ₁₀ ° C./G ′ ₃₀ ° C. Is preferably 4 or less, and most preferably 2 or less. Further, in the present invention, by setting the value of tan δ at 10 ° C. to 30 ° C. of the composition to be used to 0.4 or more, a high damping damper near room temperature is realized.
The value of tan δ at 〜30 ° C. is preferably 0.5 or more, and most preferably 0.7 or more.

The isobutylene-based block copolymer which can be used in the present invention is one having a polymer block containing isobutylene as a monomer main component and a polymer block containing no isobutylene as a monomer main component. There are no particular restrictions,
For example, any of block copolymers, diblock copolymers, triblock copolymers, and multiblock copolymers having a linear, branched, or star-like structure can be selected, and the viscoelastic properties can be selected. Alternatively, a material that meets the requirements of physical properties such as maximum strain rate and shear strength and workability may be selected.

The monomer component not containing isobutylene as a main component of the present invention means a monomer component having an isobutylene content of 30% by weight or less. The content of isobutylene in the monomer component containing no isobutylene as a main component is preferably 10% by weight or less, more preferably 3% by weight or less.

The monomer other than isobutylene in the monomer component not containing isobutylene as a main component of the present invention is not particularly limited as long as it is a monomer component capable of cationic polymerization. Monomers such as olefins, dienes, vinyl ethers, silanes, vinyl carbazole, β-pinene, acenaphthylene and the like can be exemplified. These may be used alone or in combination of two or more.

Examples of the aromatic vinyl monomer include styrene, o-, m- or 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-, m- or 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, o-, m- or pt-butylstyrene, o-, m- or p-methoxystyrene, o-,
m- or p-chloromethylstyrene, o-, m- or p
-Bromomethylstyrene, a styrene derivative substituted with a silyl group, indene, vinylnaphthalene and the like. These may be used alone or in combination of two or more.

Examples of the aliphatic olefin monomer include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, and 4-methyl-1-pentene. , Vinylcyclohexane, octene, norbornene and the like.
These may be used alone or in combination of two or more.

Examples of the diene monomer include butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, and ethylidene norbornene. These may be used alone or in combination of two or more.

Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, (n-, iso) propyl vinyl ether, (n-, sec-, te
rt-, iso) butyl vinyl ether, methylpropenyl ether, ethylpropenyl ether and the like. These may be used alone or in combination of two or more.

Examples of the silane compound include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-
Examples thereof include divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.
These may be used alone or in combination of two or more.

The monomer component of the present invention not containing isobutylene as a main component is preferably a monomer component containing an aromatic vinyl monomer as a main component in view of the balance between physical properties and polymerization characteristics. The aromatic vinyl-based monomer of the present invention indicates a monomer component having a content of aromatic vinyl-based monomer of 60% by weight or more, preferably 80% by weight or more. As the aromatic vinyl monomer, styrene, α-methylstyrene, p
It is preferable to use at least one monomer selected from the group consisting of -methylstyrene and indene, and it is particularly preferable to use styrene, α-methylstyrene, or a mixture thereof in terms of cost.

The monomer component containing isobutylene as the main component of the present invention may or may not contain a monomer other than isobutylene. Usually, isobutylene contains 60% by weight or more, preferably 80% by weight or more. It is a monomer component contained by weight or more. The monomer other than isobutylene is not particularly limited as long as it is a monomer capable of cationic polymerization, and examples thereof include the above-mentioned monomers.

The ratio of the polymer block containing isobutylene as the main component and the polymer block not containing isobutylene as the main component is not particularly limited. However, isobutylene is simply used in consideration of the balance between physical properties and processability. 98 to 40% by weight of a polymer block containing a monomer as a main component, and 2 to 60% of a polymer block containing no isobutylene as a monomer.
%, Preferably 95 to 60% by weight of a polymer block containing isobutylene as a monomer main component, and 5 to 40% by weight of a polymer block containing no isobutylene as a monomer main component. preferable.

The preferred structure of the isobutylene-based block copolymer of the present invention is a polymer block containing an aromatic vinyl-based monomer as a main component in view of the physical properties and processability of the resulting composition. -A polymer block containing isobutylene as a monomer main component-a triblock copolymer formed from a polymer block containing an aromatic vinyl monomer as a monomer main component, and isobutylene as a monomer main component. Polymer block-a polymer block containing an aromatic vinyl monomer as a main component-a triblock copolymer formed from a polymer block containing isobutylene as a main component, an aromatic vinyl compound A polymer block containing a monomer as a main component; a diblock copolymer formed from a polymer block containing isobutylene as a main component; and a single monomer of an aromatic vinyl monomer. Polymer block composed mainly - is at least one diblock copolymer formed isobutylene from the polymer block whose monomer major component is selected from the group consisting of star-shaped polymer to be the arm.

