JP6438660B2 - POLYMER COMPOSITION, PROCESS FOR PRODUCING THE SAME, AND USE - Google Patents

Description

  The present invention relates to a polymer composition excellent in vibration damping properties and soundproofing properties and a method for producing the same, and also relates to a vibration damping material and a soundproofing material using the polymer composition.

  In recent years, with the development of transportation facilities such as automobiles, noise and vibration caused by this have become major social problems. In addition, high-level characteristics such as low vibration and low noise have been required inside automobiles. In general households, office machines such as copiers and printers are widely used, and reduction of noise and vibration generated by these machines is an important issue. Furthermore, household appliances are becoming larger due to changes in lifestyle, and low vibration and quietness due to low vibration of equipment such as refrigerators, washing machines and vacuum cleaners are also important performance features. It has become one.

  Conventionally, various springs, anti-vibration rubber, and the like have been used to reduce the vibration and noise. This method is to reduce the generation of vibrations and noises by interrupting the transmission of vibrations, but the current situation is that it cannot fully meet the various requirements described above.

  In addition to this, a so-called vibration suppression method that suppresses vibrations generated from various devices has become widespread. That is, it is a method of suppressing the occurrence of vibrations by sticking or sandwiching various viscoelastic bodies to a vibrating material as a damping material. As a damping material used for this purpose, for example, a block copolymer composed of a block composed of a diene monomer and a block composed of an aromatic vinyl monomer is known.

However, such a block copolymer may not exhibit sufficient vibration damping performance due to a change in ambient temperature or the like when actually used.
In Patent Document 1, it is used for anti-vibration of a light load that contains a non-aromatic rubber softener for the purpose of reducing the hardness of a thermoplastic elastomer such as hydrogenated styrene-butadiene-styrene block copolymer. Anti-vibration materials are described. However, in this document, there is no disclosure of vibration damping properties, and the vibration damping performance is insufficient when the specifically disclosed softener is used. Also, depending on the type of softener, flexibility and weather resistance were insufficient.

  Patent Document 2 describes a resin composition having low hardness, high loss (vibration suppression), and good gas permeability, including an isobutylene block copolymer and a polyolefin resin. Furthermore, it describes that a non-aromatic rubber softener is blended for the purpose of lowering the hardness. However, when the softener specifically disclosed in this document is used, the vibration damping performance is insufficient. Also, depending on the type of softener, flexibility and weather resistance were insufficient.

JP 2000-169826 A International Publication No. 2003/27183 Pamphlet

  The present invention provides a polymer composition that is excellent in vibration damping properties and can be suitably used for vibration damping materials and soundproofing materials, a method for producing the same, and a vibration damping material and soundproofing material that are excellent in vibration damping properties. It is an issue.

The present invention relates to the following [1] to [10].
[1] (a) 100 parts by weight of a block copolymer containing a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound or a hydrogenated product thereof When,
(B) 100 ° C. kinematic viscosity of 300~5000mm ² / s, a 40 ° C. kinematic viscosity 4000~100000mm ² / s, the ethylene · alpha-olefin interpolymer of ethylene structural unit content of from 30 to 80 mol% 1 to 200 parts by weight of polymer,
(C) 1 to 200 parts by weight of oil having a 100 ° C. kinematic viscosity of 1 to 299 mm ² / s and a 40 ° C. kinematic viscosity of 1 to 3999 mm ² / s;
(D) A polymer composition comprising 0 to 100 parts by weight of a polyolefin resin having an MFR of 0.1 to 500 g / 10 minutes.

[2] A block copolymer containing a polymer block (A) mainly composed of the vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound or a hydrogenated product (a) thereof is vinyl. The polymer according to [1], wherein the polymer is a hydrogenated product of a block copolymer containing a polymer block (A) mainly composed of an aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound. Composition.
[3] The [1] or [1], wherein the 100 ° C. kinematic viscosity V _{B of the} ethylene / α-olefin copolymer (b) and the 100 ° C. kinematic viscosity V _{C of the} oil (c) have the following relationship: The polymer composition according to [2].
V _B −V _C ≧ 200 mm ² / s
[4] The polymer composition according to any one of [1] to [3], wherein the ethylene / α-olefin copolymer (b) has a kinematic viscosity at 100 ° C. of 500 to 3500 mm ² / s.
[5] The polymer composition according to any one of [1] to [4], wherein the polyolefin resin (d) is a polypropylene resin.

[6] A block copolymer containing a polymer block (A) mainly composed of the vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound or a hydrogenated product thereof (a) 100 parts by weight The total content of the ethylene / α-olefin copolymer (b) and the oil (c) is 30 to 200 parts by weight, according to any one of [1] to [5]. Polymer composition.
[7] The ethylene / α-olefin copolymer (b) and the oil (c) are mixed in advance, and the polymer block (A) mainly composed of the vinyl aromatic compound and the conjugated diene compound are mainly composed. The block copolymer containing the polymer block (B) or the hydrogenated product (a) thereof and the polyolefin resin (d) are further kneaded, and the weight according to any one of the above [1] to [6] A method for producing a polymer composition, comprising obtaining a coalescence composition.
[8] The kneading viscosity at 100 ° C. of the mixture of the ethylene / α-olefin copolymer (b) and the oil (c) is 1 to 600 mm ² / s, as described in the above [7] A method for producing a polymer composition.
[9] A vibration damping material comprising the polymer composition according to any one of [1] to [6].
[10] A soundproof material comprising the polymer composition according to any one of [1] to [6].

  According to the present invention, a polymer composition excellent in vibration damping properties and moldability and suitable for producing a vibration damping material and a soundproof material, a method for producing the polymer composition, and a vibration damping material It is possible to provide a vibration damping material and a soundproof material that are excellent in performance and soundproofing.

FIG. 1 shows the kinematic viscosity at 40 ° C. of the mixture of the ethylene / α-olefin copolymer (b) and the oil (c) or the oil (c) and the loss of the polymer composition in Examples and Comparative Examples of the present application. It is a graph which shows the relationship with a tangent (tan-delta).

Hereinafter, the present invention will be specifically described. In the following description, “to” indicating a numerical range represents the following from the above unless otherwise specified.
The vibration damping material of the present invention is formed from the polymer composition of the present invention shown below. Moreover, although the polymer composition of this invention can be used for various uses, it is excellent in damping performance and can be used especially suitably for manufacture of a damping material and a soundproof material.

<Polymer composition>
The polymer composition of the present invention comprises a block copolymer containing a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound, or a hydrogenated product thereof ( and a), 100 ° C. kinematic viscosity of 300~5000mm ² / s, a 40 ° C. kinematic viscosity 4000~100000mm ² / s, the ethylene · alpha-olefin ethylene structural unit content of from 30 to 80 mol% Copolymer (b), oil (c) having a kinematic viscosity at 100 ° C. of 1 to 299 mm ² / s and a kinematic viscosity at 40 ° C. of 1 to 3999 mm ² / s, and MFR of 0.1 to 500 g / 10 And a polyolefin resin (d).

(A) A block copolymer containing a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound, or a hydrogenated product thereof. Polymer composition according to the present invention The component (a) is a block copolymer containing a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound, or a hydrogenated product thereof. . This block copolymer has a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound, and is hereinafter referred to as “A / B block copolymer”. Also referred to as “polymer”.

  Specific examples of the vinyl aromatic compound constituting the polymer block (A) include styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene. 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, monochlorostyrene, dichlorostyrene, methoxystyrene, indene, acenaphthylene and the like, and 1 of these vinyl aromatic compounds One kind or two or more kinds can be used. Of these, styrene is most preferred.

  The conjugated diene compound constituting the polymer block (B) is preferably a conjugated diene having 4 to 20 carbon atoms, and specific examples include butadiene, isoprene, hexadiene and the like. One kind or two or more kinds can be used. Of these, butadiene and isoprene are most preferred.

  The A / B block copolymer containing the polymer block (A) and the polymer block (B) has a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC of 30,000 to 500,000. It is preferable that it is 50,000-300,000. When the weight average molecular weight of the A / B block copolymer is 30,000 or more, mechanical properties such as compression set and strength at break of the molded product obtained from the polymer composition are improved, while 500,000 or less. If it is, moldability and workability are good. When the moldability is important, more preferably 50,000 to 300,000, the fluidity is high and the moldability is excellent, and when the mechanical property is important, more preferably 100,000 to 250, 000, particularly preferably 150,000 to 200,000 is excellent in mechanical properties such as compression set and strength at break.

