JP2005105209A - Highly damping elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly damping elastomer composition showing a high damping property, having a hardness in an appropriate range and having a small temperature dependence of its hardness. <P>SOLUTION: This highly damping elastomer composition contains (A) a styrenic block copolymer, (B) a terpene phenol resin having 90-250 acid value and (C) a butadiene-based block liquid state polymer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a high damping elastomer composition. More specifically, the present invention relates to a highly damped elastomer composition in which the composition after curing exhibits a high damping property, the hardness is in an appropriate range, and the temperature dependency of the hardness is excellent.

Seismic control devices and seismic isolation devices for buildings such as buildings and bridge pier support parts are used for the purpose of suppressing vibrations of buildings from vibrations caused by earthquakes and winds, traffic vibrations caused by traveling of large vehicles, and the like. Therefore, damping materials (damping materials) used for applications such as seismic control devices and seismic isolation devices are required to absorb vibrations from small to large amplitudes in accordance with the rigidity (hardness) of the building. Furthermore, in order to exhibit stable attenuation performance, stable attenuation performance is required in the outside air atmosphere of the building, and it is desired that the temperature dependence at a high degree is small.
As a damping material used for such an application in the construction field, a rubber component is a main component, and a glass transition temperature (Tg) is high (around 0 ° C.) and a softening point is low (100 ° C.). It is known that a rubber composition containing a thermoplastic resin or the like is used.
However, when a large damping performance is expressed with such a rubber composition, a glass transition temperature (Tg) region in which a tan δ (loss tangent) peak is mainly used is used. This glass transition temperature (Tg) Since the region is a region that undergoes a rapid change from the glass state to the rubber state, there is a problem that the temperature dependence of hardness is extremely large.

  As means for solving such a problem, Patent Document 1 discloses a high-damping elastomer composition containing at least one styrenic block polymer as a main component, and the ratio of the diblock component in the entire styrenic block polymer. Has been proposed in the range of 50 to 95% by weight.

JP 2002-138184 A

However, in a hot melt type high damping elastomer composition mainly composed of a thermoplastic elastomer such as a styrene block polymer, there is a problem that the temperature dependency of the hardness which is the ratio of the hardness at 10 ° C. and the hardness at 30 ° C. is large. It was not able to solve.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a highly damped elastomer composition that exhibits a high damping property, has a hardness in an appropriate range, and has a small temperature dependency of the hardness.

Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that an elastomer composition containing a styrene-based block copolymer, a specific terpene phenol resin, and a specific liquid polymer, and a specific Elastomer composition containing maleic anhydride-modified styrenic block copolymer, amine-modified resin, and specific terpene phenol resin exhibits high damping, hardness is in an appropriate range, and temperature dependence of hardness Has been found to be a highly attenuated elastomer composition having a small size, and the present invention has been completed.
That is, this invention provides the high attenuation | damping elastomer composition shown to following (i)-(vii).

  (I) A highly damped elastomer composition (first) containing a styrene block copolymer (A), a terpene phenol resin (B) having an acid value of 90 to 250, and a butadiene block liquid polymer (C). Embodiment).

  (Ii) The highly attenuated elastomer composition according to (i), further comprising a polyamide resin (D).

  (Iii) The styrenic block copolymer (A) has a block body represented by any one of the following formulas (1) to (3) as a rubber component, and the softening point of the terpene phenol resin (B). Is a high-damping elastomer composition as described in (i) or (ii) above.

上記式（１）〜（３）中、ｎは、それぞれ独立に６０〜２５０の整数を表す。

In said formula (1)-(3), n represents the integer of 60-250 each independently.

  (Iv) The highly damped elastomer composition according to any one of (i) to (iii), wherein the butadiene block liquid polymer (C) has a block body represented by the following formula (4) as a rubber component.

上記式（４）中、ｍおよびｎは、それぞれ独立に１０〜３００の整数を表す。

In said formula (4), m and n represent the integer of 10-300 each independently.

  (V) a maleic anhydride-modified styrene block copolymer (E) having a modification rate of 0.1 to 3.0% with maleic anhydride, and a terpene phenol resin (F) having an acid value of 90 to 250 A highly attenuated elastomer composition containing the amine-modified resin (G) (second embodiment).

  (Vi) The maleic anhydride-modified styrene block copolymer (E) has a block body represented by any one of the following formulas (5) to (7) as a rubber component, and the terpene phenol resin (F The high-damping elastomer composition according to the above (v), wherein the softening point of () is 100 ° C. or higher.

上記式（５）〜（７）中、ｎは、それぞれ独立に６０〜２５０の整数を表す。

In said formula (5)-(7), n represents the integer of 60-250 each independently.

  (Vii) The highly attenuated elastomer composition according to (v) or (vi), wherein the amine-modified resin (G) is a polyamide resin having an amino group at a terminal.