Although the number average molecular weight of the isobutylene block copolymer is not particularly limited, it is preferably 3,000 to 1,000,000 in view of physical properties and workability.
It is particularly preferred that it is 5,000 to 500,000. When the number average molecular weight of the isobutylene-based block copolymer is lower than the above range, the physical properties of the composition are not sufficiently exhibited. On the other hand, when it exceeds the above range, it is disadvantageous in terms of processability.

The composition used in the present invention is an isobutylene-based block copolymer having various functional groups in the molecular chain or at the terminal of the molecular chain, for the purpose of improving the adhesiveness to a steel sheet or a steel pipe. Can be used. Examples of the functional group include an ether group such as an epoxy group, a hydroxyl group, an amino group, an alkylamino group and an alkoxyl group, an ester group such as a carboxyl group, an alkoxycarbonyl group and an acyloxyl group, a carbamoyl group, an alkylcarbamoyl group, and an acylamino group. Amide group, acid anhydride group such as maleic anhydride, silyl group, allyl group, vinyl group and the like. The isobutylene-based block copolymer may have only one of these functional groups, or may have two or more of these functional groups. Preferred functional groups from the viewpoint of physical balance include an epoxy group, an amino group, an ether group, an ester group, an amide group, a silyl group, an allyl group, and a vinyl group.

The method for producing the isobutylene-based block copolymer is not particularly limited, and a known polymerization method can be used. For example, using a suitable polymerization initiator system,
Manufactured by polymerizing isobutylene-based monomers and non-isobutylene-based monomers, such as aromatic vinyl monomers, in an inert solvent in the order of their respective block bonds in an inert solvent. can do. Examples of the polymerization initiator system in that case include a mixture system of a Lewis acid and an organic compound that generates a cationic polymerization active species by the Lewis acid. Examples of the Lewis acid include titanium tetrachloride, tin tetrachloride, boron trichloride, and aluminum chloride. Examples of the organic compound include an organic compound having a functional group such as an alkoxy group, an acyloxy group, or a halogen group, for example, 1-chloro-1. -Methylethylbenzene [C
_{6 H 5 C (CH 3)} 2 Cl], bis (1-chloro-1-methylethyl) benzene _{[C 6 H 4 (C (} CH 3) 2 C
l) ₂ ] and tris (1-chloro-1-methylethyl) benzene [(ClC (CH ₃ ) ₂ ) ₃ C ₆ H ₃ ]. Further, together with the Lewis acid and the organic compound, if necessary, for example, a pyridine compound, an amine compound, an amide compound, a sulfoxide compound, an ester compound, or a metal compound having an oxygen atom bonded to a metal atom may be used as an electron donor component. You may use as. In addition, as an inert solvent for polymerization, hexane, cyclohexane, methylcyclohexane, toluene, methyl chloride, methylene chloride, n-butyl chloride and the like can be used.

For example, an ABA triblock copolymer is obtained by polymerizing a vinyl aromatic monomer using a Lewis acid and an organic compound having one functional group capable of generating a cationically polymerizable species as a polymerization initiator system. After forming block A, isobutylene is added to the reaction system and polymerized to form block B, and a vinyl aromatic monomer is again added to the reaction system and polymerized to form block A. can do. Alternatively, an organic compound having two functional groups that generate a Lewis acid and a cationically polymerizable active species is used as a polymerization initiator system, and isobutylene is first polymerized to form a block B located at the center. It can be produced by adding a vinyl aromatic monomer to the reaction system and carrying out polymerization to form blocks A at both ends of the block B. AB diblock copolymer and BAB triblock copolymer can be produced in the same manner. Furthermore, a method of using an organic compound having three or more functional groups that generate a Lewis acid and a cationic polymerization active species as a polymerization initiator system, or producing an AB diblock copolymer, A star polymer can be produced by a method of coupling (bonding) the diblock copolymer using a compound as a coupling agent (binder).

The viscoelastic composition that can be used in the viscoelastic damper of the present invention is an isobutylene-based block composed of a polymer block mainly composed of isobutylene and a polymer block not mainly composed of isobutylene. A storage modulus (G ') of a composition comprising a polymer as a main component, which is obtained by dynamic viscoelasticity measurement in a shear mode of the composition.
The ratio of the value at 0 ° C. to the value at 30 ° C. (G ′ ₁₀ ° C. /
G ′ ₃₀ ° C.) is 5 or less, and the loss tangent (tan δ) obtained by the above measurement is 0.4 or more at 10 ° C. to 30 ° C., other than the isobutylene-based block copolymer. Any component may be blended in the composition.

In order to satisfy the conditions of G ′ and tan δ described above, the t of the polymer block containing isobutylene as a monomer main component in the isobutylene-based block copolymer is measured.
An δ peak temperature (glass transition temperature) is −15 ° C.
Preferably it is in the range of 15 ° C.

