JP2004300408A - Hydrogenated diene-based copolymer, polymer composition and molded product given by using the polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new hydrogenated diene-based copolymer solely having excellent processability, flexibility, vibration-damping properties and mechanical characteristics, capable of giving a molded product which has rich flexibility and excellent mechanical characteristics, molded appearance, scratch resistance, weather resistance, heat resistance, vibration-damping properties and processability, and having a specified structure. <P>SOLUTION: This hydrogenated diene-based copolymer satisfying prescribed conditions is formed by hydrogenating a block copolymer which contains at least two polymer blocks (A) consisting mainly of a vinyl aromatic compound and at least one copolymer block (B) composed of the vinyl aromatic compound and a conjugated diene compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a hydrogenated block copolymer having a specific structure (hydrogenated diene copolymer), a polymer composition containing the copolymer, a powder comprising the polymer composition, and a powder comprising the polymer composition. Molded product obtained by powder molding, a molded product obtained by extruding the hydrogenated diene copolymer, a molded product obtained by extruding the polymer composition, and the hydrogenated diene copolymer. More specifically, the present invention relates to a composition for a foam, and a foam obtained by foaming the composition. More specifically, the composition is rich in flexibility, mechanical properties, molded appearance, scratch resistance, weather resistance, heat resistance, vibration damping properties, and workability. A novel hydrogenated diene-based copolymer having a specific structure capable of giving an excellent molded article, a polymer composition containing the hydrogenated diene-based copolymer, a powder comprising the polymer composition, A compact formed by powder molding of the powder; A molded article obtained by extruding an ene copolymer, a molded article obtained by extruding the polymer composition, a foam composition containing the hydrogenated diene copolymer, and foaming the foamed composition And foams.

2. Description of the Related Art Conventionally, as a powder molding method using a soft powder material, a powder slush molding method (powder slush molding method) using a soft vinyl chloride resin powder has been used for an automobile interior material such as an instrument panel, a console box, and a door trim. Widely used for molding. A molded article made of a soft vinyl chloride resin has a soft feel, can be provided with embossing and stitching, and has good design properties such as a large degree of freedom in design. However, such a soft vinyl chloride resin is not only inferior in lightness, but also generates an acidic substance due to vinyl chloride when incinerated after use, and thus has a problem on environmental hygiene. As a solution to such a problem, there has been proposed a thermoplastic elastomer powder composed of an olefin-based thermoplastic elastomer obtained by blending a polypropylene resin and ethylene-propylene rubber (for example, see Patent Document 1).

However, since the molded product obtained by powder molding of such a thermoplastic elastomer powder is harder than a vinyl chloride resin molded product and has a property of being easily whitened when bent, it is removed from the mold after molding. In such cases, the bent portions tend to whiten, resulting in poor appearance. To improve such bending whitening, thermoplastic elastomer powders in which a polypropylene resin and a styrene-based thermoplastic elastomer having a low styrene content are blended have been proposed (for example, see Patent Documents 2 to 5).

Molded articles obtained by powder molding of the thermoplastic elastomer powders proposed in the above-mentioned Patent Documents 2 to 5 are improved in bending whitening by lowering the styrene content of the hydrogenated diene copolymer to increase the fluidity. Have been. However, since the styrene content is low, the tensile strength of the hydrogenated diene copolymer / olefin polymer composition is low, and the molded article of the composition has insufficient scratch resistance.

In addition, when these compositions are used for extrusion molding of packaging films, industrial material films, sheets, and the like, when they come into contact with other objects such as wood, rub, or collide, damage or appearance due to wear or scratches occurs. There is a problem that a defect occurs.

On the other hand, various block copolymers comprising a vinyl aromatic polymer block and a conjugated diene compound polymer block have been proposed, and these simple substances or blends thereof with other materials can be used as vulcanized rubber or soft vinyl chloride. It is used in various molded products as a substitute for resin. In addition, a hydrogenated styrene-isoprene-styrene block copolymer (SEPS) and a hydrogenated styrene-styrene-isoprene-styrene block copolymer in which the conjugated diene compound polymer block in such a block copolymer is made of isoprene. (SSEPS) (for example, see Patent Document 6) is known to exhibit vibration damping properties at around normal temperature by controlling the content of these 1,2- and 3,4-bonds. .

However, when compared with a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) in which the conjugated diene compound polymer block is composed of butadiene, the degradation is more likely to occur due to the large amount of tertiary carbon, and the weather resistance and In some cases, heat resistance was insufficient.

Also, when the content of 1,2-bonds of butadiene in SEBS is increased, the tan δ peak temperature showing a correlation with the glass transition temperature does not become sufficiently high, so that the problem of not exhibiting vibration damping properties at around normal temperature is obtained. There is. Therefore, while having excellent vibration damping properties, flexibility, mechanical properties, weather resistance, and a copolymer excellent in moldability, or a composition containing the same, at present, it has not been found yet. is there.
JP-A-5-1183 JP-A-7-82433 JP 2001-49051 A JP 2001-49052 A JP-A-2002-166498 JP-A-2002-284830

The present invention has been made against the background of the above-mentioned conventional technical problems, and has as its object to independently have excellent workability, flexibility, vibration damping properties, and mechanical properties, and Novel hydrogenated diene-based copolymer having a specific structure that is capable of providing a molded article having excellent properties, excellent mechanical properties, molded appearance, scratch resistance, weather resistance, heat resistance, vibration damping properties, and workability A polymer composition containing the hydrogenated diene copolymer, a powder composed of the polymer composition, a molded product obtained by powder molding the powder, and extrusion molding of the hydrogenated diene copolymer. The present invention provides a molded article formed by extrusion, a molded article obtained by extruding the polymer composition, a composition for a foam containing the hydrogenated diene copolymer, and a foam obtained by foaming the composition. .