INDUSTRIAL APPLICABILITY According to the present invention, a highly damped elastomer composition that exhibits a high damping property, has a hardness in an appropriate range, and has a low temperature dependency of the hardness is useful because it can be provided. Therefore, the high damping elastomer composition according to the first and second aspects of the present invention can withstand use in various climatic conditions from cold to hot and humid, and is not limited to buildings, This is useful because it can be suitably used for vibration damping materials and vibration proofing materials for railways, ships, airplanes, industrial / home appliances and the like.
Here, regarding the attenuation, if the operating temperature range is 0 to 50 ° C., it is useful that tan δ (20 ° C.) at 20 ° C. is 0.5 or more to show high attenuation.
Moreover, about hardness, when the composition is too small, the cured composition becomes brittle, and when it is too large, the damping property decreases. Therefore, it is appropriate that the storage shear modulus G ′ (25 ° C.) at 25 ° C., which shows the characteristics of hardness, be in the range of 10 ^{4 to} 5 × 10 ⁵ .
Further, regarding the temperature dependence of hardness, if the operating temperature range is 0 to 50 ° C., the storage shear modulus G ′ (10 ° C.) at 10 ° C. and the storage shear modulus G ′ (30 ° C.) at 30 ° C. It is useful that the ratio “G ′ (10 ° C.) / G ′ (30 ° C.)” is 1.5 or less as a good temperature dependency.

Hereinafter, the present invention will be described in detail.
The highly attenuated elastomer composition according to the first aspect of the present invention (hereinafter sometimes simply referred to as “the highly attenuated elastomer composition of the present invention”) has a styrenic block copolymer (A) and an acid value of It is a highly attenuated elastomer composition containing a terpene phenol resin (B) of 90 to 250 and a butadiene block liquid polymer (C), and preferably further contains a polyamide resin (D).
Next, the styrene block copolymer (A), the terpene phenol resin (B), the butadiene block liquid polymer (C), and the polyamide resin (D) that form the highly attenuated elastomer composition of the present invention will be described in detail.

<Styrenic block copolymer (A)>
The styrenic block copolymer (A) used in the highly attenuated elastomer composition of the present invention includes polyethylene, polypropylene, polyisoprene (including 3,4-polyisoprene), hydrogenated polyisoprene (hydrogenated 3,4- From the group consisting of polyisoprene, hydrogenation rate 100%), polybutadiene (including 1,2-polybutadiene), hydrogenated polybutadiene (including hydrogenated 1,2-polybutadiene, hydrogenation rate 100%) and polyisobutylene. A copolymer of one or more selected block bodies (rubber components) and polystyrene blocks; or; a mixture of the copolymers.
Moreover, it is preferable that the said styrene-type block copolymer (A) has a block body represented by either of following formula (1)-(3) as a rubber component.

上記式（１）〜（３）中、ｎは、それぞれ独立に６０〜２５０の整数を表す。

In said formula (1)-(3), n represents the integer of 60-250 each independently.

The hydrogenation rate of the above-mentioned hydrogenated polyisoprene and hydrogenated polybutadiene is 100%. A hydrogenation rate of 100% is preferred because of excellent heat aging resistance and weather resistance when a vibration damping elastomer composition for construction is used.
In the present invention, polyisoprene includes 3,4-polyisoprene (hereinafter sometimes simply referred to as “vinyl isoprene”) and means 1,4-polyisoprene and / or 3,4-polyisoprene. . The hydrogenated polyisoprene includes hydrogenated 3,4-polyisoprene (hereinafter sometimes simply referred to as “hydrogenated vinyl isoprene”), polyethylene and polypropylene, and includes hydrogenated 1,4-polyisoprene and hydrogenated. It means one or more selected from the group consisting of 3,4-polyisoprene, polyethylene and propylene.
Similarly, polybutadiene includes 1,2-polybutadiene and means 1,4-polybutadiene and / or 1,2-polybutadiene. The hydrogenated polybutadiene includes hydrogenated 1,2-polybutadiene and polyethylene, and means one or more selected from the group consisting of hydrogenated 1,4-polybutadiene, hydrogenated 1,2-polybutadiene and polyethylene.

  Specific examples of such a styrenic block copolymer (A) include polystyrene-hydrogenated polybutadiene block copolymers (including polystyrene-polyethylene block copolymers), polystyrene-polyisobutylene block copolymers. Polymer, polystyrene-hydrogenated polyisoprene block copolymer, polystyrene-hydrogenated polybutadiene-hydrogenated polyisoprene block copolymer, polystyrene-hydrogenated polybutadiene-polystyrene block copolymer (hydrogenated SBS), polystyrene-polyisoprene- Polystyrene block copolymer (SIS), polystyrene-polybutadiene-polystyrene block copolymer (SBS), polystyrene-polyisobutylene-polystyrene block copolymer (SIBS), polystyrene -Hydrogenated polyisoprene-polystyrene block copolymer (including polystyrene- (polyethylene-polypropylene) -polystyrene block copolymer (SEPS)), polystyrene-hydrogenated polybutadiene-polyisoprene-polystyrene copolymer, etc. These may be used alone or in combination of two or more.