Components that control the glass transition temperature of the polymer block containing isobutylene as a monomer main component in the isobutylene-based block copolymer include tackifying resins and plasticizers. The tackifier resin has the effect of shifting the glass transition temperature of the polymer block containing isobutylene as a monomer main component in the isobutylene-based block copolymer to a higher temperature side, increasing tan δ at the glass transition temperature, and has a plasticizer effect. Has the effect of moving the glass transition temperature of a polymer block containing isobutylene as a monomer main component in an isobutylene-based block copolymer to a lower temperature side, and increasing tan δ at the glass transition temperature. The original glass transition temperature of a polymer block containing isobutylene as a monomer main component of an isobutylene-based block copolymer is -40 to 40.
Since the temperature is as low as about −35 ° C., it is preferable to add a tackifier resin to move the glass transition temperature to a range of −15 ° C. to 15 ° C. Further, when it is desired to add a tackifier resin in order to increase tan δ, a plasticizer may be added to adjust the glass transition temperature to be in a range of −15 ° C. to 15 ° C. Such an effect differs depending on the type of the tackifier resin and the plasticizer, and appropriately selects a preferable type, and adjusts the blending amount so that the glass transition temperature of the composition is −15 ° C. or higher.
What is necessary is just to adjust to 15 degreeC.

The tackifying resin that can be blended in the composition used in the present invention includes a number average molecular weight of 300 to 3000,
A low molecular weight resin having a softening point of 60 to 150 ° C. based on the ring and ball method defined in JIS K-2207, comprising rosin and rosin derivatives, polyterpene resins, aromatic modified terpene resins and their hydrides, terpene phenols Resin, coumarone-indene resin, aliphatic petroleum resin,
Alicyclic petroleum resin and hydride thereof, aromatic petroleum resin and hydride thereof, aliphatic aromatic copolymer petroleum resin and hydride thereof, dicyclopentadiene petroleum resin and hydride thereof, styrene or substituted styrene Low molecular weight polymers.

In order to achieve the object of the present invention, it is desirable to incorporate a tackifier resin compatible with a polymer block containing isobutylene as a monomer main component in the isobutylene-based block copolymer. Alicyclic petroleum resins and hydrides thereof, aliphatic petroleum resins, hydrides of aromatic petroleum resins, and polyterpene resins are preferably used. In the same type of tackifying resin, the higher the softening point, the higher the effect of moving the glass transition temperature of the polymer block containing isobutylene as a monomer main component of the isobutylene-based block copolymer to a higher temperature side. When it is desired to reduce the amount of the tackifier resin, a resin having a high softening point may be selected, and when it is desired to increase the resin, a resin having a low softening point may be selected. For example,
When using Alcon (manufactured by Arakawa Chemical Industries, Ltd.), which is a hydride of a C9-based alicyclic petroleum resin, the softening point is 10 per 100 parts by weight of the isobutylene-based block copolymer.
30 to 70 parts by weight of P-100 at 0 ° C. and 10 to 55 parts by weight of M-135 having a softening point of 135 ° C. When isobutylene of the isobutylene block copolymer is used as a monomer main component, The glass transition temperature of the resulting polymer block can be adjusted in the range of -15C to 15C.

Examples of the plasticizer which can be added to the composition used in the present invention include petroleum-based process oils such as paraffin-based process oils, naphthenic-based process oils and aromatic process oils, and natural oils such as castor oil and tall oil. Dialkyl dibasic acid such as dibutyl phthalate, dioctyl phthalate or dibutyl adipate;
Examples thereof include low molecular weight liquid polymers such as liquid polybutene and liquid polyisoprene, and any of these can be used.

In order to achieve the object of the present invention, it is desirable to add a plasticizer compatible with a polymer block containing isobutylene as a monomer main component in the isobutylene-based block copolymer. And liquid polybutene are preferably used. The effect of lowering the glass transition temperature of the polymer block containing isobutylene as a monomer main component of the isobutylene-based block copolymer described above,
Depends on the type of plasticizer. For example, Diana process oil PW-3 which is a paraffin-based process oil
When 80 (manufactured by Idemitsu Kosan Co., Ltd.) is used, PW-380 is mixed up to 40 parts by weight with a composition comprising 100 parts by weight of an isobutylene-based block copolymer and 50 parts by weight of Alcon P-100 as a tackifier resin. However, the glass transition temperature of the polymer block containing isobutylene as a monomer main component of the isobutylene-based block copolymer is -15 ° C to 1 ° C.
It can be adjusted to 5 ° C. A composition comprising 100 parts by weight of an isobutylene-based block copolymer and 50 parts by weight of Alcon M-135 as a tackifier resin was added to PW-3.
Even if 80 is mixed up to 60 parts by weight, the glass transition temperature of a polymer block containing isobutylene as a monomer main component of an isobutylene-based block copolymer can be adjusted to a range of -15 ° C to 15 ° C. M-1 in which the system block copolymer is 100 parts by weight and a tackifier resin
When 35 is a composition consisting of 60 parts by weight, the glass transition temperature of the polymer block containing isobutylene as a monomer main component is 35 ° C., but by mixing 20 parts by weight to 70 parts by weight of PW-380. The glass transition temperature of a polymer block containing isobutylene as a monomer main component of an isobutylene-based block copolymer can be adjusted to a range of -15 ° C to 15 ° C.