The present inventors have conducted intensive studies to achieve the above object, and as a result, by copolymerizing a vinyl aromatic compound at a specific ratio in a block of a hydrogenated diene-based copolymer, the blended material was not reduced in flowability. It has been found that the tensile strength of the molded article can be improved and the scratch resistance of the molded article can be improved, thereby completing the present invention.

That is, according to the present invention, the following hydrogenated diene-based copolymer, a polymer composition containing the hydrogenated diene-based copolymer, a powder composed of the polymer composition, and a powder formed from the powder. Molded article, molded article obtained by extruding the hydrogenated diene copolymer, molded article obtained by extruding the polymer composition, foam composition containing the hydrogenated diene copolymer, Further, a foam obtained by foaming the foam is provided.

[1] A block copolymer containing at least two polymer blocks (A) mainly containing a vinyl aromatic compound and at least one copolymer block (B) of a vinyl aromatic compound and a conjugated diene compound A hydrogenated diene copolymer which satisfies all of the following conditions (1) to (3) obtained by hydrogenating the coalesced copolymer.
(1): The total content of the vinyl aromatic compound units in the hydrogenated diene copolymer is 20 to 70% by mass.
(2): The ratio (BS) of the vinyl aromatic compound unit content contained in the block (B) to the total vinyl aromatic compound unit content in the hydrogenated diene copolymer is 10 to 80%. It is.
(3): The content of the vinyl bond derived from the conjugated diene compound in the hydrogenated diene-based copolymer is 30 to 75%.

[2] A block copolymer containing at least two polymer blocks (A) mainly containing a vinyl aromatic compound and at least one copolymer block (B) of a vinyl aromatic compound and a conjugated diene compound. A hydrogenated diene copolymer which satisfies all of the following conditions (1) to (3) obtained by hydrogenating the coalesced copolymer.
(1): The total content of the vinyl aromatic compound units in the hydrogenated diene copolymer is 20 to 70% by mass.
(2): The ratio (LS) of the long-chain vinyl aromatic compound unit content to the total vinyl aromatic compound unit content in the hydrogenated diene copolymer is 10 to 80%.
(3): The content of the vinyl bond derived from the conjugated diene compound in the hydrogenated diene-based copolymer is 30 to 75%.

[3] The hydrogenated diene-based copolymer according to [1] or [2], wherein 90% or more of the double bonds derived from the conjugated diene compound are hydrogenated.

[4] The hydrogenated diene-based copolymer according to any one of the above [1] to [3], wherein a melt flow rate (MFR) measured at 230 ° C and a load of 21.2 N is 10 to 200 g / 10 minutes. .

[5] The hydrogenated diene-based copolymer according to any one of the above [1] to [3], wherein the melt flow rate (MFR) measured at 230 ° C. under a load of 21.2 N is 0.01 to 100 g / 10 min. Polymer.

[6] The hydrogenated diene copolymer according to any one of [1] to [4], wherein the melt viscosity at 230 ° C. and 0.1 Hz is 2,000 Pa · s or less.

[7] The hydrogenated diene-based copolymer (a) according to any of the above [1] to [6], and a thermoplastic polymer (b) other than the hydrogenated diene-based copolymer (a) Is contained in a mass ratio of (a) / (b) = 99/1 to 1/99.

[8] The polymer composition according to [7], wherein the thermoplastic polymer (b) is a propylene-based polymer.

[9] A powder obtained by subjecting the polymer composition according to [8] to mechanical pulverization, die face cutting, or strand cutting.

[10] The powder according to the above [9], which has a bulk specific gravity of 0.38 or more and a sphere-converted average particle size of 1.2 mm or less.

[11] A molded product obtained by powder molding the powder according to [9] or [10].

[12] A molded product obtained by extruding the hydrogenated diene copolymer according to [5].

[13] The hydrogenated diene copolymer (a) according to the above [5] and the thermoplastic polymer (c) are (a) / (b) = 99/1 to 1/99 by mass ratio. A molded product obtained by extrusion-molding a polymer composition contained at a ratio of 1.

[14] A foam composition comprising the hydrogenated diene-based copolymer according to any one of [1] to [6] and a foaming agent.

[15] The foam composition according to [14], further comprising a thermoplastic polymer other than the hydrogenated diene-based copolymer.

[16] A foam obtained by foaming the foam composition according to [14] or [15].

The hydrogenated diene copolymer having a specific structure of the present invention has excellent processability, flexibility, weather resistance, vibration damping properties, and mechanical properties alone, and is rich in flexibility, mechanical properties, It can provide a molded article having excellent molding appearance, scratch resistance, weather resistance, heat resistance, vibration damping properties, and workability. Further, the polymer composition of the present invention is rich in flexibility and excellent in mechanical properties, molded appearance, weather resistance, vibration damping properties, and heat resistance. Further, the molded article of the present invention has excellent flexibility, weather resistance, vibration damping properties, and mechanical properties. Further, the foam composition of the present invention has excellent processability and is a composition that can provide a foam excellent in flexibility, mechanical properties, and vibration damping properties. Furthermore, the foam of the present invention is excellent in flexibility and mechanical properties and extremely excellent in damping.

Hereinafter, the best mode for carrying out the hydrogenated diene copolymer of the present invention will be specifically described.

(A) Hydrogenated Diene Copolymer The hydrogenated diene copolymer of the present invention is composed of “at least two polymer blocks (A) mainly composed of a vinyl aromatic compound and at least one vinyl aromatic compound. A hydrogenated diene copolymer satisfying all the following conditions (1) to (3), obtained by hydrogenating a block copolymer containing a compound and a copolymer block (B) of a conjugated diene compound. (Hereinafter also referred to as “component (a) component”) ”.
(1): The total content of the vinyl aromatic compound units in the hydrogenated diene copolymer is 20 to 70% by mass.
(2): The ratio (BS) of the vinyl aromatic compound unit content contained in the block (B) to the total vinyl aromatic compound unit content in the hydrogenated diene copolymer is from 10 to 80%. Alternatively, the ratio (LS) of the long-chain vinyl aromatic compound unit content to the total vinyl aromatic compound unit content in the hydrogenated diene copolymer is 10 to 80%.
(3): The content of the vinyl bond derived from the conjugated diene compound in the hydrogenated diene copolymer is 30 to 75%.