In addition, polybutadiene, hydrogenated polybutadiene, polyisoprene exemplified as the block body constituting the styrene block copolymer (A) (hereinafter sometimes referred to as “rubber component of the styrene block copolymer (A)”). Since the hydrogenated polyisoprene contains polymers having different structures as described above (for example, 1,2- and 1,4-polybutadiene, 1,4- and 3,4-polyisoprene), styrene exemplified above. The system block copolymer (A) may also be composed of such block bodies having different structures.
Specifically, for example, polystyrene-polyethylene-hydrogenated polyisoprene-polystyrene block copolymer (SEEPS), polystyrene-hydrogenated polybutadiene-hydrogenated 1,2-polybutadiene-polystyrene block copolymer (SEBS), polystyrene- ( Examples thereof include vinyl isoprene) -polystyrene block copolymer (SVIS), polystyrene- (hydrogenated vinyl isoprene) -polystyrene block copolymer (SHVIS), and the like.
Moreover, the bonding mode of the block body of the styrenic block copolymer (A) is not particularly limited. For example, in the case of polybutadiene, 1,2-polybutadiene or 1,4-polybutadiene may be regularly bonded to form a block body, and 1,2-polybutadiene and 1,4-polybutadiene are randomly formed. They may be combined to form a block body.

Among the styrene block copolymers (A) exemplified above, polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS), polystyrene- (vinylisoprene) -polystyrene block copolymer (SVIS), polystyrene- (Hydrogenated vinylisoprene) -polystyrene block copolymer (SHVIS) is obtained. The highly attenuated elastomer composition of the present invention has processability, adhesiveness to metal, and other composition components (for example, liquid rubber, heat described later) It is preferable because it is excellent in compatibility and strength with a plastic resin or the like.
In particular, polystyrene- (vinyl isoprene) -polystyrene block copolymer (SVIS) and polystyrene- (hydrogenated vinyl isoprene) -polystyrene block copolymer (SHVIS) are obtained at 0 ° C. of the highly attenuated elastomer composition of the present invention obtained. It is preferable because tan δ (damping property) in the vicinity can be improved. This is because the vinyl and hydrogenated vinyl groups which are the side chains of the rubber component of these styrene block copolymers (A) are crystalline, so that the styrene block copolymer (A) is 0 ° C. This is considered to be because it has a glass transition temperature (Tg) in the vicinity.

The styrenic block copolymer (A) preferably has a glass transition temperature (Tg) of −65 to 10 ° C., a number average molecular weight of 50,000 to 500,000, and a styrene content of 40% by mass or less. It is more preferable that (Tg) is −60 to 0 ° C., the number average molecular weight is 50000 to 300000, particularly 70000 to 200000, and the styrene content is 35% by mass or less, particularly 30% by mass.
If the glass transition temperature (Tg) is within the above range, it is preferable because the processability of the resulting highly attenuated elastomer composition of the present invention is excellent.
Moreover, if the number average molecular weight is within the above range, the melt viscosity of the styrenic block copolymer (A) is lowered, and the resulting highly attenuated elastomer composition of the present invention is excellent in workability, which is preferable.
Furthermore, if the styrene content is within the above-mentioned range, the hard segment portion (styrene block) in the styrene block copolymer (A) is appropriately reduced, it is easy to adjust to low hardness, and with other composition components It is preferable because it is excellent in compatibility and physical properties (for example, elongation at break and strength at break).
The styrene content (bound styrene content) of the styrenic block copolymer (A) can be determined according to the test method described in JIS K6383-1995 (Test method for synthetic rubber SBR).

The styrenic block copolymer (A) can be obtained by copolymerizing a block body as a rubber component and a styrene block under the conditions normally used. The hydrogenated body is usually obtained by copolymerizing the block body. Obtained by hydrogenating (hydrogenating) under the conditions used and then copolymerizing with the styrene block, or by copolymerizing the block and the styrene block and then hydrogenating (hydrogenating) under the conditions normally used. Can do.
The styrenic block copolymer (A) may be a commercially available product. Specifically, for example, Kuraray's Septon (registered trademark) series (SEPS series, SEBS (random copolymer) series, SEEPS (Random Copolymer) series), Hiblur (registered trademark) series (SVIS series, SHVIS series) and the like. SVIS5125 (manufactured by Kuraray Co., Ltd., 13% by mass of styrene), SHVIS7125 (manufactured by Kuraray Co., Ltd., 13% by mass of styrene, 100% hydrogenation rate) and the like.

<Terpene phenol resin (B)>
The terpene phenol resin (B) used in the highly attenuated elastomer composition of the present invention is not particularly limited as long as it is a resin represented by the following formula (8) having an acid value of 90 to 250.

上記式（８）中、ｓは１〜５の整数で、ｒは１〜４の整数を表す。

In said formula (8), s is an integer of 1-5 and r represents the integer of 1-4.

The terpene phenol resin (B) preferably has a softening point of 100 ° C. or higher, more preferably 110 to 150 ° C., and still more preferably 115 to 145 ° C. If the softening point is within this range, the processability of the resulting highly attenuated elastomer composition of the present invention is excellent, which is preferable.
Moreover, a commercial item can also be used for the said terpene phenol resin (B), for example, YS resin-N-125 (acid value: 114, Yashara Chemical Co., Ltd.) etc. are mentioned, for example.