The composition ratio of the composition used in the present invention is determined by comparing the value at 10 ° C. of the storage elastic modulus (G ′) obtained by measuring the dynamic viscoelasticity of the composition in a shear mode with 30%.
The value ratio (G ′ ₁₀ ° C./G ′ ₃₀ ° C.) at 5 ° C. is 5 or less, and the loss tangent (tan) obtained by the aforementioned measurement is
If δ) is 0.4 or more at 10 ° C. to 30 ° C., any mixing ratio may be used. In order to satisfy such a condition, as described above, the glass transition temperature of the polymer block containing isobutylene as a monomer main component in the isobutylene-based block copolymer is in the range of −15 ° C. to 15 ° C. It is preferable to set the mixing ratio in such a manner. For example, the tackifier resin is contained in an amount of 30 to 200 parts by weight, preferably 30 to 1 part by weight, based on 100 parts by weight of the isobutylene-based block copolymer.
00 parts by weight, 0-100 parts by weight of a plasticizer, preferably 0
When it is blended in the range of 70 to 70 parts by weight, the desired composition can be obtained.

In the present invention, other polymers can be used in combination within a range that does not substantially hinder the object of the present invention, and further, a filler, a stabilizer, a pigment, a lubricant, a flame retardant and the like are blended. be able to.

Examples of other polymers include natural rubber; synthetic rubber such as isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber and butyl rubber; aromatic vinyl-conjugated diene block copolymer and its water Thermoplastic elastomers such as additives, thermoplastic polyurethanes, polyester-polyether copolymers, aromatic polyester-aliphatic polyester copolymers, polyamide-polyether copolymers, polyolefin / ethylene-propylene rubber compositions; polyethylene, Polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-vinyl acetate copolymer,
Examples include thermoplastic resins such as polyamide, polyester, polycarbonate, polyphenylene ether, and polyphenylene sulfide. The content of these polymers is preferably 30 parts by weight or less based on 100 parts by weight of the isobutylene-based block copolymer used in the present invention.

Examples of the filler include powder fillers such as mica, carbon black, silica, calcium carbonate, talc, graphite, stainless steel, and aluminum; and fibrous fillers such as glass fibers and metal fibers. . Among them, mica is preferable because it has an effect of improving the damping property. In addition, spot welding becomes possible by incorporating various metal powders such as stainless steel powder and aluminum powder, metal fibers, or conductive particles such as carbon black and graphite.

Examples of other compounding agents include stabilizers such as triphenyl phosphite, hindered phenol, and dibutyltin maleate; lubricants such as polyethylene wax, polypropylene wax and montanic acid wax;
Flame retardants such as triphenyl phosphate, tricresyl phosphate, decabromobiphenyl, decabromobiphenyl ether, and antimony trioxide; and pigments such as titanium oxide, zinc sulfide, and zinc oxide.

The method for producing the composition used in the present invention is as follows.
There is no particular limitation, and a method of mechanically mixing using a melting pot equipped with a roll, a Banbury mixer, a kneader, a stirrer, or a single-screw or twin-screw extruder can be used. At this time, heating can be performed if necessary. Also, put the compounding agent in a suitable solvent,
After stirring to obtain a uniform solution of the composition, the solvent may be distilled off.

The material of the steel sheet or the steel pipe used in the viscoelastic damper of the present invention is not particularly limited, and examples thereof include general structural steel sheets, cold rolled steel sheets, carbon steel sheets, stainless steel sheets, and low alloy steel sheets.

The viscoelastic damper of the present invention is a viscoelastic damper obtained by alternately laminating a layer using a viscoelastic composition satisfying the requirements of the present invention as a vibration damping material and a steel plate layer. It is preferable that the number of layers of the steel sheet is more than that of the layer using as a vibration damping material, and the layers using the viscoelastic composition as the vibration damping material and the layers of the steel sheet are alternately and concentrically. The viscoelastic damper is preferably laminated so that the number of steel plates is greater. The viscoelastic damper will be described with reference to the accompanying drawings.