Specific examples include hydrogenated block copolymers represented by the following structural formulas (1) to (3).
(AB) m ... Structural formula (1)
(AB) mY Structural formula (2)
A- (BA) n ... Structural formula (3)
(In the above structural formulas (1) to (3), A is a polymer block mainly composed of a vinyl aromatic compound (hereinafter also referred to as “(A) block”). The polymer block may contain a conjugated diene compound partially, preferably contains a vinyl aromatic compound in an amount of 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 99% by mass or more. B is a copolymer block of a vinyl aromatic compound and a conjugated diene compound (hereinafter, also referred to as “(B) block”), preferably 20% by mass of the conjugated diene compound. It is a copolymer block of a vinyl aromatic compound and a conjugated diene compound contained above, Y is a residue of a coupling agent, m is an integer of 2 to 5, and n is an integer of 1 to 5. It Are represented.)

Here, two or more “(A) blocks” in the block copolymers represented by the above structural formulas (1) to (3) may be the same, and have different compositions or molecular weights. It may be. Similarly, when two or more “(B) blocks” are contained in the block copolymer, the two or more “(B) blocks” may be the same, and may have different compositions or different molecular weights. There may be. Further, other polymer blocks (hereinafter, also referred to as “(C) blocks”) other than the above polymer blocks or copolymer blocks, for example, a polymer in which a conjugated diene compound is hydrogenated, One or more copolymers may be copolymerized at the terminal of the copolymer or in the block copolymer chain.

The block copolymers represented by the structural formulas (1) to (3) include, for example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; and cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane. In an alicyclic hydrocarbon solvent or an inert organic solvent such as an aromatic hydrocarbon solvent such as benzene, xylene, toluene, and ethylbenzene, a vinyl aromatic compound and a conjugated diene compound, or a vinyl aromatic compound and a conjugated diene compound, and Can be obtained by living anionic polymerization using an organic alkali metal compound as a polymerization initiator, and this block copolymer (hereinafter, also referred to as “pre-hydrogenated polymer”) By hydrogenating, the hydrogenated diene copolymer of the present invention can be easily obtained.

Examples of the vinyl aromatic compound include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N, N-diethyl -P-aminoethylstyrene, vinylpyridine and the like. Of these, styrene is preferred. Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadiene, and 1,3-butadiene. Examples thereof include hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, and chloroprene. Of these, 1,3-butadiene and isoprene are preferred.

Examples of the organic alkali metal compound serving as a polymerization initiator include an organic lithium compound and an organic sodium compound, and an organic lithium compound such as n-butyllithium, sec-butyllithium, and tert-butyllithium is particularly preferable. There is no particular limitation on the amount of the organic alkali metal compound used, and various amounts can be used as necessary. Usually, the amount is 0.02 to 15% by mass per 100% by mass of the monomer, preferably 0.03 to 15% by mass. Used in an amount of 5% by weight.

The polymerization temperature is generally -10 to 150C, preferably 0 to 120C. Further, it is desirable to replace the atmosphere of the polymerization system with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited as long as the polymerization is performed within a pressure range sufficient to maintain the monomer and the solvent in the liquid phase in the above-mentioned polymerization range.

Further, in the process of polymerizing a copolymer block containing a vinyl aromatic compound and a conjugated diene compound, a method of introducing monomers of these compounds into a polymerization system is not particularly limited, and may be collectively, continuously, intermittently. Target or a method combining these. Further, when polymerizing a copolymer block containing a vinyl aromatic compound and a conjugated diene compound, the amounts of other copolymer components added, the amounts of polar substances, the number and type of polymerization containers, and the like, The method for introducing the monomer may be selected so that the physical properties of the obtained hydrogenated diene copolymer, its composition, and the molded product of the composition are favorable.

The pre-hydrogenated polymer of the present invention is obtained by obtaining a block copolymer by the above method, and then using a coupling agent to obtain a copolymer in which the copolymer molecular chain is a copolymer via a coupling residue. Good.

As the coupling agent used, for example, divinylbenzene, 1,2,4-trivinylbenzene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene-1,2,4-triisocyanate Nato, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, pyromellitic dianhydride, diethyl carbonate, 1,1,2,2-tetrachloroethane, 1,4-bis (trichloromethyl) benzene, trichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, (dichloromethyl) trichlorosilane, hexachlorodisilane, tetraethoxysilane, tetrachlorotin, 1,3-dichloro-2 − Ropanon, and the like. Among them, divinylbenzene, epoxidized 1,2-polybutadiene, trichlorosilane, methyltrichlorosilane, and tetrachlorosilane are preferable.

The hydrogenated diene copolymer of the present invention is obtained by partially or selectively hydrogenating the block copolymer obtained as described above. The hydrogenation method and reaction conditions are not particularly limited, and the hydrogenation is usually performed at 20 to 150 ° C. and under a hydrogen pressure of 0.1 to 10 MPa in the presence of a hydrogenation catalyst.