  The use of such a terpene phenol resin (B) is preferable because the temperature dependency of the hardness of the resulting highly attenuated elastomer composition of the present invention is improved and the attenuation and tackiness are also excellent. This is compatible with the rubber component of the styrenic block copolymer (A) when a terpene phenol resin having a low acid value (for example, YS resin-TO-125 used in Comparative Examples described later) is used. However, when the terpene phenol resin (B) having an acid value of 90 to 250 is used, such compatibility does not occur and the dispersion is microdispersed in the system. It is believed that there is.

Content of the said terpene phenol resin (B) is not specifically limited, In the range which does not impair the characteristic of this invention, it can adjust according to the objective, a use, etc. Specifically, the amount is preferably 20 to 80 parts by mass, more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the styrene block copolymer (A).
If the content of the terpene phenol resin (B) is within this range, the resulting highly attenuated elastomer composition of the present invention has an excellent workability because the viscosity at the time of heat processing is appropriately reduced, and after processing (when used) This is preferable because the hardness and the dampening property are good, and the temperature dependency of the hardness is also good.

<Butadiene-based block liquid polymer (C)>
The butadiene block liquid polymer (C) used in the highly attenuating elastomer composition of the present invention is particularly a liquid polymer having a butadiene block represented by the following formula (9) and other block bodies as rubber components. It is not limited.

上記式（９）中、ｎは、１０〜３００の整数を表す。

In said formula (9), n represents the integer of 10-300.

  As other block bodies, specifically, for example, polyethylene, polypropylene, polyisoprene (including 3,4-polyisoprene), hydrogenated polyisoprene (including hydrogenated 3,4-polyisoprene, hydrogenation rate) 100%), hydrogenated polyisoprene (hydrogenation rate of 80% or more, iodine value of 60 g / 100 g or less), 1,2-polybutadiene, hydrogenated polybutadiene (including hydrogenated 1,2-polybutadiene, hydrogenation rate of 100%) And at least one block selected from the group consisting of polyisobutylene.

Here, the iodine value is used as a measure (degree of unsaturation) of double bonds derived from diene components remaining in hydrogenated diene polymers such as hydrogenated polyisoprene and hydrogenated polybutadiene. It is the number of grams of iodine absorbed in 100 g of added polyisoprene and the like. The iodine value generally has a correlation with the hydrogenation rate.
The iodine value is preferably 60 g / 100 g or less, and more preferably 40 g / 100 g or less. The hydrogenation rate is preferably 80% or more, and more preferably 85% or more.
If the iodine value and the hydrogenation rate are within the above ranges, the butadiene-based block liquid polymer (C) and the rubber component of the styrene-based block copolymer (A) are appropriately compatible and further obtained. The highly attenuated elastomer composition of the invention is preferable because it can exhibit characteristics excellent in heat resistance and weather resistance.

Specific examples of such butadiene block liquid polymer (C) include polybutadiene-polyisoprene block liquid polymer, polybutadiene-hydrogenated polyisoprene block liquid polymer, polybutadiene-hydrogenated polybutadiene block liquid polymer (polybutadiene- Polyethylene block liquid polymer), polybutadiene-polyisobutylene block liquid polymer, polybutadiene-polyisoprene-polybutadiene block liquid polymer, polybutadiene-hydrogenated polyisoprene-polybutadiene block liquid polymer, polybutadiene-hydrogenated polybutadiene-polybutadiene block liquid polymer (polybutadiene) -Including polyethylene-polybutadiene block liquid polymer), polybutadiene Down - polyisobutylene - polybutadiene liquid polymer,
Examples include polybutadiene-hydrogenated polybutadiene-hydrogenated polyisoprene block liquid polymer, polybutadiene-hydrogenated polybutadiene-polyisoprene-polybutadiene liquid polymer, and the like. These may be used alone or in combination of two or more.

  Among these, the said butadiene type block liquid polymer (C) has the block body represented by following formula (4) as a rubber component, ie, polybutadiene-polyisoprene block liquid polymer, polybutadiene-polyisoprene- A polybutadiene block liquid polymer and a polybutadiene-hydrogenated polybutadiene-polyisoprene-polybutadiene liquid polymer are preferred.

上記式（４）中、ｍおよびｎは、それぞれ独立に１０〜３００の整数を表す。

In said formula (4), m and n represent the integer of 10-300 each independently.

The butadiene-based block liquid polymer (C) preferably has a number average molecular weight of 50,000 or less, more preferably 5,000 to 40,000, and even more preferably 10,000 to 35,000. If the number average molecular weight is within this range, the processability of the resulting highly attenuated elastomer composition of the present invention is excellent, which is preferable.
Moreover, a commercial item can also be used for the said butadiene type block liquid polymer (C), for example, various Claprene LIR (made by Kuraray Co., Ltd.) etc. are mentioned, for example.