FIG. 1 shows a structure in which one layer of a vibration damping material using a viscoelastic composition and two layers of steel plates are alternately laminated, and the one shown in FIG. 2 uses a viscoelastic composition. This is a structure in which two layers of damping material and three layers of steel plate are alternately laminated. Also,
FIG. 3 shows a vibration damping material 1 using a viscoelastic composition.
This is an example of a structure in which layers and two steel pipe layers are alternately stacked concentrically. These structures are properly used depending on the workability of the vibration damping material, the site where the viscoelastic damper is used, and the purpose of use.

In order to manufacture a viscoelastic damper having the above-mentioned structure, for example, a method of forming a damping material using a viscoelastic composition into a sheet shape and bonding it to a steel plate, or a method of heating and melting the damping material is used. And a method of pouring between steel plates or between steel pipes. In the case of using the former method, it is necessary to form the vibration damping material into a sheet shape, but a known method used for forming a sheet of a thermoplastic resin can be used. For example, extrusion molding, calendar molding, press molding and the like can be mentioned. In any of the methods, the adhesiveness of the damping material itself may be used to bond the damping material to the steel plate or the steel pipe, or if the adhesive strength is insufficient, an adhesive may be used. You may. Regardless of whether an adhesive is used or not, in order to improve the adhesive strength, the surface of steel plates and steel pipes and the surface of damping materials can be treated with a primer, or chemically treated with chemicals such as acids and bases. Or a method of mechanical treatment such as buffing.

As the above-mentioned adhesive, for example, an epoxy-based, rubber-based, acrylic-based, urethane-based adhesive, etc., which is generally commercially available as a metal adhesive can be used. Epoxy adhesives are composed of epoxy resins such as glycidyl ether type, glycidyl ester type, glycidylamine type, alicyclic type, and curing agents such as polyamideamine, polythiol, and acid anhydride, catalysts, fillers and the like. Is exemplified. Epoxy resin is bisphenol type,
A phenol novolak type or an ortho-cresol novolak type modified or rubber-modified, or a rubber-modified amine curing agent is used as necessary. Rubber-based adhesives include chlorinated natural rubber, chloroprene, polybutadiene and other rubbers and tetramethylthiuram disulfide (T
T) or a low-temperature curing agent such as tetramethylthiuram monosulfide (TS), a phenol resin, a resole resin, or, if necessary, a solution type to which isocyanate or the like is added. It is preferable to add carbon black, titanium, calcium carbonate, or the like as a filler. As the acrylic adhesive, for example, those containing an acrylic monomer or an acrylic oligomer, a catalyst, and an elastomer can be used, and may include a curing catalyst, an accelerator, a stabilizer, and the like, as necessary. Examples of the acrylic monomer include methyl methacrylate, methacrylic acid, ethylene glycol dimethacrylate, and butyl methacrylate. The urethane-based adhesive is based on a prepolymer containing polyisocyanate and polyether or polyester polyol as main raw materials, and blends fillers such as calcium carbonate and carbon black with additives such as tertiary amine and tin catalyst. It may be used.
As the polyol, epoxy-modified or rubber-modified products, those having a hydroxyl group added to the terminal or inside of the rubber, and phenol resins are also suitably used for improving the adhesiveness. As an example of a commercially available adhesive for such a metal,
Chemrock, fuser, versa lock, tie light,
Tycell (all manufactured by Lord Far East, Inc.), Bond Sylex, Bond Eflex, Bond MOS10 (all manufactured by Konishi Co., Ltd.), Aron Alpha (manufactured by Toagosei Co., Ltd.), Technolink R Series (Taoka Chemical Industry Co., Ltd.) and Sumicanol (Sumitomo Chemical Industry Co., Ltd.). Among them, Chemlock is preferable in terms of adhesive strength.

The method of installing the viscoelastic damper of the present invention is not particularly limited, and examples thereof include a method of installing it as a brace, a method of installing it as a wall, and a method of installing it on a stud.

[0052]

The present invention will be described more specifically with reference to the following examples. It should be noted that the present invention is not limited in any way by these embodiments, and can be appropriately changed and implemented without changing the gist thereof. Hereinafter, measurement methods and the like will be described prior to the examples. (Dynamic Viscoelastic Property)
5mm x 6mm x 1.7mm according to K-6394
Using two test pieces, frequency 0.5 Hz, shear strain 0.
Measured at 05%. The device used was a dynamic viscoelasticity measuring device DVA-200 (manufactured by IT Measurement Control Co., Ltd.). Regarding the obtained storage elastic modulus (G ′), the value of G ′ at ₁₀ ° C. (G ′ ₁₀ ° C.) and the value of G ′ at 30 ° C. (G ′)
₃₀ ° C.) (G ′ ₁₀ ° C./G ′ ₃₀ ° C.). Also,
About the obtained loss tangent (tan δ), 10 ° C., 20
° C., the value of 30 ° C. (respectively, tanδ ₁₀ ℃, tanδ ₂₀
° C, tan δ ₃₀ ° C) and the temperature at which tan δ has a maximum value was taken as the glass transition temperature (Tg).