  The ratio of the polymer block (A) to the polymer block (B) in the A / B block copolymer is the number average molecular weight of the A / B block copolymer, the polymer block (A), and the polymer block (B). Depending on the number average molecular weight of the polymer, the ratio of the polymer block (A) is generally 5 to 80% by weight and the ratio of the polymer block (B) is 95 to 95% based on the weight of the A / B block copolymer. It is preferably 20% by weight, more preferably 10 to 75% by weight of the polymer block (A) and 90 to 25% by weight of the polymer block (B), and 20 to 20% of the polymer block (A). More preferably, the polymer block (B) is 40 to 80% by weight at 40% by weight. In the A / B block copolymer, when the ratio of the polymer block (A) is 5% by weight or more (that is, the ratio of the polymer block (B) is 95% by weight or less), the A / B block The mechanical properties of the polymer composition containing the copolymer and the molded product obtained therefrom are good, while the proportion of the polymer block (A) is 80% by weight or less (that is, the polymer block ( When the proportion of B) is 20% by weight or more, the melt viscosity does not become too high and the moldability and workability are good.

  The A / B block copolymer may be either linear or branched into two or more, and at least one polymer block (A) and at least one branch in the molecule. What is necessary is just to have a polymer block (B), and the structure in particular is not restrict | limited. From the balance of mechanical properties, heat resistance and workability, an ABA type triblock structure is particularly preferable.

  Specific examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a styrene-butadiene / isoprene-styrene block copolymer. For example, a styrene-butadiene-styrene block copolymer means a block copolymer in the form of polystyrene block-polybutadiene block-polystyrene block.

  The production method of the A / B block copolymer is not particularly limited. For example, using a suitable polymerization initiator system, a vinyl aromatic compound such as styrene and a conjugated diene compound such as butadiene are sequentially polymerized in an inert solvent. Can be manufactured. Examples of the polymerization initiator system in this case include a mixed system of 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 organic compounds having a functional group such as an alkoxy group, an acyloxy group, or a halogen such as bis (2-methoxy- 2-propyl) benzene, bis (2-acetoxy-2-propyl) benzene, bis (2-chloro-2-propyl) benzene and the like. Furthermore, together with the above Lewis acid and organic compound, amides such as N, N-dimethylacetamide and esters such as ethyl acetate may be used as the third component as necessary. Further, as an inert solvent for polymerization, hexane, cyclohexane, methylcyclohexane, methyl chloride, methylene chloride and the like can be used.

  The linear A / B block copolymer can be obtained by, for example, (1) using a compound having one functional group that generates a Lewis acid and a cationic polymerization active species as a polymerization initiator system, After polymerizing to form a polymer block (A), a conjugated diene compound is added to the reaction system and polymerized to form a polymer block (B), and if necessary, a vinyl aromatic compound is further added. A method of forming a polymer block (A) by polymerization, (2) using a compound having two functional groups that generate a Lewis acid and a cationic polymerization active species as a polymerization initiator system, After polymerizing to form a polymer block (B), it can be produced by a method in which a vinyl aromatic compound is added to the reaction system and polymerization is performed to form a polymer block (A).

  The branched A / B block copolymer is prepared by first polymerizing a conjugated diene compound using, for example, a compound having three or more functional groups that generate a Lewis acid and a cationic polymerization active species as a polymerization initiator system. To form a polymer block (B), and then, a vinyl aromatic compound is added and polymerized to form a polymer block (A).

  In the polymer composition of the present invention, as the component (a), a hydrogenated product of the A / B block copolymer can be used. The use of a hydrogenated product is preferable in that heat resistance and weather resistance are improved by reducing the number of aliphatic double bonds in the A / B block copolymer by hydrogenation.

  In the present invention, as the hydrogenated A / B block copolymer used as the component (a), 90% to 100% of the aliphatic double bonds of the A / B block copolymer are hydrogenated, and 0 % To 10% aromatic double bonds are preferred, especially 99 to 100% aliphatic double bonds are hydrogenated and 0% to 5% aromatic double bonds are hydrogenated. What was formed is preferable. In such a hydrogenated A / B block copolymer, the polymer block (B) in which the aliphatic double bond is hydrogenated substantially becomes a block having a polyolefin structure.

  A known method can be employed for hydrogenation of the A / B block copolymer. Examples of the hydrogenation catalyst include nickel, porous diatomaceous earth, Raney nickel, copper dichromate, molybdenum sulfide, etc., and a carrier such as carbon carrying platinum, palladium, or the like.

  Hydrogenation is performed at an arbitrary pressure (for example, atmospheric pressure to 300 atmospheric pressure, preferably 5 to 200 atmospheric pressure), an arbitrary temperature (for example, 20 ° C. to 350 ° C.), and an arbitrary time (for example, 0.2 to 10 hours). Can do.

As the A / B block copolymer used as the component (a) according to the present invention, two or more A / B block copolymers having different properties such as molecular weight and styrene content may be used in combination.
The A / B block copolymer used as the component (a) is commercially available, and these commercially available products can be used. Non-hydrogenated products include, for example, Kraton "D Series", JSR "TR Series", Asahi Kasei "Tuffprene" and "Asaprene". Examples of hydrogenated products include “Septon” and “Hibler” manufactured by Kuraray Co., Ltd., “Tough Tech” manufactured by Asahi Kasei Co., Ltd., “Dynalon” manufactured by JSR, and “G Series” manufactured by Kraton Polymer.

(B) Ethylene / α-olefin copolymer The ethylene / α-olefin copolymer as the component (b) of the polymer composition according to the present invention has a kinematic viscosity at 100 ° C. of 300 to 5000 mm ² / s. , preferably 500~3500mm ² / s, more preferably 600~2500mm ² / s, more preferably 900~2500mm ² / s. (B) When the kinematic viscosity at 100 ° C. of the ethylene / α-olefin copolymer is 300 mm ² / s or more and 5000 mm ² / s or less, the vibration damping performance and handling properties of the obtained polymer composition and vibration damping material The balance is extremely good.

Ethylene · alpha-olefin copolymer component (b) of the polymer composition according to the present invention has a kinematic viscosity at 40 ° C. is 4000~100000mm ² / s, preferably 7000~60000mm ² / s, more Preferably it is 9000-40000 mm < ² > / s, More preferably, it is 15000-40000 mm < ² > / s. (B) kinematic viscosity at 40 ° C. of the ethylene · alpha-olefin copolymer, it is not more than 4000 mm ² / s or more 100,000 mm ² / s, the resulting polymer composition and the damping material damping performance and handling properties The balance is extremely good.

The vibration damping performance of the polymer composition was subjected to vibration with the molecular end of the block copolymer as the component (a) or the ethylene / α-olefin copolymer (b) intertwined with the hydrogenated product. In that case, it is presumed that the entanglement is derived from a behavior that can be solved. When the kinematic viscosity at 100 ° C. of the ethylene / α-olefin copolymer (b) is less than 300 mm ² / s, or the kinematic viscosity at 40 ° C. is less than 4000 mm ² / s, the block copolymer as the component (a) Alternatively, the entanglement with the hydrogenated product is difficult to occur, and the component (a) and the ethylene / α-olefin copolymer (b) move independently without being entangled. Hateful. When the kinematic viscosity at 100 ° C. of the ethylene / α-olefin copolymer (b) exceeds 5000 mm ² / s or the kinematic viscosity at 40 ° C. exceeds 100000 mm ² / s, the ethylene / α-olefin copolymer ( The number of molecular ends per unit volume in b) is relatively small, and the vibration damping performance is lowered. When the kinematic viscosity at 100 ° C. of the ethylene / α-olefin copolymer (b) exceeds 5000 mm ² / s or the kinematic viscosity at 40 ° C. exceeds 100000 mm ² / s, the component (a) and the ethylene / α-olefin Compatibility with the copolymer (b) is lowered, vibration damping and transparency are lowered, handling properties are lowered, and kneading and molding become difficult.

  The ethylene / α-olefin copolymer (b) is similar in structure to the polymer block (B) in which the aliphatic double bond of the A / B block copolymer of component (a) is hydrogenated. In addition, since it has a feature that entanglement is likely to occur, vibration damping performance is easily exhibited.