  Use of such a butadiene block liquid polymer (C) is preferable because tan δ (damping property) at 20 ° C. or higher of the obtained highly damped elastomer composition of the present invention can be improved. This is because the butadiene block acts as a crystalline phase in the highly attenuated elastomer composition of the present invention containing the butadiene block liquid polymer (C), and the other block bodies are the styrene block copolymer (A) and / or Or it is thought that it is because there exists an effect | action compatible with the said terpene phenol resin (B).

The content of the butadiene-based block liquid polymer (C) is not particularly limited, and can be adjusted according to the purpose, application and the like within a range not impairing the characteristics of the present invention. Specifically, it is preferably 50 to 150 parts by mass, and more preferably 70 to 120 parts by mass with respect to 100 parts by mass of the styrene block copolymer (A).
If the content of the butadiene block liquid polymer (C) is within this range, the resulting highly attenuated elastomer composition of the present invention will have a suitably low viscosity during heat processing, so that it is excellent in workability and after processing (use Is preferable because the hardness and damping properties are further improved.

<Polyamide resin (D)>
The polyamide resin (D) used in the highly attenuated elastomer composition of the present invention is not particularly limited, and a conventionally known polyamide resin can be used. Specific examples thereof include nylon 46, nylon 6, nylon 66, and nylon 610. , Nylon 611, nylon 612, nylon 11, nylon 12, nylon 666, nylon MXD6, nylon 6T, nylon 6/66 copolymer, nylon 6/66/610 copolymer, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer, polyamide resin having an aromatic ring such as metaxylenediamine in the main chain, polyamide / modified polyolefin blend resin, and the like. You may use 2 or more types together.
Of these, nylon 6, nylon 66, nylon 666 and copolymers thereof are preferred. These polyamide resins may be used alone or in combination of two or more, and may be used in combination with other resins.

The polyamide resin (D) preferably has a number average molecular weight of 30000 or less, more preferably 5000 to 20000, and still more preferably 10,000 to 15000. If the number average molecular weight is within this range, the processability of the resulting highly attenuated elastomer composition of the present invention is excellent, which is preferable.
Moreover, it is preferable that the said polyamide resin (D) has a softening point of 100 degreeC or more, It is more preferable that it is 110-150 degreeC, It is further more preferable that it is 115-145 degreeC. If the softening point is within this range, the processability of the resulting highly attenuated elastomer composition of the present invention is excellent, which is preferable.
A commercial item can also be used for the said polyamide resin (D), for example, Sanwa Chemical Co., Ltd. # 560B, # 563M, # 15K-5 etc. are mentioned.

  It is preferable to use such a polyamide resin (D) because tan δ (damping property) of the obtained highly-damped elastomer composition of the present invention can be further improved. This is because the polyamide resin (D) has high crystallinity and is incompatible with the styrenic block copolymer (A), is microdispersed, and further absorbs vibration energy (changes to heat). It is thought that this is because.

Content of the said polyamide resin (D) is not specifically limited, In the range which does not impair the characteristic of this invention, it can adjust according to the objective, a use, etc. Specifically, the amount is preferably 20 to 80 parts by mass, and more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the styrene block copolymer (A).
If the content of the polyamide resin (D) is within this range, the resulting highly attenuated elastomer composition of the present invention has a suitably low viscosity at the time of heat processing, so that the workability is excellent and after processing (when used). This is preferable because the hardness and damping properties are further improved while maintaining the temperature dependence of the hardness.

  The high-damping elastomer composition according to the first aspect of the present invention includes, in addition to the above-described components, other polymers (liquid rubber); thermoplastic resins; carbon as long as the object of the present invention is not impaired. Fillers such as black and clay; softeners such as paraffinic oils (for example, process oil); cross-linking agents (vulcanizing agents); cross-linking accelerators (vulcanizing accelerators); vulcanizing aids; plasticizers; Auxiliary agent; Pigment; Dye; Tackifier; Antioxidant (anti-aging agent); Brightener; Flame retardant; Foaming agent; Foaming aid; Ozone degradation inhibitor; Anti-blocking agent; Various compounding agents such as a compatibilizer, a surfactant, an antistatic agent, a lubricant, and the like can be blended.

Specific examples of the liquid rubber include liquid polymers formed only from other block bodies constituting the butadiene-based block liquid polymer (C).
When such a liquid rubber is used, the liquid rubber is preferable because it functions as a softening agent by being compatible with the soft segment portion (block body) in the styrene block copolymer (A).
Moreover, a commercial item can also be used for such a liquid rubber, for example, Nisseki HV-100 (polybutene, Nippon Petrochemical Co., Ltd.), LIR-50 (polyisoprene, Kuraray Co., Ltd.). Etc.
Furthermore, the content of the liquid rubber that can be blended as necessary is not particularly limited, but the total content with the butadiene block liquid polymer (C) is 100% of the styrene block copolymer (A) 100. It is preferable that it is 50-150 mass parts with respect to a mass part, and it is more preferable that it is 80-120 mass parts.

  The method for producing the highly attenuated elastomer composition according to the first aspect of the present invention is not particularly limited. Specifically, for example, the above-described components are mixed into a roll, a kneader, an extruder, a universal agitator, a twin-screw extruder, The method of manufacturing by kneading using a Banbury mixer etc. is mentioned. Furthermore, this highly attenuating elastomer composition can be used as a product by heating it to a melting temperature or higher, melting it, pouring it into a mold, allowing it to cool and molding it into a predetermined shape.