(Evaluation of Vibration Suppression Property) The temperature dependence of rigidity near room temperature and the damping property near room temperature were evaluated in three steps based on the following criteria. [Evaluation criteria] ：: Excellent. Δ: Range usable as a viscoelastic damper for construction. X: Cannot be used as a viscoelastic damper for construction.

(Meaning of symbols and abbreviations) [P100]: Hydride of C9-based alicyclic petroleum resin Alcon P-100, softening point 100 ° C, molecular weight 610 (manufactured by Arakawa Chemical Industries, Ltd.) [P140]: C9 Hydride of alicyclic petroleum resin Alcon P-140, softening point 140 ° C, molecular weight 860 (manufactured by Arakawa Chemical Industry Co., Ltd.) [M135]: Hydride of a C9-type alicyclic petroleum resin Alcon M-135, Softening point 135 ° C, molecular weight 860 (manufactured by Arakawa Chemical Industry Co., Ltd.) [M90]: Hydride of C9-based alicyclic petroleum resin Archon M-90, softening point 90 ° C, molecular weight 580 (manufactured by Arakawa Chemical Industry Co., Ltd.) [R100]: C5 aliphatic petroleum resin Quinton R
100, softening point 96 ° C, molecular weight 1100 (manufactured by Zeon Corporation) [300H]: polybutene oil Idemitsu Polybutene 30
0H, viscosity 32,000 cSt (40 ° C.), density 0.9
00 g / cm ³ , pour point 0 ° C. (manufactured by Idemitsu Petrochemical Co., Ltd.) [PW380]: paraffinic oil Diana Process Oil PW-380, viscosity 380 cSt (40 ° C.),
Density 0.8769 g / cm3, pour point -15 ° C (manufactured by Idemitsu Kosan Co., Ltd.) [SC-60]: filler flake graphite SC-
60 (manufactured by Chuetsu Graphite Co., Ltd.) VS1: high vinyl-styrene-isoprene block copolymer High blur VS-1, styrene content 20% (manufactured by Kuraray Co., Ltd.) [HVS3]: high vinyl-styrene-isoprene block copolymer Hybler HVS-3, styrene content 20% (Kuraray Co., Ltd.) [SEBS]: Styrene-butadiene block copolymer hydride Clayton G-1650, styrene content 29% (Shell Japan Co., Ltd.) ( Reference Example 1 Production of isobutylene-based block copolymer)
In a 2 L reaction vessel equipped with a stirrer, 691 mL of 1-chlorobutane (dried by molecular sieve), 480 mL of hexane (dried by molecular sieve),
0.596 g of p-dicumyl chloride was added. After cooling the reaction vessel to -70 ° C, dimethylacetamide 1.
12 g and 232 mL of isobutylene were added. Further, 8.7 mL of titanium tetrachloride was added to initiate polymerization, and the temperature was reduced to -70 ° C.
The solution was reacted for 1.5 hours with stirring. Next, 77.9 g of styrene was added to the reaction solution, and the reaction was further continued for 60 minutes. Then, the reaction solution was poured into a large amount of water to stop the reaction.

When the state of separation between the organic layer and the aqueous layer was visually confirmed, the separation was good and the separation could be easily performed with a separating funnel. After performing water washing twice, after confirming that the aqueous layer is neutral, the organic layer is poured into a large amount of methanol to precipitate a polymer, and the obtained polymer is kept at 60 ° C. for 24 hours. By vacuum drying, an isobutylene-based block copolymer (SIBS-1) was obtained.

The isobutylene block copolymer (SI
GPC analysis of BS-1) revealed a weight average molecular weight of 83,700 and a molecular weight distribution of 1.8. Also
^The styrene content determined by ¹ H-NMR was 29% by weight. (Examples 1 to 9) Compositions containing the isobutylene-based block copolymer in the mixing ratio shown in Table 1 were prepared. The composition is
Using Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.), 17
What was melt-kneaded at 0 ° C. and 50 rpm for 10 minutes,
Sheets were formed by hot press molding. Two 5 mm x 6 mm x 1.7 mm vibration damping material test pieces were cut out from the obtained sheet, and laminated in the order of a 2 mm thick steel sheet, a damping material, a 1.5 mm thick steel sheet, a damping material, and a 2 mm thick steel sheet. Then, they were bonded by finger pressure to create a small viscoelastic damper. Table 1 shows the measurement results of the dynamic viscoelastic properties of the obtained viscoelastic damper in the shear mode.