In this case, the hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, or the reaction time. As the hydrogenation catalyst, a compound containing any of the metals of the periodic table Ib, IVb, Vb, VIb, VIIb, or Group VIII is usually used, such as Ti, V, Co, Ni, Zr, Ru, Rh, Pd, and Hf. Compounds containing Re and Pt atoms can be used. Specifically, for example, metal such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, and Re, and metal such as Pd, Ni, Pt, Rh, and Ru are used as carbon, silica, and alumina. , A supported heterogeneous catalyst supported on a carrier such as diatomaceous earth, a homogeneous Ziegler-type catalyst obtained by combining an organic salt or acetylacetone salt of a metal element such as Ni and Co with a reducing agent such as organic aluminum, Ru, Rh And fullerenes and carbon nanotubes that have absorbed hydrogen. Among them, a metallocene compound containing any of Ti, Zr, Hf, Co, and Ni is preferable in that a hydrogenation reaction can be performed uniformly in an inert organic solvent. Further, a metallocene compound containing any of Ti, Zr, and Hf is preferable. Particularly, a hydrogenation catalyst obtained by reacting a titanocene compound with alkyllithium is preferable because it is an inexpensive and industrially particularly useful catalyst. The hydrogenation catalyst may be used alone or in combination of two or more. After hydrogenation, the catalyst residue is removed, if necessary, or a phenolic or amine-based antioxidant is added. Thereafter, the hydrogenated diene-based copolymer of the present invention is removed from the hydrogenated diene-based copolymer solution. Isolate the coalescence. Isolation of the hydrogenated diene-based copolymer is carried out, for example, by adding acetone or alcohol to the hydrogenated diene-based copolymer solution and precipitating the solution, throwing the hydrogenated diene-based copolymer solution into boiling water with stirring. And a method of removing the solvent by distillation.

The content of all vinyl aromatic compound units in the hydrogenated diene copolymer of the present invention (hereinafter, also referred to as “total vinyl aromatic compound unit content”) is 20 to 70% by mass, preferably 25% by mass. ６５65% by mass. If the total content of the vinyl aromatic compound units exceeds 70% by mass, a molded article obtained using the hydrogenated diene copolymer tends to be hard. When the total content of the vinyl aromatic compound units is less than 20% by mass, the mechanical strength of the obtained molded article tends to decrease.

(B) The ratio of the content of the vinyl aromatic compound unit contained in the block (B) to the total content of the vinyl aromatic compound unit in the hydrogenated diene copolymer of the present invention (BS) (hereinafter simply referred to as “BS ratio”) ) Is in the range of 10 to 80%, preferably 25 to 75%, more preferably 30 to 70%. If the BS ratio is less than 10%, the mechanical strength of a molded article obtained using this hydrogenated diene copolymer decreases, while if it exceeds 80%, the flexibility of the molded article decreases.

Note that the BS ratio is determined from the charged amount of the vinyl aromatic compound at the time of polymerization using the following formula.
BS ratio (%) = (total amount of vinyl aromatic compound charged in each (B) block of hydrogenated diene copolymer / total vinyl aromatic compound in the hydrogenated diene copolymer) Total amount) x 100

In addition, the hydrogenated diene copolymer of the present invention has a ratio (LS) (hereinafter referred to as "LS") of the content of the unit of the long-chain vinyl aromatic compound to the total content of the vinyl aromatic compound units in the hydrogenated diene copolymer. , Simply referred to as “LS ratio”) is within the range of 10 to 80%, preferably 20 to 70%, and more preferably 30 to 50%. If the LS ratio is less than 10%, the mechanical strength of a molded article obtained by using this hydrogenated diene copolymer may decrease. If it exceeds 80%, the flexibility of the molded article may decrease. Here, the LS ratio is a value described below.

In general, in the ¹ H-NMR spectrum of a styrene-butadiene copolymer, the phenyl proton of styrene shows two peaks whose chemical shifts are around 7 ppm and around 6.5 ppm, and the peak around 6.5 ppm shows a long chain. It is believed to be a phenyl proton at the ortho position of the formed styrene (Bovey et al., J. Polym. Sci. Vol 38, 1959, pp. 73-90). Therefore, in the present invention, as shown in the ¹ H-NMR spectrum in the 7.6 to 6.0 ppm region of the hydrogenated diene copolymer (H-2) produced according to Production Example 1 described below (FIG. 1). Of these peaks, the peak near 6.5 ppm on the high magnetic field side is regarded as a “long-chain vinyl aromatic compound”, and the area of a 7.6 to 6.0 ppm portion measured by ¹ H-NMR at 270 MHz. The strength is defined as the total vinyl aromatic compound unit content, the area strength of the 6.8 to 6.0 ppm portion is defined as the long chain vinyl aromatic compound unit content, and the LS ratio is determined using the following equation.
LS ratio (%) = [(area intensity of 6.8 to 6.0 ppm portion × 2.5) / (area intensity of 7.6 to 6.0 ppm portion)] × 100

The content of vinyl bonds (1,2- and 3,4-vinyl bonds) derived from the conjugated diene compound in the hydrogenated diene copolymer of the present invention before hydrogenation is 30 to 75%, preferably 40 to 75%, More preferably it is in the range of 50-75%, most preferably in the range of 60-75%. When the content is less than 30%, a molded article obtained by using the hydrogenated diene copolymer tends to be hard. On the other hand, if it exceeds 75%, the heat resistance and mechanical strength of the molded body tend to decrease.

In the hydrogenated diene copolymer of the present invention, it is preferable that 90% or more, particularly 95% or more, of the double bond derived from the conjugated diene compound is hydrogenated. When the degree of hydrogenation is less than 90%, the weatherability of a molded article obtained by using this hydrogenated diene copolymer tends to decrease. The double bond derived from the conjugated diene compound includes 1,2- and 3,4-vinyl bonds as side chain double bonds and 1,4-bond as main chain double bonds. Of these, at least 90% or more of the 1,2- and 3,4-vinyl bonds are preferably hydrogenated.

The melt flow rate (MFR) of the hydrogenated diene copolymer of the present invention measured at a temperature of 230 ° C. and a load of 21.2 N varies depending on the intended use. When used for powder molding, the melt flow rate is 10 to 200 g / 10 min. Preferably, it is 15 to 100 g / 10 min, particularly preferably 20 to 100 g / 10 min. When the melt flow rate (MFR) is less than 10 g / 10 minutes, a fine powder tends not to be easily obtained, and a molded article obtained tends to have poor appearance. On the other hand, when the melt flow rate (MFR) exceeds 200 g / 10 minutes, the heat resistance, weather resistance, and mechanical strength of the obtained molded article tend to be inferior.