  As described above, the high attenuation elastomer composition according to the first aspect of the present invention has good attenuation and hardness after heat processing, and further, since the temperature dependence of hardness becomes small, from a cold state to a high temperature and high humidity state, It can withstand use in various climatic conditions and can be suitably used not only for buildings, but also for applications such as automobiles, railways, ships, aircraft, industrial and home appliances, and vibration control materials.

The highly attenuated elastomer composition according to the second aspect of the present invention (hereinafter sometimes simply referred to as “the highly attenuated elastomer composition of the present invention”) has a modification rate with maleic anhydride of 0.1 to 3.0. % High-strength elastomer composition containing a maleic anhydride-modified styrene block copolymer (E), an terpene phenol resin (F) having an acid value of 90 to 250, and an amine-modified resin (G). is there.
Next, the maleic anhydride-modified styrene block copolymer (E), the terpene phenol resin (F) and the amine-modified resin (G) that form the highly attenuated elastomer composition of the present invention will be described in detail.

<Maleic anhydride modified styrene block copolymer (E)>
The maleic anhydride-modified styrenic block copolymer (E) used in the highly attenuated elastomer composition of the present invention is obtained by adding the styrenic block copolymer (A) according to the first aspect described above to a maleic anhydride in an amount of 0.001. 1-3.0%, preferably 0.2-2.0% modified.
Here, the modification rate with maleic anhydride is calculated from the amount of maleic anhydride used for modification, and is based on the modification with respect to the mass of the resulting maleic anhydride-modified styrene block copolymer (E). It is the mass% of the maleic anhydride used.

Specific examples of the maleic anhydride-modified styrene block copolymer (E) include, for example, modified products of the styrene block copolymer (A) exemplified above with maleic anhydride.
Among these, polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS), polystyrene- (hydrogenated vinylisoprene) -polystyrene block copolymer (SHVIS), polystyrene-polyisobutylene-polystyrene block copolymer (SIBS). SEPS-MAH, SHVIS-MAH, SIBS-MAH modified with maleic anhydride in terms of processability and physical properties (for example, breaking elongation, breaking strength, etc.) of the resulting highly attenuated elastomer composition of the present invention. It is preferable because it is excellent. This is considered to maintain compatibility with other composition components.

The maleic anhydride-modified styrenic block copolymer (E) has been described above under normal modification conditions using maleic anhydride (for example, pressureless heating without solvent, heating in a solvent, etc.). It can be obtained by an addition reaction between the styrenic block copolymer (A) according to the first embodiment and maleic anhydride.
Specifically, for example, SEPS-MAH is prepared by dissolving polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS) in toluene and adding maleic anhydride thereto, as shown in the examples described later. It is obtained by heating and stirring and removing the solvent after completion of the reaction. The modification rate can be calculated from the amount of unreacted maleic anhydride remaining in the solvent that has been removed.

<Terpene phenol resin (F)>
The terpene phenol resin (F) used in the highly attenuated elastomer composition of the present invention is the same resin as the terpene phenol resin (B) according to the first aspect described above.
By using such a terpene phenol resin (F), as in the first embodiment of the present invention, the temperature dependency of the hardness of the resulting highly attenuated elastomer composition of the present invention is improved, and further, the attenuation and tackiness are increased. Is also preferable.

Content of the said terpene phenol resin (F) is not specifically limited, In the range which does not impair the characteristic of this invention, it can adjust according to the objective, a use, etc. Specifically, it is preferably 20 to 80 parts by mass, and more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the maleic anhydride-modified styrene block copolymer (E).
If the content of the terpene phenol resin (F) is within this range, as in the first embodiment of the present invention, the viscosity of the resulting highly attenuated elastomer composition of the present invention at the time of heat processing is appropriately reduced. It is preferable because it has excellent properties, hardness after processing (in use) and damping properties become good, and temperature dependency of hardness becomes good.

<Amine modified resin (G)>
The amine-modified resin (G) used in the highly attenuating elastomer composition of the present invention is not particularly limited as long as it is a resin having one or more amino groups in the molecule. As a specific example thereof, a polyamide resin is amine-modified. Examples include amine-modified polyamide resins; amine-modified polyurethane resins obtained by amine-modifying polyurethane resins; amine-modified polyurea resins obtained by amine-modifying polyurea resins; amine-modified epoxy resins obtained by amine-modifying epoxy resins;
The amine-modified polyamide resin is a resin in which an amino group is introduced at the end of the polyamide resin (D) exemplified above, more specifically, raw materials such as unsaturated dicarboxylic acid and ethylenediamine, adipic acid and metaxylylenediamine. Preferred examples include those obtained by excessively reacting the diamine component in the combination.
More specifically, examples of the amine-modified polyurethane resin include amine-based curing agents having a urethane structure in the main skeleton (for example, LIA-146 (manufactured by Sanwa Chemical Co., Ltd.)).
More specifically, the amine-modified polyurea resin includes an isocyanate group (NCO) -terminated prepolymer or other functional isocyanate and an excessive amount of an amine-based curing agent (for example, LIR-146 (manufactured by Sanwa Chemical Co., Ltd.)). What is obtained by making it react is suitably illustrated.
More specifically, examples of the amine-modified epoxy resin include those obtained by reacting an epoxy resin with an excess amount of an amine curing agent (for example, LIA-146 (manufactured by Sanwa Chemical Co., Ltd.)). Preferably exemplified.