  The intrinsic viscosity [η] measured in decalin at 135 ° C. of the ethylene / α-olefin copolymer as the component (b) of the polymer composition according to the present invention is not particularly limited, but is preferably 0. 0.01 or more and 0.5 or less, more preferably 0.05 or more and 0.4 or less, and particularly preferably 0.09 or more and 0.3 or less. When the intrinsic viscosity [η] measured in decalin at 135 ° C. is decreased, the block copolymer or its hydrogenated product as the component (a) is less likely to be entangled, and the component (a) is copolymerized with ethylene / α-olefin. Since the union (b) moves independently without being entangled, the damping performance may be lowered. When the intrinsic viscosity [η] measured in decalin at 135 ° C. is increased, the number of molecular ends per unit volume of the ethylene / α-olefin copolymer (b) is relatively decreased, and the vibration damping performance may be deteriorated. . When the intrinsic viscosity [η] measured in decalin at 135 ° C. is increased, the compatibility between the component (a) and the ethylene / α-olefin copolymer (b) is decreased, and the vibration damping / transparency is decreased. Handling properties are reduced, making kneading and molding difficult.

  The ethylene / α-olefin copolymer (b) according to the present invention has an ethylene structural unit content of 30 to 80 mol%, preferably 40 to 75 mol%, more preferably 40 to 60 mol%. If the ethylene content is too much or too little, the crystallinity becomes high, and the flexibility, low temperature characteristics, and damping properties of the polymer composition and damping material may be lowered. On the other hand, if the ethylene content is too high or too low, the compatibility between the component (a) and the ethylene / α-olefin copolymer (b) may be reduced, and vibration damping / transparency may be reduced.

(B) The ethylene content of the ethylene / α-olefin copolymer can be measured by ¹³ C-NMR method. For example, it is described in the method described later and “Polymer Analysis Handbook” (published by Asakura Shoten, P163-170). Peak identification and quantification can be performed according to the method.

  Further, (b) α-olefin constituting the ethylene / α-olefin copolymer includes propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1, undecene- 1, C3-C20 α-olefins such as 1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1 It can be illustrated. (B) Two or more of these α-olefins may be used in combination in the ethylene / α-olefin copolymer. Among these α-olefins, α-olefins having 3 to 10 carbon atoms are preferable, and propylene is particularly preferable in terms of imparting good flexibility, vibration damping properties, and weather resistance to the polymer composition.

  The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer that is the component (b) of the polymer composition of the present invention is not particularly limited, but is usually 1.0 to 3.0, Preferably it is 1.4-2.5. When the molecular weight distribution is wide (Mw / Mn is large), it is not preferable because it contains many low molecular weight components that are not easily entangled with the component (a) and high molecular weight components that are inferior in compatibility.

  The (b) ethylene / α-olefin copolymer according to the present invention has a blockness (B value) measured by NMR of usually 0.9 or more, preferably 1.0 or more, and usually 1.5 or less. is there. The B value is a parameter indicating the randomness of the copolymer monomer chain distribution. When the B value is small, the crystallinity is high, and the flexibility and low temperature characteristics of the polymer composition are lowered.

  The (b) ethylene / α-olefin copolymer according to the present invention can be produced using a known method without limitation. For example, there is a method of copolymerizing ethylene and an α-olefin in the presence of a catalyst comprising a transition metal compound such as vanadium, zirconium, or titanium and an organoaluminum compound (organoaluminum oxy compound) and / or an ionized ionic compound. Can be mentioned. Such a method is described, for example, in International Publication No. 00/34420 pamphlet and JP-A-62-1121710.

The (b) ethylene / α-olefin copolymer according to the present invention has a kinematic viscosity at 100 ° C. satisfying 300 to 5000 mm ² / s as the whole (b) ethylene / α-olefin copolymer. Two or more ethylene / α-olefin copolymers having different properties such as kinematic viscosity and ethylene content may be used in combination.

  When two or more ethylene / α-olefin copolymers are used in combination, the preferred range of the ethylene structural unit content and molecular weight distribution of each ethylene / α-olefin copolymer is the above-mentioned ethylene / α-olefin copolymer weight. It is the same as the union (b). Further, the proportion of each ethylene / α-olefin copolymer used in combination can be arbitrarily changed as long as the definition of (b) ethylene / α-olefin copolymer is satisfied.

  Although not included in the component (b) of the present application, examples of the liquid polymer having the same viscosity as the component (b) include liquid polybutene. Liquid polybutene is generally obtained by isobutylene obtained by naphtha decomposition or the like and C4 hydrocarbon fraction containing butene-1, butene-2 or the like, or isobutylene obtained by refining the fraction, aluminum chloride, chloride Friedel-Crafts catalysts such as magnesium, boron fluoride, and titanium tetrachloride, or their complex compounds are used as catalysts, trace moisture in the reaction system, organic halides and hydrochloric acid are used as promoters, or promoters are used in particular. Without polymerization. Such liquid polybutene contains a large amount of tertiary carbon, so that the main chain is stiffer than the ethylene / α-olefin copolymer, and is considered to be inferior in flexibility modification performance. Moreover, since liquid polybutene contains many double bonds, it is easily oxidized by heat and sunlight, and is considered to be inferior in weather resistance. Although it is possible to hydrogenate part of the double bonds of the liquid polybutene using known methods, such as nickel or nickel molybdate catalysts, it is technically possible to hydrogenate the double bonds completely. Difficulty is practically impossible. Such liquid polybutenes are commercially available, such as JX “Nisseki Polybutene”, Ineos “Indopol”, BASF “Opanol”, ExxonMobil Chemical “Vistanex” and the like.

  The polymer composition according to the present invention may contain a small amount of a liquid polymer other than the component (b) such as the above-mentioned liquid polybutene in addition to the component (b) as long as the object of the present invention is not impaired. The content of the liquid polymer other than the component (b) can be, for example, 50 parts by weight or less, preferably 30 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of the component (a).

(C) Oil The oil which is the component (c) of the polymer composition according to the present invention has a 100 ° C. kinematic viscosity of 1 to 299 mm ² / s, preferably ² to 200 mm ² / s, more preferably 5 to 5 mm. 150 mm ² / s, more preferably from 8~100mm ² / s. (C) When the kinematic viscosity at 100 ° C. of the oil is 1 mm ² / s or less, there are many low-molecular-weight easily volatile components, and the heat resistance and fogging property of the polymer composition may be significantly deteriorated. On the other hand, if it exceeds 299 mm ² / s, the high molecular weight component is increased and the fluidity is lowered, so that the workability improvement effect may not be sufficiently obtained.

The (c) oil of the polymer composition according to the present invention has a kinematic viscosity at 40 ° C. of 1 to 3999 mm ² / s, preferably 5 to 3000 mm ² / s, more preferably 10 to 2000 mm ² / s. More preferably, it is 50-1000 mm < ² > / s. Oils having a kinematic viscosity at 40 ° C. of less than 1 mm ² / s have many low molecular weight readily volatile components, and the heat resistance and fogging properties of the polymer composition may be significantly deteriorated. On the other hand, if it exceeds 3999 mm ² / s, the high molecular weight component is increased and the fluidity is lowered, so that the workability improvement effect may not be sufficiently obtained.

  Examples of the oil that is the component (c) of the polymer composition according to the present invention include mineral oil obtained by refining petroleum, synthetic hydrocarbon oil obtained by polymerizing monomers such as ethylene and α-olefin, and the like. A conventionally well-known oil is mentioned. These can be used alone or in combination of two or more.

  Mineral oil generally has several grades depending on the method of refining, but as component (c), any of API classification groups (I) to (III) may be used. In general, mineral oils containing 0.5 to 10% wax are used. For example, a highly refined oil having a composition mainly composed of isoparaffin having a low pour point and a high viscosity index produced by a hydrogenolysis refining method can be used. Among them, the group of mineral oil products generally sold as process oils has a particularly low volatile content, and is suitable as a softening agent for the block copolymer or its hydrogenated product as component (a). (C) It is preferably used as an oil. Specific examples of the process oil include paraffinic process oil, aromatic process oil, and naphthenic process oil. Among them, paraffinic process oils with a low content of unsaturated components such as aromatic components are excellent in heat resistance and weather resistance and are preferably used. Further, synthetic oil (GTL) obtained by polymerizing natural gas by a Fischer-Trops reaction and performing hydrogenolysis purification can also be used.

Among these, process oil is preferable from the viewpoint of availability and low volatility, and paraffinic process oil is particularly preferable from the viewpoint of heat resistance and weather resistance.
Synthetic hydrocarbon oils include, for example, ethylene / α-olefin copolymers, α-olefin copolymers (PAO), alkylbenzenes, alkylnaphthalenes, and the like. These may be used alone or in combination of two or more. Can be used. Among these, a synthetic hydrocarbon oil composed of an ethylene / α-olefin copolymer has good compatibility with the component (a) and is particularly suitable as the (c) oil according to the present invention.