(Comparative Examples 1 to 7) Small viscoelastic dampers were prepared using the compositions prepared in the proportions shown in Table 1, and the same evaluations as in Examples 1 to 9 were performed. Table 1 shows the results
Shown in

[0058]

[Table 1] From Table 1, the glass transition temperature of the composition was -15 ° C to 15 ° C.
By adjusting the range of the value of _{G '10 ℃ / G' 30} ℃ 5
Tan at 10 ° C., 20 ° C., and 30 ° C.
It can be seen that a composition having δ of 0.4 or more can be obtained. Further, the viscoelastic damper using the composition containing the isobutylene-based block copolymer of the present invention as a main component as a vibration damping material has a low temperature dependence of rigidity, shows a high damping property near room temperature, and has a high damping property in the building field. It can also be seen that it is excellent as a vibration damping material for a viscoelastic damper.

On the other hand, Comparative Example 1 using an isobutylene-based block copolymer alone as a vibration damping material described in Examples of WO93 / 14135 and JP-A-7-137194, WO93 / 14135 Isobutylene-based block copolymer / polybutene / flake graphite = 100/15 /
Comparative Example 2 using a composition of 50 (parts by weight) as a vibration damping material, isobutylene-based block copolymer / alcon P-100 = 100/25 described in Examples of JP-A-7-137194. In Comparative Example 3 in which the composition consisting of (parts by weight) was used as a vibration damping material, the glass transition temperature was not in the range of −15 ° C. to 15 ° C., and tan δ near room temperature was low. It turns out that it does not have the characteristic which can be used as a damping material for viscoelastic dampers in the field. In addition, the glass transition temperature is 1
In Comparative Example 4 higher than 5 ° C., although tan δ near room temperature is high, the stiffness has a large temperature dependence, and does not have characteristics that can be used as a vibration damping material for a viscoelastic damper.

Further, thermoplastic elastomers known to be used as ordinary vibration damping materials as shown in Comparative Examples 5 to 7 can be used as vibration damping materials for viscoelastic dampers in the field of construction. It can also be seen that it has no characteristics.

(Example 10) The composition containing the isobutylene-based block copolymer described in Example 6 was subjected to 25 × 25 ×
A sheet formed to 1.7 mm and a rolled steel sheet for general structure (SS400 (JIS G-3101)) of 25 mm × 10 previously subjected to surface treatment by sandblasting.
An adhesive Chemloc 487A / B (manufactured by Lord Far East, Inc.) was applied to the surface of a surface-treated steel sheet of 0 mm × 5 mm, dried at room temperature for 1 hour, and then sheeted with two sheets of the surface-treated steel sheet. To form a small viscoelastic damper. In order to accelerate the curing of the adhesive, it was heated in an oven at 100 ° C. for 10 minutes, and then left at room temperature for 24 hours. The obtained viscoelastic damper is used for Autograph AG-10TB (manufactured by Shimadzu Corporation).
And pull in the shear direction at a speed of 300 mm / min.
The maximum strain before the sheet was peeled or broken was measured. As a result, the maximum strain was 690%. The destruction was a cohesive destruction of the vibration damping material portion, and no interfacial peeling occurred.

(Example 11) In the same manner as in Example 10,
Using the composition containing the isobutylene-based block copolymer described in Example 6 as a vibration damping material, a shear test was performed on a viscoelastic damper bonded only by finger pressure without using an adhesive for bonding to a steel plate. And the interface was peeled at a maximum strain of 80%.

When the viscoelastic damper breaks due to a large earthquake or the like, it is dangerous if interfacial peeling occurs. However, from the above-mentioned results, the use of the adhesive may cause cohesive failure in the vibration damping material. It can be seen that a sufficient adhesive strength is obtained, and a viscoelastic damper with high safety during an earthquake is obtained.

(Example 12) The composition containing the isobutylene-based block copolymer described in Example 6 was applied to a 50 x 50 x 5
mm and a rolled steel sheet for general structure (SS4
00 (JIS G-3101)) previously subjected to surface treatment by sandblasting.
Adhesive Chemlock 48 on the surface of 7 mm surface-treated steel sheet
After applying 7A / B (manufactured by Lord Far East, Inc.) and drying at room temperature for 1 hour,
A small viscoelastic damper as shown in FIG. 4 was created by bonding two sheets between three surface-treated steel sheets. 1 in an oven at 100 ° C to accelerate the curing of the adhesive
After heating for 0 minutes, it was left at room temperature for 24 hours. The obtained viscoelastic damper was fixed to a vibrator with a jig, and a dynamic vibration test was performed. The test equipment includes 831 Ela manufactured by MTS.
The stmer Test System was used, and a thermostat was used for temperature control. The measurement conditions were a frequency of 0.5 Hz,
Strain 50%, 100%, 200%, temperature 10 ° C, 20
℃, 30 ℃. Table 2 shows the equivalent rigidity (Keq) and the equivalent damping constant (heq) calculated from the obtained hysteresis curve.
FIG. 5 shows a hysteresis curve at 20 ° C. Keq and heq were calculated using the calculation formulas described in JP-A-11-199714.