When the hydrogenated diene copolymer of the present invention is used for extrusion molding, it is preferably 0.01 to 100 g / 10 minutes, more preferably 0.05 to 50 g / 10 minutes, and particularly preferably 0.1 to 50 g / 10 minutes. 05 to 15 g / 10 min. If the melt flow rate (MFR) is less than 0.01 g / 10 minutes, the load at the time of extrusion molding becomes excessive and the surface of the extruded product may be rough, which is not preferable. On the other hand, if the melt flow rate (MFR) exceeds 100 g / 10 minutes, there is a possibility that a problem may occur in the extrusion moldability such as drawdown, which is not preferable. Furthermore, when the hydrogenated diene copolymer of the present invention is used for injection molding, it is preferably 0.1 to 200 g / 10 min, more preferably 0.1 to 100 g / 10 min, and particularly preferably. 0.1 to 50 g / 10 min. If the melt flow rate (MFR) is less than 0.01 g / 10 minutes, the appearance of the injection molded article may be poor, which is not preferable. On the other hand, if the melt flow rate (MFR) exceeds 200 g / 10 minutes, the mechanical strength of the obtained molded article may be undesirably reduced.

On the other hand, when the hydrogenated diene-based copolymer of the present invention is used for foaming, a rubber processing machine such as a Banbury mixer, a pressure kneader, or two open rolls is used depending on the molding and processing method. In this case, it is preferably 0.01 to 100 g / 10 min, more preferably 0.05 to 50 g / 10 min, and particularly preferably 0.05 to 15 g / 10 min. If the melt flow rate (MFR) is less than 0.01 g / 10 minutes, the load at the time of processing the polymer blend may be undesirably large. On the other hand, if the melt flow rate (MFR) exceeds 100 g / 10 minutes, there is a possibility that problems may occur in processability such as dischargeability from a processing machine and adhesiveness, which is not preferable.

The melt viscosity at 230 ° C. and 0.1 Hz of the hydrogenated diene copolymer of the present invention is preferably 2,000 Pa · s or less, and when used for powder molding, it is particularly preferably 10 to 1500 Pa · s. preferable.

The weight average molecular weight (Mw) of the hydrogenated diene copolymer of the present invention is preferably 30,000 to 400,000, and particularly preferably 50,000 to 300,000 in order to obtain a molded article having excellent appearance and strength. Is preferred. When the weight average molecular weight is less than 30,000, the resulting molded article may have tackiness and insufficient heat resistance and weather resistance. When the weight average molecular weight is more than 400,000, a molded product having sufficient appearance and mechanical strength may not be obtained due to poor fluidity.

The glass transition temperature (Tg) of the hydrogenated diene copolymer of the present invention may affect heat resistance and cold resistance. When the hydrogenated diene-based copolymer has at least two Tg, and the highest temperature Tg is Tg (A) and the lowest temperature Tg is Tg (B), the hydrogenated diene copolymer is used as a composition for powder slush application or the like. The Tg (A) is 80 to 110C, preferably 90 to 110C, and the Tg (B) is -60 to 10C, preferably -55 to 5C. When cold resistance is required, Tg (B) is desirably −55 to −30 ° C. On the other hand, when damping is required, Tg (B) is preferably closer to the temperature region where damping is required.

Incidentally, the hydrogenated diene copolymer of the present invention, amino groups, alkoxysilyl groups, hydroxyl groups, acid anhydride groups, functional groups such as epoxy groups are introduced, as a modified hydrogenated diene copolymer. It is also possible to use. Examples of such modified hydrogenated diene copolymers include the following copolymers ((a) to (f)).

(A) A copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound in the presence of an organic alkali metal compound having an amino group, and hydrogenating the obtained copolymer.

(B) A copolymer obtained by copolymerizing a vinyl aromatic compound, a conjugated diene compound, and an unsaturated monomer having an amino group in the presence of an organic alkali metal compound, and hydrogenating the obtained copolymer. United.

(C) A vinyl aromatic compound and a conjugated diene compound are copolymerized in the presence of an organic alkali metal compound to form a copolymer obtained by reacting an alkoxysilane compound with an active site of the obtained copolymer. A copolymer obtained by hydrogenating a copolymer.

(D) A vinyl aromatic compound and a conjugated diene compound are copolymerized in the presence of an organic alkali metal compound to form a copolymer in which an active site of the obtained copolymer is reacted with an epoxy compound or a ketone compound. , A copolymer obtained by hydrogenating the copolymer.

(E) A vinyl aromatic compound and a conjugated diene compound are copolymerized in the presence of an organic alkali metal compound, and a (meth) acryloyl group-containing compound, an epoxy group A copolymer obtained by reacting at least one selected from a compound containing and maleic anhydride in a solution or a kneader such as an extruder. Furthermore,

(F) A vinyl aromatic compound and a conjugated diene compound are copolymerized in the presence of an organic alkali metal compound, and epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, and benzene are used as coupling agents. By using -1,2,4-triisocyanate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, dianhydride pyromellitic acid, and the like, A copolymer having a functional group such as -OH group, -NH-CO group, -NH group introduced at the center of a molecular chain.

The hydrogenated diene-based copolymer of the present invention can contain conventional auxiliary additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, coloring agents, and flame retardants. The hydrogenated diene copolymer of the present invention is used alone or as various resin modifiers, and is useful for molded articles such as automobile parts, electric / electronic parts, and other films and sheet products.

On the other hand, the hydrogenated diene copolymer of the present invention is rich in flexibility, mechanical properties, molded appearance, scratch resistance, weather resistance, heat resistance by blending with a thermoplastic polymer, especially an olefin polymer. It is useful for films, sheets, and automotive interior materials because it can give a molded article having excellent heat resistance and cold resistance. The details will be described below.