  The ethylene / α-olefin copolymer used as a synthetic hydrocarbon oil is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. As the α-olefin, propylene, 1-butene, 1- Pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene linear α-olefin, 3-methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6 Examples include α-olefins having a branch such as -methyl-1-undecene and 6,8-dimethyl-1-decene, preferably linear α-olefins. A fin, one kind or two or more kinds of these may be used if necessary. Among these α-olefins, α-olefins having 3 to 10 carbon atoms are preferable, and propylene is particularly preferable in terms of imparting good flexibility, vibration damping properties, and weather resistance to the polymer composition.

  The ethylene / α-olefin copolymer used as the synthetic hydrocarbon oil has an ethylene structural unit content of 30 to 80 mol%, preferably 40 to 75 mol%, more preferably 40 to 60 mol%. If the ethylene content is too much or too little, the crystallinity becomes high, and the flexibility, low temperature characteristics, and damping properties of the polymer composition and damping material are lowered. On the other hand, if the ethylene content is too much or too little, the compatibility between the component (a) and the oil (c) using the ethylene / α-olefin copolymer is lowered, and the vibration damping / transparency is lowered. .

The ethylene content of the ethylene / α-olefin copolymer used as the synthetic hydrocarbon oil can be measured by a ¹³ C-NMR method. For example, the method described later and “Polymer Analysis Handbook” (published by Asakura Shoten, P163-170). The peak can be identified and quantified according to the method described in (1).

  The intrinsic viscosity [η] measured in 135 ° C. decalin is not particularly limited for the ethylene / α-olefin copolymer used as the synthetic hydrocarbon oil, but is preferably 0.01 or more and 0.5 or less, More preferably, it is 0.02 or more and 0.30 or less, and particularly preferably 0.02 or more and 0.10 or less. When the intrinsic viscosity [η] measured in decalin at 135 ° C. becomes small, the entanglement with the component (a) hardly occurs, and the component (a) and the oil (c) using the ethylene / α-olefin copolymer are entangled. Since it does not fit and exercises independently, vibration control may be reduced. When the intrinsic viscosity [η] measured in decalin at 135 ° C. is increased, the number of molecular ends per unit volume of the ethylene / α-olefin copolymer (b) is relatively decreased, and the vibration damping performance may be lowered. . When the intrinsic viscosity [η] measured in decalin at 135 ° C. is increased, the compatibility between the component (a) and the oil (c) using the ethylene / α-olefin copolymer is reduced, and the vibration damping / transparent May decrease.

  Furthermore, such an ethylene / α-olefin copolymer generally has a number average molecular weight (Mn) of 100 to 30000, preferably 100 to 20000. When the number average molecular weight (Mn) is less than 100, low molecular weight components that are likely to volatilize increase, and heat resistance may deteriorate. On the other hand, when the number average molecular weight (Mn) exceeds 30000, the high molecular weight component increases and the processability improving effect may be reduced.

  The molecular weight distribution (Mw / Mn) of the oil (c) is not particularly limited, but is usually 1.0 to 3.0, preferably 1.4 to 2.5. When the molecular weight distribution (Mw / Mn) exceeds 3, generally, low molecular weight components that are likely to volatilize increase, and heat resistance may be deteriorated.

  The ethylene / α-olefin copolymer used as the oil (c) according to the present invention has a blockness (B value) measured by NMR of usually 0.9 or more, preferably 1.0 or more, usually 1 .5 or less. The B value is a parameter indicating the randomness of the copolymer monomer chain distribution. When the B value is small, the crystallinity is high, and the flexibility and low temperature characteristics of the polymer composition may be lowered.

  The ethylene / α-olefin copolymer used as the (c) oil according to the present invention can be produced using a known method without limitation. For example, there is a method of copolymerizing ethylene and an α-olefin in the presence of a catalyst comprising a transition metal compound such as vanadium, zirconium, or titanium and an organoaluminum compound (organoaluminum oxy compound) and / or an ionized ionic compound. Can be mentioned. Such a method is described, for example, in International Publication No. 00/34420 pamphlet and JP-A-62-1121710.

The α-olefin (co) polymer (PAO) used as such a synthetic hydrocarbon oil is a (co) polymer of an α-olefin having 6 to 20 carbon atoms, and the α-olefin (co) polymer is , A polymer of a monomer composed of at least one kind of α-olefin having 6 to 20 carbon atoms, or a copolymer with ethylene. Furthermore, a C3-C6 alpha olefin can also be contained as a copolymerization component as needed. Generally, since such higher poly-α-olefins do not have a continuous methylene chain, the structure of the polymer block (B) in which the aliphatic double bond of the A / B block copolymer is hydrogenated is used. Are not similar and inferior in compatibility with the A / B block copolymer as compared with the ethylene-α-olefin copolymer. In order to ensure compatibility, it is necessary to keep the molecular weight low, and it is preferable that the kinematic viscosity at 100 ° C. be in the range of 1 to 299 mm ² / s.

  The α-olefin (co) polymer (PAO) as described above is described in US Pat. No. 3,780,128, US Pat. No. 4,032,591, and JP-A-1-163136. It can be obtained by acid catalyzed oligomerization. It can also be obtained by a method using a catalyst system containing a metallocene compound. Such α-olefin (co) polymers (PAO) are commercially available, such as ExxonMobil Chemical, Inc. “Spectrasyn”, “Spectrasyn Plus”, “Spectrasyn Elite”, “Spectrasyn Ultra”, Ineos “Durasyn”, “Chemturon”, etc. There is.

  The alkylbenzenes and alkylnaphthalenes used as the oil (c) according to the present invention are usually dialkylbenzene or dialkylnaphthalene having an alkyl chain length of 6 to 14 carbon atoms. Such alkylbenzenes or alkylnaphthalenes are: Produced by Friedel-Craft alkylation reaction of benzene or naphthalene with olefins. The alkylated olefin used in the production of alkylbenzenes or alkylnaphthalenes may be a linear or branched olefin or a combination thereof. These production methods are described, for example, in US Pat. No. 3,909,432.

(D) Polyolefin-based resin The polymer composition of the present invention may optionally include (d) a polyolefin-based resin having an MFR (melt flow rate) of 0.1 to 500 g / 10 minutes.

The (d) component polyolefin resin that may be contained in the polymer composition of the present invention is a polymer or copolymer of at least one olefin monomer.
A polyolefin resin having an MFR of 0.1 to 500 g / 10 min has a kinematic viscosity at 100 ° C. of 20000 or more, and it is substantially difficult to measure the kinematic viscosity at 100 ° C. and 40 ° C. That according to (d) according to the invention a polyolefin resin are typically those kinematic viscosity at 100 ° C. is the kinematic viscosity at 5000mm ² / s, 40 ℃ greater than 100,000 mm ² / s.

  The (d) polyolefin resin according to the present invention is not particularly limited as long as it is a polymer mainly composed of olefin and has an MFR satisfying 0.1 to 500 g / 10 min. These olefin polymers can be used. For example, ethylene, propylene, butene-1, pentene-1, 4-methyl-1-pentene, hexene-1, heptene-1, octene-1, decene-1, undecene-1, dodecene-1, tridecene-1, Examples thereof include mono- or copolymers of α-olefins having 2 to 20 carbon atoms, such as tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, and eicosene-1. Specifically, high pressure method low density polyethylene, linear low density polyethylene (so-called LLDPE), medium density polyethylene, high density polyethylene, polypropylene, polypropylene random copolymer, polypropylene block copolymer, poly 1-butene, poly 4 -Methyl 1-pentene, low crystalline or amorphous ethylene / propylene random copolymer, ethylene / butene-1 random copolymer, olefin polymer such as propylene / butene-1 random copolymer alone or A composition containing two or more kinds, an ethylene / vinyl acetate copolymer (EVA), an ethylene / (meth) acrylic acid copolymer or a metal salt thereof, an ethylene-cyclic olefin copolymer, and the like can be given. The (d) polyolefin resin may contain a non-conjugated diene as an olefin copolymerization component. Specific examples of non-conjugated dienes include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6. -Chain non-conjugated dienes such as octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene Cyclic non-conjugated dienes such as 6-chloromethyl-5-isopropylenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl- Examples include triene such as 2,2-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene. Of these, 1,4-hexadiene and cyclic non-conjugated dienes, particularly dicyclopentadiene and 5-ethylidene-2-norbornene are preferably used. Furthermore, these polyolefin resins may be polymers obtained by graft modification with polar compounds such as maleic acid and silane compounds. Among these, an α-olefin polymer or copolymer having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, is desirable.