  The use of such an amine-modified resin (G) is preferable because the resulting highly-damped elastomer composition of the present invention has good hardness temperature dependency and damping properties, and is also excellent in tackiness and breaking properties. This is presumably because the amino group of the amine-modified resin (G) and the maleic anhydride group of the maleic anhydride-modified styrene block copolymer (E) act as pseudo-crosslinking points.

The content of the amine-modified resin (G) with respect to the maleic anhydride-modified styrene block copolymer (E) is such that the amino group of the amine-modified resin (G) and the maleic anhydride-modified styrene block copolymer ( If it contains so that the maleic anhydride group of E) may become 1.0 equivalent or an amino group may become excess, it will not specifically limit. In terms of parts by mass, although it depends on the modification rate of maleic anhydride and the number of amino groups introduced, about 20 to 80 parts by mass with respect to 100 parts by mass of the maleic anhydride-modified styrene block copolymer (E). It is.
When the content of the amine-modified resin (G) is within this range, the resulting highly attenuated elastomer composition of the present invention has an excellent workability because the viscosity at the time of heat processing is appropriately reduced, and after processing (when used) Is preferable because the hardness and damping properties of the steel are good and the temperature dependence of the hardness is good.

  The highly damped elastomer composition according to the second aspect of the present invention is a butadiene-based block liquid polymer according to the first aspect described above as long as it does not impair the object of the present invention, if necessary. (C) and other polymers (liquid rubber) and various compounding agents exemplified above can be blended in the same manner as in the first aspect of the present invention.

  The method for producing the highly attenuated elastomer composition according to the second aspect of the present invention is not particularly limited, and specifically, as in the first aspect of the present invention, each of the above components is mixed into a roll, a kneader, and an extruder. Examples thereof include a method of producing by kneading using a universal stirrer, a twin screw extruder, a Banbury mixer or the like. Furthermore, this highly attenuating elastomer composition can be used as a product by heating it to a melting temperature or higher, melting it, pouring it into a mold, allowing it to cool and molding it into a predetermined shape.

  As described above, the high attenuation elastomer composition according to the second aspect of the present invention has good attenuation and hardness after heat processing, and further, since the temperature dependence of hardness is reduced, from a cold state to a high temperature and high humidity state, It can withstand use in various climatic conditions and can be suitably used not only for buildings, but also for applications such as automobiles, railways, ships, aircraft, industrial and home appliances, and vibration control materials.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
(Examples 1-6, Comparative Examples 1 and 2)
SEPS (Septon 2063, manufactured by Kuraray Co., Ltd.), SHVIS (Hibler 7125, manufactured by Kuraray Co., Ltd.), SVIS (Hibler 5125, Kuraray Co., Ltd.) as the styrene-based block copolymer (A) shown in Table 1 below. Manufactured by using YS Resin-N-125 (acid value: 114, manufactured by Yasuhara Chemical Co., Ltd.) as the terpene phenol resin (B), and Claprene LIR-390 (manufactured by Kuraray Co., Ltd.) as the butadiene block liquid polymer (C). Using Examples # 1-6, Comparative Example 1, and # 560B (manufactured by Sanwa Chemical Co., Ltd.) as the polyamide resin (D) and polybutene (HV-100, manufactured by Nippon Petrochemical Co., Ltd.) as the liquid rubber Two elastomer compositions were prepared. In Comparative Example 1, YS resin-TO-125 (acid value: 75, manufactured by Yasuhara Chemical Co., Ltd.) was used instead of YS resin-N-125.

  About each obtained elastomer composition, the hardness at 20 ° C. (tan δ (20 ° C.)), the hardness at 25 ° C. (G ′ (25 ° C.)), and the hardness obtained by comparing the hardness at 10 ° C. and 30 ° C. The temperature dependence (G ′ (10 ° C.) / G ′ (30 ° C.)) was measured by the following test. The results are shown in Table 1 below.

(1) Preparation of test body Around the polypropylene sheet (length 15 cm x width 15 cm x height 2 cm), a frame is produced with a polyethylene foam sheet, and each elastomer composition obtained by kneader processing is prepared therein. Poured and cured for 16 hours under conditions of 20 ° C. and 65% humidity. A cured product obtained by removing the polyethylene foam sheet after curing was used as a test specimen.

(2) Damping property at 20 ° C. (tan δ (20 ° C.))
With respect to each specimen obtained in (1), the loss angle tangent (tan δ) at a temperature of 20 ° C. during forced shear excitation at a frequency of 5 Hz was measured.