(B) Thermoplastic polymer The hydrogenated diene copolymer (component (a)) of the present invention is blended with a thermoplastic polymer (hereinafter also referred to as “component (b)”) (hereinafter referred to as “the present invention”). (Also referred to as "polymer composition"). The ratio of the hydrogenated diene-based copolymer to the thermoplastic polymer to be blended is (a) / (b) = 99/1 to 1/99, preferably 3/97 to 97/3 by mass ratio. The optimum mixing ratio differs depending on the purpose of use. However, the modification effect of the hydrogenated diene copolymer (component (a)) of the present invention may not be sufficiently exerted with the addition of less than 1% by mass.

Here, the component (b) (thermoplastic polymer) contained in the polymer composition of the present invention excludes the component (a) (hydrogenated diene copolymer), and includes a nonpolar polymer, Alternatively, it may be any of a polar polymer. Examples of the non-polar polymer include an olefin polymer and a styrene polymer described below. Examples of the styrene-based polymer include styrene homopolymer (PS), high-impact polystyrene (HIPS), ethylene-styrene copolymer (ESI), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene. Copolymer (ABS), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES), acrylonitrile / chlorinated polystyrene / styrene copolymer (ACS), styrene / methyl methacrylate copolymer (MS), butadiene / styrene -Methyl methacrylate copolymer (MBS), styrene / maleic anhydride copolymer (SMA) and the like.

Examples of the polar polymer include an acrylic polymer. Examples of the acrylic polymer include poly (methyl) acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, poly (meth) acrylate 2-ethylhexyl, and poly (meth) acrylate cyclohexyl And the like. Other than these acrylic polymers, aromatic polycarbonate, polymethacrylonitrile, polyacetal, polyoxymethylene, ionomer, chlorinated polyethylene, coumarone-indene resin, regenerated cellulose, petroleum resin, cellulose derivative, alkali cellulose, cellulose Ester, cellulose acetate, cellulose acetate butyrate, cellulose xanthate, cellulose nitrate, cellulose ether, carboxymethyl cellulose, cellulose ether ester, fluororesin, FEP, polychlorotrifluoroethylene, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride Fats such as vinyl, nylon 11, nylon 12, nylon 6, nylon 6,10, nylon 6,12, nylon 6,6, nylon 4,6 Aromatic polyamide such as polyamide, polyphenylene isophthalamide, polyphenylene terephthalamide, meta-xylylenediamine, polyimide, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyamide imide, polyarylate, polyvinylidene chloride, polyvinyl chloride, chlorinated polyethylene And aromatic polyesters such as chlorosulfonated polyethylene, polysulfone, polyether sulfone, polysulfonamide, polyvinyl alcohol, polyvinyl ester, polyisobutyl vinyl ether, polymethyl vinyl ether, polyphenylene oxide, polyethylene terephthalate, and polybutylene terephthalate. Among these, preferred thermoplastic polymers are the following olefin polymers.

Examples of the olefin polymer include polyethylene, polypropylene, poly 1-butene, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, ethylene / 1-hexene Copolymer, ethylene / 1-octene copolymer, ethylene / propylene copolymer (EPM), ethylene / propylene / non-conjugated diene copolymer (EPDM), ethylene / 1-butene copolymer (EBM), ethylene Ethylene / α-olefin / (nonconjugated diene) copolymer such as 1-butene / non-conjugated diene copolymer (EBDM), polar group-containing ethylene / α-olefin copolymer, and its metal crosslinked product, ethylene・ Vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene -Methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-butyl acrylate copolymer and the like can be mentioned, and these can be used alone or in combination of two or more. Among them, polyethylene and polypropylene are preferred, and polypropylene is particularly preferred because the resulting composition has excellent heat resistance.

Among the above-mentioned olefin-based polymers, when used as a powder for powder molding described later or when used as a raw material for extrusion molding, propylene homopolymer, propylene and other α-olefin of 20 mol% or less are used. And a propylene-based polymer such as a block copolymer of propylene and 30% by mole or less of other α-olefin. Particularly, polypropylene having a crystallinity of 50% or more, a density of 0.89 g / cm ³ or more, an ethylene unit content of 20 mol% or less, and a melting point of 100 ° C. or more, and a copolymer of propylene and ethylene. It is particularly preferred to use a polymer. Such applications include ethylene / propylene copolymer (EPM), ethylene / propylene / non-conjugated diene copolymer (EPDM), ethylene / 1-butene copolymer (EBM), ethylene / 1-butene -Non-conjugated diene copolymers (EBDM), polar group-containing ethylene / α-olefin copolymers, and blends with olefin-based rubbers such as metal cross-linked products, and dynamics of these blends in the presence of a cross-linking agent It may be a crosslinked thermoplastic elastomer.

The melt flow rate (MFR) of the thermoplastic polymer (component (b)) contained in the polymer composition of the present invention measured at 230 ° C. and a load of 21.2 N varies depending on the use, and is suitable for powder molding. When used, it is 10 to 500 g / 10 min, preferably 15 to 500 g / 10 min, and more preferably 20 to 500 g / 10 min. When used for extrusion molding, it is 0.01 to 100 g / 10 min, preferably 0.01 to 50 g / 10 min, more preferably 0.05 to 15 g / 10 min. When used for injection molding, it is 1 to 500 g / 10 min, preferably 5 to 500 g / 10 min, more preferably 10 to 500 g / 10 min.

The polymer composition of the present invention may contain, if necessary, various additives such as heat stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine-based, and amide-based, weather-resistant stabilizers, and metal-free materials. Activators, UV absorbers, antistatic agents, light stabilizers, stabilizers such as copper damage inhibitors, antibacterial and antifungal agents, antibacterial agents, dispersants, mineral oil softeners, plasticizers, lubricants, and foaming agents , Foaming aids, titanium oxide, pigments, metal powders such as ferrite, glass fibers, inorganic fibers such as metal fibers, organic fibers such as carbon fibers and aramid fibers, composite fibers, inorganic whiskers such as potassium titanate whiskers, and glass beads. , Glass balloon, glass flake, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, evo , A filler such as cotton floc, cork powder, barium sulfate, fluororesin, polymer beads, or a mixture thereof, a filler such as polyolefin wax, cellulose powder, rubber powder, and a low molecular weight polymer. .