  Suitable examples of such (d) polyolefin-based resins include the above-mentioned polyethylene-based resins, polypropylene-based resins, polybutene-based resins, and the like, and in particular, polymers or copolymers mainly composed of propylene. Polypropylene resin is preferable in terms of improving the heat resistance and mechanical strength of the polymer composition and improving the solidification rate.

  Such (d) polyolefin resin is not particularly limited in intrinsic viscosity [η] measured in decalin at 135 ° C., but is preferably 0.5 dl / g or more and 5 dl / g or less, more preferably Is 0.8 or more and 4 or less, more preferably 1.0 or more and 3 or less. When the intrinsic viscosity [η] measured in decalin at 135 ° C. decreases, the mechanical strength of the polymer composition decreases. As the intrinsic viscosity [η] increases, the moldability deteriorates.

  Examples of the polypropylene resin include a propylene homopolymer, and a copolymer of propylene and ethylene and at least one monomer selected from ethylene and an α-olefin having 4 to 20 carbon atoms. When the polypropylene resin is a copolymer, the constituent unit derived from propylene is preferably 90 mol% or more, and more preferably 93 to 99 mol%.

In the present invention, (d) MFR (melt flow rate) of the polyolefin-based resin is a value measured according to JISK7210, and is 190 ° C. for polyethylene (polymer or copolymer mainly composed of ethylene). The value measured under the condition of 16 kg load means the value measured under the conditions of 230 ° C. and 2.16 kg load for polyolefin resins other than polyethylene such as polypropylene. The MFR is preferably 0.1 to 200 g / 10 minutes, more preferably 0.5 to 100 g / 10 minutes, and particularly preferably 1 to 30 g / 10 minutes. When MFR becomes small, the mechanical strength of the polymer composition decreases, and when MFR becomes large, moldability tends to deteriorate.
The (d) polyolefin resin according to the present invention may be a combination of two or more polyolefin resins having different properties such as the type and MFR.

Polymer Composition The polymer composition of the present invention comprises the above-described component (a) (polymer block (A) mainly composed of vinyl aromatic compound and polymer block (B) mainly composed of conjugated diene compound). Block copolymer or hydrogenated product thereof (a)) and the component (b) described above (the kinematic viscosity at 100 ° C. is 300 to 5000 mm ² / s, and the kinematic viscosity at 40 ° C. is 4000 to 100000 mm ² / s. An ethylene / α-olefin copolymer (b) having an ethylene structural unit content of 30 to 80 mol%, and the component (c) described above (kinematic viscosity at 100 ° C. of 1 to 299 mm ² / s). There, a composition kinematic viscosity at 40 ° C. contains as an essential component and an oil (c)) is 1~3999mm ² / s, the above-mentioned component (d) (MFR optionally 0.1 Containing 500 g / 10 min at which polyolefin resin (d)).

  In such a polymer composition of the present invention, the component (b) is 1 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the component (a). The component (c) is contained in an amount of 1 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight. When the content of component (b) with respect to 100 parts by weight of component (a) is 1 part by weight or more, the effect of improving damping properties by component (b) is sufficiently exerted, and at 200 parts by weight or less. When it exists, since the bleed-out of a polymer composition does not arise easily, it is preferable. When the content of the component (c) with respect to 100 parts by weight of the component (a) is 30 parts by weight or more, the moldability improving effect by the component (c) is sufficiently exerted, and is 200 parts by weight or less. The bleed-out of the polymer composition is less likely to occur, which is preferable.

  Further, when the total content of the component (b) and the component (c) is 30 parts by weight to 200 parts by weight, preferably 50 to 150 parts by weight with respect to 100 parts by weight of the component (a), It is preferable in that it has a good balance of vibration damping properties, moldability, and flexibility and hardly causes bleed out.

  Moreover, (d) component is contained in the ratio of 0-100 weight part with respect to 100 weight part of (a) component, Preferably it is 1-80 weight part, More preferably, it is 10-60 weight part. When the polymer composition of this invention contains (d) component, the heat resistance of a polymer composition, mechanical strength, and a solidification rate improve, and it is preferable.

When the polymer composition of the present invention has (c) the 100 ° C. kinematic viscosity of oil as V _C and (b) the 100 ° C. kinematic viscosity of the ethylene / α-olefin copolymer as V _B , V _B and The difference from V _C is preferably in the following relationship.
V _B −V _C ≧ 200 mm ² / s
The difference (V _B −V _C ) between V _B and V _C is preferably 200 mm ² / s or more, more preferably 500 mm ² / s or more, and particularly preferably 1000 or more. The upper limit of the difference between V _B and V _C is usually 4999 mm ² / s. When the difference between V _B and V _C is in the above relationship, it is excellent in terms of the balance between vibration damping properties and handling properties.

  The polymer composition of this invention may contain components other than said (a), (b), (c), (d) in the range which does not impair the objective of this invention. The components that may be included in the polymer composition of the present invention include resin components other than the above (a), (b), (c), and (d), various weather resistance stabilizers, heat resistance stabilizers, and antioxidants. UV absorber, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, nucleating agent, lubricant, pigment, dye, anti-aging agent, hydrochloric acid absorbent, inorganic or organic filler, organic or inorganic Examples include foaming agents, crosslinking agents, co-crosslinking agents, crosslinking aids, pressure-sensitive adhesives, softeners, flame retardants, and the like.

  As the filler, inorganic fillers are preferable, and powder fillers such as mica, carbon black, silica, calcium carbonate, talc, graphite, stainless steel, and aluminum; and fibrous fillers such as glass fiber and metal fiber are exemplified. it can. Among these, mica is preferable because it has an effect of improving the attenuation. The content of the filler in the polymer composition of the present invention is 150 parts by weight or less, preferably 30 to 100 parts by weight with respect to a total of 100 parts by weight of the components (a), (b), (c) and (d). The amount is desirably about 100 parts by weight.

Production of Polymer Composition The polymer composition of the present invention can be produced by kneading (melt-kneading) each component by a conventionally known method. Kneading is performed after performing a step of mixing two or more components in advance or without a mixing step. A mixing process may be performed by mixing each component of a composition simultaneously, or may be performed sequentially, for example, can be mixed with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, etc. The kneading can be produced by adopting a method of granulation, molding or pulverization after melt kneading with a single screw extruder, twin screw extruder, plast mill, kneader, kneader ruder, Banbury mixer or the like. In the kneading, the components of the composition may be charged simultaneously into the kneading part or sequentially, and the mixture having undergone the above-described mixing step may be charged all at once.

  When the polymer composition of the present invention is produced by kneading the mixture (b) and the component (c) in advance and kneading the mixture with the component (a) and the component (d), It is preferable at the point which can provide damping property, improving the handleability of a certain (b) component. By kneading the component (b) and the component (c) in advance when kneading the polymer composition, the viscosity of the liquid component becomes a certain level or less and can be handled in a lump. As a result, handling is improved, such as easy metering, less load on the pump when feeding to the extruder, and faster impregnation rate into component (a).

Moreover, the 100 degreeC kinematic viscosity of the mixture which mixed (b) and (c) previously is 1-600 mm < ² > / s, Preferably it is 5-500 mm < ² > / s, Most preferably, it is 10-300 mm < ² > / s, 40 degreeC kinematic viscosity. Is 1 to 10000 mm ² / s, preferably 5 to 6000 mm ² / s, particularly preferably 10 to 4000 mm ² / s, which is excellent in the balance between handling property and vibration damping property. In particular, the 40 ° C. kinematic viscosity of the blend is close to the handling temperature at the time of kneading, and is preferably 10,000 mm ² / s or less because of excellent handling properties. As a result of earnest examination this time, by mixing (b) and (c) in advance, (b) an ethylene / α-olefin copolymer having the same handling property and having a kinematic viscosity of 1 to 100 ° C. It has been found that the value of loss tangent tan δ is larger than that obtained when (c) the oil of 299 mm ² / s is used alone, and excellent vibration damping can be obtained. The reason for this is not clear, but it is considered that the high-viscosity component effectively contributes to the improvement of vibration damping properties and at the same time the low-viscosity component can improve the handling property.