[0065]

[Table 2] From Table 2, the viscoelastic damper using the composition containing the isobutylene-based block copolymer of the present invention as a main component as a vibration damping material has a low temperature dependence of rigidity even when the actual damper performance is measured. It can be seen that the material exhibits high attenuation near room temperature. FIG. 5 shows that the hysteretic damper using the composition containing the isobutylene-based block copolymer of the present invention as a main component as a vibration damping material has a hysteresis curve that increases concentrically when the strain is changed, and the strain is increased. It can be seen that this is an excellent building viscoelastic damper with small dependence (high linearity).

[0066]

The viscoelastic damper characterized in that the viscoelastic composition containing the isobutylene-based block copolymer of the present invention as a main component is used as a vibration damping material. Provides excellent viscoelastic damper with low temperature dependence as an architectural viscoelastic damper, and provides a viscoelastic damper with sufficient adhesion between steel plate and damping material by bonding with metal adhesive can do.

[Brief description of the drawings]

FIG. 1 is a model diagram of a viscoelastic damper having a structure in which one layer of a vibration damping material using a viscoelastic composition and two layers of a steel plate are alternately laminated.

FIG. 2 is a model diagram of a viscoelastic damper having a structure in which two layers of a vibration damping material using a viscoelastic composition and three layers of a steel plate are alternately laminated.

FIG. 3 is a model diagram of a viscoelastic damper having a structure in which one layer of a vibration damping material using a viscoelastic composition and two layers of steel pipes are alternately laminated concentrically.

FIG. 4 is a cross-sectional view of a small viscoelastic damper used to measure the damper performance of the viscoelastic damper and having a structure in which two layers of a vibration damping material using a viscoelastic composition and three layers of steel plates are alternately laminated.

FIG. 5 is a hysteresis curve showing the relationship between displacement and load, showing the damper performance of the viscoelastic damper.

[Explanation of symbols]

 1: damping material 2: steel plate 3: steel pipe 4: damping material 5: surface-treated steel plate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/00 C09K 3/00 P F16F 7/00 F16F 7/00 F 15/02 15/02 L 15 / 08 15/08 DF term (reference) 3J048 AA07 AC05 BD01 BD08 EA38 3J066 AA01 AA22 AA26 BA10 BB04 BD10 4J002 AE05Y AF02X BA00X BA01X BC03X BK00X BP01W BP03W CE00X EH096 EH146 FD02Y FD026B04H03B03H03B03H03B04H03B04H02B HB08 HB10 HB13 HB14 HB15 HB16 HB17 HB27 HB32 HB39 HB45 HB48

Claims (7)

[Claims] 1. A composition mainly comprising an isobutylene-based block copolymer comprising a polymer block mainly composed of isobutylene and a polymer block not mainly composed of isobutylene. The storage modulus (G ′) of the composition obtained by dynamic viscoelasticity measurement in shear mode of 1
The ratio of the values at 0 ° C. and 30 ° C. (G ′ ₁₀ ° C./G ′ ₃₀ ° C.) is 5 or less, and the loss tangent (tan δ) obtained by the measurement is 0.4 or more at 10 ° C. to 30 ° C. Certain viscoelastic compositions 2. A composition comprising, as a main component, an isobutylene-based block copolymer comprising a polymer block containing isobutylene as a main component and a polymer block not containing isobutylene as a main component. The storage modulus (G ′) of the composition obtained by dynamic viscoelasticity measurement in shear mode of 1
The ratio of the values at 0 ° C. and 30 ° C. (G ′ ₁₀ ° C./G ′ ₃₀ ° C.) is 4 or less, and the loss tangent (tan δ) obtained by the measurement is 0.5 or more at 10 ° C. to 30 ° C. Certain viscoelastic compositions. 3. A loss tangent (tan) obtained by a dynamic viscoelasticity measurement in a shear mode, comprising a composition comprising an isobutylene-based block copolymer and a tackifier resin.
The viscoelastic composition according to claim 1 or 2, wherein the peak temperature of δ) is in the range of -15 to 15 ° C. 4. The viscoelastic composition according to claim 3, which is a composition obtained by further blending a plasticizer with the isobutylene-based block copolymer and the tackifier resin. 5. A viscoelastic damper in which a layer using the viscoelastic composition according to any one of claims 1 to 4 and a steel sheet layer are alternately laminated, wherein the layer using the composition is used. Also, a viscoelastic damper characterized by having more steel layers. 6. A viscoelastic damper in which layers using a viscoelastic composition and layers of steel pipes are alternately and concentrically laminated, wherein the number of steel pipe layers is larger. 7. The viscoelasticity according to claim 5, wherein an adhesive surface of a layer using the viscoelastic composition and a layer of a steel plate or a steel pipe is bonded via an adhesive. Damper.