The use of silicone oil, silicone gum, fatty acid amide, or fluororesin as a lubricant further improves the scratch resistance of the obtained molded article. Further, the polymer composition of the present invention can be subjected to crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, silane crosslinking, and resin crosslinking, if necessary, by a conventionally known method.

Examples of a method for obtaining the polymer composition of the present invention include a method of melt-kneading the components (a) and (b). For kneading, a single-screw extruder, a twin-screw extruder, a kneader, a roll, or the like can be used. In addition, the above-mentioned various additives and various polymers are compounded, for example, by using a mixture of the components (a) and (b) in which these additives are preliminarily mixed, or when mixing the above components. Can be performed.

If the polymer composition of the present invention is used, injection molding, two-color injection molding, extrusion molding, rotational molding, press molding, hollow molding, sandwich molding, compression molding, vacuum molding, powder (powder slash) molding, double flash molding A molded product having a desired shape can be manufactured by a known method such as lamination molding, calendar molding, or blow molding. If necessary, processing such as foaming, stretching, bonding, printing, painting, and plating may be performed. In the case of extrusion molding, it can be widely applied to extrusion molding applications such as profile extrusion, sheet extrusion, and multilayer extrusion.

Extrusion molding, and the molding temperature when performing melt molding such as injection molding are appropriately set depending on the melting point of the polymer composition and other additives, the type of molding machine used, and the like. 350 ° C. A molded article of the polymer composition of the present invention obtained by a known molding method using an extruder, an injection molding machine, or the like is used alone or in combination with another material such as a surface material of a multilayer laminate. be able to. As a method for forming a multilayer laminate in which the surface material is the polymer composition of the present invention, (a) the base material layer and the surface layer are formed into a film or sheet by a usual method such as a T-die method, and then heat-bonded. (B) a method of directly laminating and molding by an extrusion molding machine, (c) a method of extruding and laminating the other layer on at least one surface of a base layer or a surface layer previously molded by, for example, the method (a). And (d) a known method such as a method of directly laminating and molding by an injection molding machine.

In the case of using the above-mentioned “(b) Direct lamination molding method using an extrusion molding machine”, the surface layer is formed by extruding the polymer composition of the present invention on the surface of the base material layer prepared in advance. Alternatively, two or more extruders may be connected to one die, and one extruder may be supplied with a material for forming a base material layer, and the other extruder may be provided with the present invention. By supplying the polymer composition of (1) and simultaneously operating each extruder, the lower substrate layer and the surface layer may be simultaneously formed inside the die. Such a method is described in, for example, JP-A-2001-10418.

When the above-mentioned “(d) Method for directly laminating and molding by an injection molding machine” is used, the base material prepared in advance is placed in a mold, and the polymer composition of the present invention is injection-molded. By using two injection molding machines and one mold, the polymer composition of the present invention is supplied to one injection molding machine and the other injection molding machine is used. The base material layer and the surface layer may be continuously formed in a mold by supplying a material to be used as a base material layer and continuously operating two injection molding machines.

When powder (powder slush) is formed, the powder can be produced by a method of mechanically pulverizing the polymer composition of the present invention, or a strand cut method or a die face cut method. As a method of mechanical pulverization, for example, a method of freezing or normal temperature pulverization using a pulverizer such as a turbo mill, a roller mill, a ball mill, a pin mill, a hammer mill, and a centrifugal pulverizer can be exemplified.

The method of producing powder by strand cutting refers to a method in which a molten polymer composition is extruded from a die into air or water to form a strand, which is cooled and cut. The discharge diameter of the die is usually in the range of 0.1 to 3 mm, preferably 0.2 to 2 mm. The discharge speed of the polymer composition per one discharge port of the die is usually in the range of 0.1 to 5 kg / hour, preferably 0.5 to 3 kg / hour. The take-off speed of the strand is usually in the range of 1 to 100 m / min, preferably 5 to 50 m / min. The cooled strand is usually cut to 1.2 mm or less, preferably 0.1 to 1.0 mm.

The method of producing a powder by die face cutting refers to a method of cutting while extruding a molten polymer composition from a die into water. The discharge diameter of the die is usually in the range of 0.1 to 3 mm, preferably 0.2 to 2 mm. The discharge speed of the polymer composition per one discharge port of the die is usually in the range of 0.1 to 5 kg / hour, preferably 0.5 to 3 kg / hour. The temperature of the water is usually in the range from 30 to 70C, preferably from 40 to 60C.

By the method of mechanically pulverizing the polymer composition described above, the bulk specific gravity is 0.38 or more, preferably 0.40 or more, 0.70 or less, and the sphere-equivalent average particle diameter is 1.2 mm or less, preferably A powder suitable for powder molding applications having a diameter of 0.1 to 0.7 mm can be easily obtained. Here, the sphere-equivalent average particle diameter of the powder is defined as the diameter of a sphere having the same volume as the average volume of the powder. The average volume (V) of the powder is expressed by a relational expression (100) of the total mass (W) of 100 particles of powder taken at random, the density (D) of the polymer composition, and the average volume (V). V = W / D). The bulk specific gravity of the powder is defined and measured according to JIS K6721.