  The polymer composition of the present invention preferably has a loss tangent tan δ (E ″ / E ′) of dynamic viscoelasticity measured in a tensile mode at 0 ° C. and a frequency of 1 Hz of 0.01 or more. It is more preferably 03 or more, more preferably 0.05 or more, and further preferably 0.10 or more. As the value of the loss tangent tan δ increases, the energy is absorbed, the rebound resilience decreases, and the damping effect tends to increase. Specifically, the loss tangent tan δ can be obtained by a measurement method described later. Since the polymer composition of the present invention has an excellent vibration damping effect, it is particularly suitably used as a vibration damping material and its raw material. When tan δ is 0.01 or more, the polymer composition is preferable because it exhibits an excellent vibration damping effect. The upper limit of the value of the loss tangent tan δ is not particularly limited, but can be, for example, 5.00 or 3.00. Practically, an upper limit of 2.00 is sufficient.

  The polymer composition of the present invention has a melt flow rate (MFR) based on ASTM D1238 at a load of 2.16 kg at 190 ° C. of 0.1 to 200 g / 10 min, more preferably 0.5 to 100 g / 10 min, Preferably it is 1-50 g / 10min. When the MFR value is within this range, it is preferable because the balance between mechanical strength and moldability is excellent, and a good molded body appearance is easily obtained particularly during extrusion molding.

  The polymer composition of the present invention preferably has a surface hardness (instantaneous value) based on ASTM D2240 of 5 to 90, more preferably 5 to 70, and even more preferably 5 to 60. If the surface hardness exceeds this range, the flexibility is lowered and the tactile sensation is deteriorated. When the surface hardness is below this range, the mechanical strength is lowered.

  The polymer composition of the present invention has excellent vibration damping properties, vibration proofing properties, sound absorption properties, etc., low environmental impact, excellent moldability, heat resistance, flexibility and rubber elasticity, and no stickiness. In addition, it has excellent durability.

  The polymer composition of the present invention can be used without limitation for various applications, but because of its excellent vibration damping effect, it is preferably used for manufacturing applications such as a vibration damping material, a vibration damping material, a sound absorbing material, and a soundproofing agent. And can be particularly suitably used as a raw material for producing vibration damping materials and soundproofing materials.

Molded body The polymer composition of the present invention described above can be appropriately molded by a conventionally known method and used as a molded body. Examples of the molding method include injection molding, various extrusion moldings, compression molding, calendar molding, and vacuum molding. Moreover, it can be foamed by a known method using a known chemical foaming agent at the time of molding or a known physical foaming agent such as carbon dioxide gas, nitrogen gas, water, etc., to obtain a foamed molded product.

  The polymer composition can be used in combination with a hard resin or metal support. There is no restriction | limiting in particular as hard resin, Engineering plastics, such as polyolefin, such as a polypropylene, polyethylene, polybutene, polyamide, polycarbonate, polyethylene terephthalate, polyacetal, polyphenylene ether, polybutylene terephthalate, polysulfone, a polyimide, can be used. The metal is not particularly limited, and is appropriately selected from, for example, a cold-rolled steel sheet, a galvanized steel sheet, an aluminum / zinc alloy-plated steel sheet, a stainless steel sheet, an aluminum plate, an aluminum alloy plate, a magnesium plate, and a magnesium alloy plate. Can be used. Moreover, what injection-molded magnesium can also be used.

  As a method of combining the polymer composition with the support, a conventionally known molding method such as injection molding or extrusion molding can be employed. Although not particularly limited, for example, a hard resin as a support is melt-injected into a mold, and then the polymer composition of the present invention is melt-injected and molded onto the surface of the hard resin molding. An injection two-color molding method in which the polymer composition is laminated and integrated can be employed. Alternatively, first, a hard resin is melt-injected and molded into a mold, the molded product is inserted into another mold, and the polymer composition of the present invention is melt-injected and molded on the surface thereof to form a plastic molded product. It is possible to employ an insert molding method in which the polymer composition is laminated and integrated on the surface. Alternatively, a metal support can be inserted into a mold, the polymer composition of the present invention can be melt injection molded on the surface, and the polymer composition can be laminated on the surface of a plastic molded product. . Alternatively, it is possible to employ extrusion two-color molding in which a support and the polymer composition of the present invention are simultaneously extruded in a multilayer form with a molding machine having a plurality of extruders. Or the molded object obtained from a polymer composition can also be fixed to the surface of a support body using various adhesives.

  The molded product obtained from the polymer composition of the present invention is not limited in its shape and use at all. Damping materials, vibration-proof materials, sound-absorbing materials, sound-proof materials, interior materials, skin materials, grips, seals It can be used for materials, belts, and the like, and final applications include various automotive parts, industrial parts, household electrical appliances, sports equipment, toys, tableware, medical parts, and the like. Especially, it can use suitably for a vibration damping material, a vibration proof material, a sound absorption material, and a sound insulation material, and can use it especially suitably for the use of a vibration damping material or a sound insulation material.

<Damping material>
The vibration damping material according to the present invention is formed from the above-described polymer composition of the present invention. The vibration damping material according to the present invention may be formed only from the polymer composition of the present invention, or may be formed by combining the polymer composition of the present invention and another material.

  The polymer composition according to the present invention and the vibration damping material formed from the polymer composition are used for automobiles, railways, aircraft, ships, electrical and electronic equipment, information-related equipment, acoustic equipment such as speakers, printing for printers, etc. It can be suitably used for various vibration damping applications or vibration damping applications such as equipment, and can be particularly suitably used as a vibration damping material / vibration damping material for automobiles. For example, in a tire, improvement in vibration damping contributes to running stability.

<Soundproof material>
The soundproofing material according to the present invention is formed from the above-described polymer composition of the present invention. The soundproofing material according to the present invention may be formed only from the polymer composition of the present invention, or may be formed by combining the polymer composition of the present invention and another material.

  The polymer composition according to the present invention and the soundproofing material formed from the polymer composition are used for various soundproofing applications such as automobiles, railways, aircraft, ships, electrical and electronic equipment, information-related equipment, and acoustic equipment such as speakers. It can be preferably used.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the following examples and comparative examples, each physical property was measured or evaluated by the following method.

[Ethylene content, propylene content, blockness (B value)]
The ethylene content, propylene content and blockness (B value) in the ethylene / propylene copolymer obtained in Production Example were measured by ¹³ C-NMR using the following apparatus and conditions.

Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / heavy benzene (80/20% by volume) as a solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, 27.50 ppm as standard for chemical shift Measured as a value.

The B value is a parameter indicating the randomness of the copolymerization monomer chain distribution, and is preferably in the range of 1.0 to 1.4. The B value is an index representing the composition distribution state of the structural units in the copolymer chain, and can be calculated by the following equation.
B value = POE / (2PO · PE)
(Wherein PE and PO are the mole fraction of the ethylene component and the mole fraction of the α-olefin component, respectively, contained in the ethylene / α-olefin random copolymer, and POE is the total dyad (dyad)). ) Ratio of ethylene / α-olefin alternating chain number to chain number.)

Ethylene content, propylene content, PE, PO and POE values from the measured ¹³ C-NMR spectrum as described above, G. J. et al. Ray (Macromolecules, 10, 773 (1977)), J. MoI. C. Randall (Macro-molecules, 15, 353 (1982)), K. et al. It can be determined based on the report of Kimura (Polymer, 25, 4418 (1984)).

[Kinematic viscosity]
Based on ASTM D445, the measurement was performed using a fully automatic viscometer CAV-4 manufactured by Canon.

[Loss tangent (tan δ)]
Using a 1 mm thick press sheet obtained by press molding, a strip of 5 mm width necessary for dynamic viscoelasticity measurement was cut out. Using TA Instruments RSA-III, the temperature dependence of dynamic viscoelasticity was measured while increasing the temperature at a rate of 3 ° C./min from −60 to 150 ° C. at a frequency of 1 Hz. The value of loss tangent (tan δ) due to the glass transition temperature was measured, and tan δ at 0 ° C. was determined.

[surface hardness]
In accordance with ASTM D2240, two 2 mm-thick sheets obtained by press molding were overlapped, and the surface hardness (Shore A, instantaneous value) was measured.

[Molecular weight (Mw, Mn) and molecular weight distribution (Mw / Mn)]
(Method A): (a) Measurement of hydrogenated product of A / B block copolymer The molecular weight was measured using a liquid chromatograph: Waters ALC / GPC150-C plus type (suggested refractometer detector integrated type), column As a mobile phase medium, two GMH6-HT × 2 and GMH6-HTL × 2 manufactured by Tosoh Corporation were connected in series, and the flow rate was measured at 140 ° C. at a flow rate of 1.0 ml / min.
Mw / Mn value was calculated by analyzing the obtained chromatogram by a known method using a calibration curve using a standard polystyrene sample. The measurement time per sample was 60 minutes.