(3) Hardness at 25 ° C. (G ′ (25 ° C.))
About each test body obtained by (1), the storage shear elastic modulus G '(25 degreeC) in the temperature of 25 degreeC at the time of the forced shear vibration of frequency 5Hz was measured.

(4) Temperature dependence of hardness (G ′ (10 ° C.) / G ′ (30 ° C.))
For each specimen obtained in (1), the storage shear elastic moduli G ′ (10 ° C.) and G ′ (30 ° C.) at temperatures 10 and 30 ° C. at the time of forced extension with a frequency of 5 Hz were measured. '(10 ° C) / G' (30 ° C) was determined.

(Examples 7 to 10, Comparative Examples 3 and 4)
As the maleic anhydride-modified styrene block copolymer (E), SEPS (Septon 2063, manufactured by Kuraray Co., Ltd.), SEPS-MAH, SHVIS-MAH or SIBS-MAH, with the composition components (parts by mass) shown in Table 2 below. As a terpene phenol resin (F), YS resin-N-125 (acid value: 114, manufactured by Yasuhara Chemical Co., Ltd.) is used, an amine-modified resin (G) is an amine-terminated polyamide resin, and a liquid rubber is used. The elastomer compositions of Examples 7 to 10 and Comparative Examples 3 and 4 were prepared using polybutene (HV-100, manufactured by Nippon Petrochemical Co., Ltd.). In Comparative Example 3, # 560B (manufactured by Sanwa Chemical Co., Ltd.) was used as the polyamide resin instead of the amine-terminated polyamide resin.

Here, the SEPS-MAH is a modified product obtained by modifying a polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS) with maleic anhydride as described above, and 100 g of SEPS is dissolved in 1 L of toluene. Was obtained by adding 1.5 g of maleic anhydride and stirring them at 180 ° C. for 5 hours, and the modification rate was 1.4%.
Similarly, SHVIS-MAH is a modified product obtained by modifying polystyrene- (hydrogenated vinylisoprene) -polystyrene block copolymer (SHVIS) with maleic anhydride, in which 100 g of SHVIS is dissolved in 1 L of toluene, and maleic anhydride is dissolved therein. It was obtained by adding 1.7 g and stirring them at 180 ° C. for 6 hours, and the modification rate was 1.5%.
Similarly, SIBS-MAH is a modified product obtained by modifying a polystyrene-polyisobutylene-polystyrene block copolymer (SIBS) with maleic anhydride, and 100 g of SIBS is dissolved in 1 L of toluene, and 1.6 g of maleic anhydride is added thereto. They were added and stirred at 180 ° C. for 8 hours, and the modification rate was 1.3%.

  The amine-terminated polyamide resin is prepared by adding 2 equivalents of ethylenediamine to unsaturated dicarboxylic acid that is a raw material of the polyamide resin (# 560B, manufactured by Sanwa Chemical Co., Ltd.) used in Comparative Example 3, and stirring with heating. What was obtained was used.

  About the cured | curing material of each obtained elastomer composition, the attenuation | damping property (tan (delta) (20 degreeC)) in 20 degreeC, the hardness in 25 degreeC (G '(25 degreeC)), and the hardness in 10 degreeC and 30 degreeC The temperature dependence of the compared hardness (G ′ (10 ° C.) / G ′ (30 ° C.)) was measured by the test described above. The results are shown in Table 2 below.

  From the results shown in Table 1 and Table 2 above, the elastomer compositions obtained in Examples 1 to 10 show high damping after heat processing, and the hardness after processing (in use) is in an appropriate range. It became clear that temperature dependence became small.

Claims (7)

  A highly damped elastomer composition containing a styrene block copolymer (A), a terpene phenol resin (B) having an acid value of 90 to 250, and a butadiene block liquid polymer (C).   Furthermore, the high attenuation | damping elastomer composition of Claim 1 containing a polyamide resin (D). The styrenic block copolymer (A) has a block body represented by any one of the following formulas (1) to (3) as a rubber component, and the softening point of the terpene phenol resin (B) is 100. The high-damping elastomer composition according to claim 1 or 2, which has a temperature of ° C or higher.

(In formulas (1) to (3), n independently represents an integer of 60 to 250.) The highly damped elastomer composition according to any one of claims 1 to 3, wherein the butadiene block liquid polymer (C) has a block body represented by the following formula (4) as a rubber component.

(In formula (4), m and n each independently represents an integer of 10 to 300.)   Maleic anhydride-modified styrene block copolymer (E) having a modification rate of 0.1 to 3.0% with maleic anhydride, terpene phenol resin (F) having an acid value of 90 to 250, and amine modification A high-damping elastomer composition containing a resin (G). The maleic anhydride-modified styrene block copolymer (E) has a block body represented by any of the following formulas (5) to (7) as a rubber component, and softens the terpene phenol resin (F) The high-damping elastomer composition according to claim 5, wherein the point is 100 ° C or higher.

(In formulas (5) to (7), n independently represents an integer of 60 to 250.)   The highly attenuated elastomer composition according to claim 5 or 6, wherein the amine-modified resin (G) is a polyamide resin having an amino group at a terminal.