(Method B): Measurement in Production Examples 1 to 5 The following liquid chromatography pump, sampling device, gel permeation chromatography (GPC) column, and differential refractive index detector (RI detector) are connected to perform GPC measurement. And decided.
Liquid chromatography device: Waters 515 HPLC Pump
Sampling device: Waters 717 plus Autosampler device Mobile phase: THF (containing stabilizer, grade for liquid chromatography)
Column: One MIXED-D made by PL and one 500 mm made by PL were connected in series.
Sample concentration: 5 mg / mL
Mobile phase flow rate: 1.0 mL / min Measurement temperature: Normal temperature calibration standard sample: EasyCal PS-1 manufactured by PL

[Intrinsic viscosity [η] measured in decalin at 135 ° C.]
The intrinsic viscosity [η] [dL / g] was measured by using a fully automatic intrinsic viscometer manufactured by Rouen Co., Ltd. at a temperature of 135 ° C. and a measurement solvent: decalin.

[Melt flow rate (MFR)]
Based on ASTM D1238, the melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. was measured.

[Production Example 1]
Ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl _1.5 ) adjusted to 96 mmol / L by adding 1 liter of dehydrated and purified hexane to a continuous polymerization reactor with a stirring blade with a capacity of 2 liters sufficiently purged with nitrogen A hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 16 mmol / l as a catalyst was further supplied in an amount of 500 ml / h continuously for 1 hour, and hexane was added in an amount of 500 ml / h. It was continuously fed in an amount of 500 ml / h. On the other hand, from the upper part of the polymerization vessel, the polymerization solution was continuously extracted so that the polymerization solution in the polymerization vessel was always 1 liter. Next, ethylene gas was supplied in an amount of 47 L / h, propylene gas in an amount of 47 L / h, and hydrogen gas in an amount of 20 L / h using a bubbling tube. The copolymerization reaction was carried out at 35 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

  Thereby, a polymerization solution containing an ethylene / propylene copolymer was obtained. The obtained polymerization solution was deashed with hydrochloric acid, and then poured into a large amount of methanol to precipitate an ethylene / propylene copolymer, followed by drying under reduced pressure at 130 ° C. for 24 hours to obtain an ethylene / propylene copolymer. (B-1) was obtained. The analysis result of the obtained copolymer (b-1) is shown in Table 1.

[Production Examples 2 to 5]
In Production Example 1, ethylene / propylene copolymers listed in Table 1 were obtained by appropriately adjusting the supply amount of ethylene gas, the supply amount of propylene gas, and the supply amount of hydrogen gas. Table 1 shows the analysis results of the obtained ethylene / propylene copolymers.

[Example 1]
As component (a) (block copolymer or hydrogenated product thereof), 100 parts by weight of polystyrene-poly (ethylene / propylene) -polystyrene block copolymer (SEPS) (a-1) is used. -60 parts by weight of the ethylene / propylene copolymer (b-2) obtained in Production Example 2 was used as the olefin copolymer (b), and 40 parts by weight of PW-100 was used as the oil (c). These are blended, using a lab plast mill (biaxial batch type melt blending device) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge of 50 g (device batch volume = 60 cm ³ ), 50 rpm, 15 minutes Melt-kneaded below. The obtained resin composition was press-molded under conditions of preheating 200 ° C., 5 minutes, pressure 200 ° C., 3 minutes, cooling 10 ° C., and 5 minutes to obtain a sheet-like polymer composition (1).

Various physical properties were measured using this. The results are shown in Table 2.
Further, the ethylene / α-olefin copolymer (b) and the oil (c) were measured in a 100 ml beaker according to the above weight ratio, mixed with a magnetic stirrer for 10 minutes while being heated to 60 ° C., and then 100 ° C. and 40 ° C. The kinematic viscosity at 0 ° C. was measured. The results are shown in Table 4.

[Examples 2 to 11 and Comparative Examples 1 to 5]
Except having changed the kind and quantity ratio of the component to mix | blend as Table 2-Table 5, it melt-kneaded similarly to Example 1, and press-molded, and obtained the sheet-like polymer composition.

Various physical properties were measured using this. The results are shown in Tables 2 to 3.
Further, the ethylene / α-olefin copolymer (b) and the oil (c) were measured in a 100 ml beaker according to the above weight ratio, mixed with a magnetic stirrer for 10 minutes while being heated to 60 ° C., and then 100 ° C. and 40 ° C. The kinematic viscosity at 0 ° C. was measured. The results are shown in Tables 4 and 5.

[Comparative Example 6]
An attempt was made to obtain a sheet-like polymer composition by melt-kneading and press-molding in the same manner as in Example 3 except that the types and amount ratios of the components to be blended were changed as shown in Table 3. However, even after kneading, the polymer composition was not well-organized, resulting in remarkable bleed out, and could not be formed into a sheet by press molding. This is probably because the compatibility between the high viscosity higher poly-α-olefin and the block copolymer (a) is low.

  Further, according to the above weight ratio, the high-viscosity high-grade poly-α-olefin (b′-3) and the oil (c) are measured in a 100 ml beaker and mixed with a magnetic stirrer while heating at 60 ° C. for 10 minutes. The kinematic viscosities at ° C and 40 ° C were measured, respectively. The results are shown in Table 5.

[Comparative Example 7]
Except having changed the kind and quantity ratio of the component to mix | blend as Table 3, it melt-kneaded similarly to Example 3, and press-molded, and obtained the sheet-like polymer composition.

  Various physical properties were measured using this. The results are shown in Table 3 and compared with Example 3. In Comparative Example 7 using liquid polybutene, although tan δ was large and the expression of vibration damping was observed, the surface hardness increased and the flexibility was remarkably deteriorated. This is probably because the liquid polybutene has a structure containing a large amount of tertiary carbon, so that the main chain is stiffer than the ethylene / α-olefin copolymer and the flexibility modification performance is poor.

In addition, according to the above weight ratio, liquid polybutene (b′-4) and oil (c) are measured in a 100 ml beaker and mixed with a magnetic stirrer while heating to 60 ° C. for 10 minutes, and then the movement at 100 ° C. and 40 ° C. is performed. Each viscosity was measured. The results are shown in Table 5.
In these Examples and Comparative Examples (Tables 2 to 5), each component used is as follows.

a-1: Polystyrene-poly (ethylene / propylene) -polystyrene block copolymer (SEPS) (Septon (trademark) 2007, manufactured by Kuraray Co., Ltd., styrene content: 30% by weight, MFR ₂₃₀ ° C. = 2.4 g / 10 minutes, Mw = 80,000)
a-2: Polystyrene-poly (ethylene / butylene) -polystyrene block copolymer (SEBS) (Septon (trademark) 8007, manufactured by Kuraray Co., Ltd., styrene content: 30% by weight, MFR ₂₃₀ ° C. = 2 g / 10 min. , Mw of copolymer = 90,000)
b-1, b-2: As shown in Table 1 above, b'-3: High viscosity higher poly-α-olefin (manufactured by ExxonMobil Chemical, Spectra Syn Ultra (trademark) 1000, kinematic viscosity at 100 ° C. = 1000 mm ² / s)
b′-4: Liquid polybutene (manufactured by JX, Nisseki Polybutene (trademark) 1900, kinematic viscosity at 100 ° C. = 3710 mm ² / s)
c-1 to c-3: as shown in Table 1 c-4: paraffinic process oil (manufactured by SK Lubricants, YUBASE ™ -4, 100 ° C. kinematic viscosity = 4.25 mm ² / s, 40 ° C. kinematic viscosity = 19.5 mm ² / s)
c-5: Higher poly-α-olefin (manufactured by Neste, NEXBASE (trademark) 2004, 100 ° C. kinematic viscosity = 4 mm ² / s, 40 ° C. kinematic viscosity = 123 mm ² / s)
c-6: Paraffin-based process oil (manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-100, 100 ° C. kinematic viscosity = 12 mm ² / s, 40 ° C. kinematic viscosity = 102 mm ² / s)
c-7: Paraffin-based process oil (manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-380, 100 ° C. kinematic viscosity = 30 mm ² / s, 40 ° C. kinematic viscosity = 380 mm ² / s)
d-1: Homopolypropylene (manufactured by Prime Polymer, Prime Polypro ™)
J105G, MFR ₂₃₀ ℃ = 10g / 10min)

  In addition, among the above examples, (a) component a-1: 100 parts by weight, and (b) component and (c) a total of 100 parts by weight of the polymer composition, and comparison Among the examples, for the polymer composition comprising (a) component a-1: 100 parts by weight and (c) component 100 parts by weight, the loss tangent tan δ is expressed as (b) component and (c) component. The graph plotted with respect to kinematic viscosity in 40 degreeC of a mixed article or (c) component is shown in FIG. From this graph, compared to the comparative example using only the component (c) without using the component (b), the example using the component (b) and the component (c) has the same kinematic viscosity at 40 ° C. In this case, it is understood that the loss tangent tan δ increases and exhibits excellent vibration damping properties.

[Example 12]
In Example 3, a 15 mmφ twin-screw extruder (manufactured by Nikko Steel) was used instead of Toyo Seiki's Laboplast Mill (two-screw batch melt blending device), and the conditions were a setting temperature of 220 ° C. and a rotation speed of 50 rpm. It was melt-kneaded in the same manner as in Example 3 except that it was melt-kneaded below. The pellet-shaped component (a) was charged from a hopper, and the liquid component (b) and component (c) were side-fed separately from the extruder cylinder using two pumps. The measured value of loss tangent (tan δ) of the sheet-like polymer composition obtained by press molding the obtained kneaded body was equivalent to that of Example 3.

[Example 13]
In Example 12, melt kneading was performed in the same manner as in Example 12 except that the components (b) and (c) mixed in advance were used. The 100 ° C. kinematic viscosity of component (b) and component (c) mixed in advance was 174 mm ² / s. By mixing (b) component and (c) component in advance, it is possible to feed with one pump and to suppress the load on the pump compared to when (b) component is fed alone. I was able to. The measured value of loss tangent (tan δ) of the sheet-like polymer composition obtained by press molding the obtained kneaded body was equivalent to that of Example 3.

[Example 14]
In Example 12, the pulverized powdery component (a) was impregnated with the components (b) and (c) previously mixed, and melt-kneaded in the same manner as in Example 12 except that the components were charged all at once into the extruder hopper. . The 100 ° C. kinematic viscosity of component (b) and component (c) mixed in advance was 174 mm ² / s. By mixing in advance, the impregnation rate into the component (a) was faster than when added separately. In addition to the fact that kneading was possible without using pump equipment, the operation at the time of metering was simplified, and the torque at the time of kneading was stabilized. The measured value of loss tangent (tan δ) of the sheet-like polymer composition obtained by press molding the obtained kneaded body was equivalent to that of Example 3.

[Example 15]
In Example 12, except that the pulverized powdery component (a) was impregnated with the component (c) and charged from an extruder hopper, and the component (b) was further side-feeded and melt-kneaded using a pump. Melt kneading was carried out in the same manner as in Example 12. By impregnating the component (a) with the component (c) having a low viscosity, an effect of stabilizing the torque during the kneading was observed. The measured value of loss tangent (tan δ) of the sheet-like polymer composition obtained by press molding the obtained kneaded body was equivalent to that of Example 3.

[Example 16]
In Example 11, instead of a lab plast mill (two-screw batch melt blending device) manufactured by Toyo Seiki Co., Ltd., using a 15 mmφ twin-screw extruder (manufactured by Nikko Steel), conditions of a set temperature of 220 ° C. and a rotation speed of 50 rpm It was melt-kneaded in the same manner as in Example 11 except that it was melt-kneaded below. The pellet-shaped component (a) was charged from a hopper, and the liquid component (b) and component (c) were separately side-fed to the extruder cylinder using two pumps. With respect to the sheet-like polymer composition obtained by press-molding the obtained kneaded body, the measured value of loss tangent (tan δ) was equivalent to that of Example 11.

[Example 17]
In Example 16, melt kneading was performed in the same manner as in Example 16 except that the components (b) and (c) mixed in advance were used. The 100 ° C. kinematic viscosity of component (b) and component (c) mixed in advance was 174 mm ² / s. By mixing (b) component and (c) component in advance, it is possible to feed with one pump and to suppress the load on the pump compared to when (b) component is fed alone. I was able to. With respect to the sheet-like polymer composition obtained by press-molding the obtained kneaded body, the measured value of loss tangent (tan δ) was equivalent to that of Example 11.

[Example 18]
In Example 16, the pulverized powdery component (a) was impregnated with the components (b) and (c) previously mixed, and melt-kneaded in the same manner as in Example 16 except that the components were charged all at once into the extruder hopper. . The 100 ° C. kinematic viscosity of component (b) and component (c) mixed in advance was 174 mm ² / s. By mixing in advance, the impregnation rate into the component (a) was faster than when added separately. In addition to the fact that kneading was possible without using pump equipment, the operation at the time of metering was simplified, and the torque at the time of kneading was stabilized. With respect to the sheet-like polymer composition obtained by press-molding the obtained kneaded body, the measured value of loss tangent (tan δ) was equivalent to that of Example 11.

[Example 19]
In Example 16, except that the pulverized powdery component (a) was impregnated with the component (c) and charged from the extruder hopper, and the component (b) was further side-feeded and melt-kneaded using a pump. It was melt-kneaded in the same manner as in Example 16. By impregnating the component (a) with the component (c) having a low viscosity, an effect of stabilizing the torque during the kneading was observed. With respect to the sheet-like polymer composition obtained by press-molding the obtained kneaded body, the measured value of loss tangent (tan δ) was equivalent to that of Example 11.

  The polymer composition according to the present invention, and the vibration damping material and soundproofing material formed from the polymer composition are automobiles, railways, aircraft, ships, electrical and electronic equipment, information-related equipment, acoustic equipment such as speakers, and printing equipment such as printers. It can be suitably used for various vibration control applications such as tires, vibration isolation applications, or soundproof applications.

Claims (9)

(A) 100 parts by weight of a hydrogenated block copolymer containing a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound;
(B) 100 ° C. kinematic viscosity of 300~5000mm ² / s, a 40 ° C. kinematic viscosity 4000~100000mm ² / s, the ethylene · alpha-olefin interpolymer of ethylene structural unit content of from 30 to 80 mol% 1 to 200 parts by weight of polymer,
(C) 1 to 200 parts by weight of oil having a 100 ° C. kinematic viscosity of 1 to 299 mm ² / s and a 40 ° C. kinematic viscosity of 1 to 3999 mm ² / s;
(D) MFR is seen containing a 0 to 80 parts by weight of polyolefin resin is 0.1 to 500 g / 10 min, and,
With respect to 100 parts by weight of the hydrogenated product (a) of the block copolymer containing the polymer block (A) mainly composed of the vinyl aromatic compound and the polymer block (B) mainly composed of the conjugated diene compound, The polymer composition whose sum total of content of the said ethylene-alpha-olefin copolymer (b) and the said oil (c) is 30-150 weight part .   A block copolymer containing a polymer block (A) mainly composed of the vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound, or a hydrogenated product thereof (a) is a vinyl aromatic compound. 2. The polymer composition according to claim 1, which is a hydrogenated product of a block copolymer containing a polymer block (A) mainly comprising a conjugated diene compound and a polymer block (B) mainly comprising a conjugated diene compound. The 100 ° C. kinematic viscosity V _{B of the} ethylene / α-olefin copolymer (b) and the 100 ° C. kinematic viscosity V _{C of the} oil (c) are in the following relationship. Polymer composition.
V _B −V _C ≧ 200 mm ² / s The polymer composition according to any one of claims 1 to 3, wherein the ethylene / α-olefin copolymer (b) has a 100 ° C kinematic viscosity of 500 to 3500 mm ² / s.   The polymer composition according to any one of claims 1 to 4, wherein the polyolefin resin (d) is a polypropylene resin. The ethylene / α-olefin copolymer (b) and the oil (c) are mixed in advance, and the polymer block (A) mainly composed of the vinyl aromatic compound and the polymer mainly composed of a conjugated diene compound. The block copolymer containing the block (B) or its hydrogenated product (a) and the polyolefin resin (d) are further kneaded to obtain the polymer composition according to any one of claims 1 to 5. method for producing a polymer composition according to feature. The polymer composition according to claim 6 , wherein the mixture of the ethylene / α-olefin copolymer (b) and the oil (c) has a kinematic viscosity at 100 ° C. of 1 to 600 mm ² / s. Manufacturing method. A vibration damping material comprising the polymer composition according to any one of claims 1 to 5 . A soundproof material comprising the polymer composition according to any one of claims 1 to 5 .