The powder can be applied to various powder molding methods such as a powder molding method, a fluid immersion method, an electrostatic coating method, a powder spraying method, and a powder rotational molding method. Further, in order to improve the powder fluidity of the powder, known fluidity improving fine particles such as inorganic particles such as silica and alumina and polymer fine particles such as polypropylene powder may be added. For example, in the case of the powder molding method, the powder is put into a stainless steel rectangular container attached to a single-shaft rotary powder compacting machine equipped with a single-shaft rotary handle, and then placed at 180 to 300 ° C., preferably 200 ° C. Attach an electroforming mold of a predetermined shape heated to ~ 280 ° C, rotate the uniaxial rotating handle, and rotate the container and the electroforming mold several times at the same time to the left and right. Tap several times to remove excess powder, then remove the electroforming mold from the container, and heat in a heating furnace at 250 to 450 ° C, preferably 300 to 430 ° C for 5 to 60 seconds, preferably 10 to 30 seconds. It is performed by cooling with water after melting and taking out a molded product from a mold.

The molded body obtained by such a powder molding method has no defects such as underfill and pinholes, and has excellent mechanical properties, heat resistance, grain transferability, and scratch resistance. It is suitably used for steering wheels, curtain airbags, ceilings, doors, and seats.

Next, the foam composition of the present invention and the foam using the composition will be described. The foam of the present invention is obtained by foaming a foam composition (the foam composition of the present invention) containing at least the hydrogenated diene copolymer described above and a foaming agent. . That is, the foam of the present invention is a foam composition containing a hydrogenated diene copolymer having excellent processability, flexibility, and mechanical properties even when used alone, by a suitable foam molding method or the like described below. Since it is foamed, it has excellent vibration damping properties in addition to the above-mentioned properties of the hydrogenated diene copolymer. Therefore, the foam of the present invention is particularly required to have excellent vibration damping properties. It is suitable as various cushioning materials including foams and the like.

Next, a production example of the foam of the present invention will be described. In order to obtain the foam of the present invention, a foaming agent is blended as an essential component with the hydrogenated diene copolymer of the present invention, and a crosslinking agent such as peroxide is further blended as necessary. In addition, components other than the above may be appropriately added as necessary. It is also preferable to further blend a thermoplastic polymer other than the hydrogenated diene copolymer. Examples of the thermoplastic polymer include the same as the above-mentioned “(b) component (thermoplastic polymer)” contained in the polymer composition of the present invention.

Usually, a banbury mixer, a kneader, or an extruder can be used when compounding a polymer, an oil, a filler, and the like. However, it is preferable that the crosslinking agent and the foaming agent be compounded using an open two-roll. The obtained compound is filled in a predetermined mold, a crosslinking reaction is advanced at a predetermined temperature and time by a heating and pressing press, and the foaming agent is decomposed. The hydrogenated diene copolymer can be foamed by the pressure of the decomposition gas. In addition to this, injection foaming or extrusion foaming can be performed by selecting the type and amount of the foaming agent to be blended, processing conditions, and the like.

In the foam composition of the present invention, an inorganic filler can be blended, and the inorganic filler can also serve as a foam nucleating agent when foaming the foam composition of the present invention. . Examples of the inorganic filler include glass fiber, glass beads, potassium titanate, talc, mica, barium sulfate, carbon black, silica, carbon-silica dual phase filler, clay, calcium carbonate, magnesium carbonate, and the like. Can be. The amount of the inorganic filler is usually 200 parts by mass or less, preferably 100 parts by mass, based on the total amount of 100 parts by mass of the hydrogenated diene copolymer of the present invention and other thermoplastic resins to be blended if necessary. Not more than parts by mass. If the amount exceeds 200 parts by mass, the strength properties of the foam may be impaired, which is not preferable. In addition, as an inorganic filler, calcium carbonate, silica, and carbon black are especially preferable.

The foam composition of the present invention may contain a softener. The softener can also serve as a melt viscosity modifier when foaming the foam composition of the present invention. The softener is not particularly limited as long as it is an extender oil or a softener that is generally used for hydrogenated diene copolymers. For example, a mineral oil-based extender oil can be mentioned as a preferred example.

The mineral oil-based extender oil preferably has a viscosity specific gravity constant (or viscosity specific gravity constant; hereinafter abbreviated as VGC) of 0.790 to 0.999, and more preferably V.C.C. G. FIG. C. Is 0.790 to 0.949, particularly preferably V.I. G. FIG. C. Is 0.790 to 0.912. As the extender oil, generally, an aromatic extender oil, a naphthenic extender oil, and a paraffin extender oil are known.

Among these, as the aromatic extender oil satisfying the above viscosity specific gravity constant, Diana Process Oil AC-12, AC460, AH-16, AH-58 (all trade names) manufactured by Idemitsu Kosan Co., Ltd. ExxonMobil's Mobilzol K, 22 and 130 (all trade names), Nikko Kyoishi Co., Ltd., Kyoishi Process X50, X100 and X140 (all trade names), Shell Chemical Co., Ltd. Rezox No. 3. Dute Rex 729UK (all trade names), Nippon Oil (former Nippon Oil) Co., Ltd., Komorix 200, 300, 500, 700 (all trade names), ExxonMobil Esso Process oil 110, 120 (all trade names), manufactured by Nippon Oil (formerly Mitsubishi Oil), Mitsubishi 34 heavy process oil, Mitsubishi 44 heavy process oil, Mitsubishi 38 heavy process oil, Mitsubishi 39 heavy process oil (any Are also trade names).

Examples of the naphthenic extender oil satisfying the viscosity specific gravity constant include Diana Process Oil NS-24, NS-100, NM-26, NM-280, and NP-24 manufactured by Idemitsu Kosan Co., Ltd. ExxonMobil's Naplex 38 (trade name), Fujikosan's Fukkol FLEX # 1060N, # 1150N, # 1400N, # 2040N, # 2050N (all trade names) Kyoishi Process R25, R50, R200, R1000 (all trade names) manufactured by Nippon Kyoishi Co., Ltd., Shell Flex 371JY, 371N, 451N, 451, and N-40, manufactured by Shell Chemical Co., Ltd. 22, 22R, 32R, 100R, 100S, 100SA, 220RS, 220S, 260, 320R, 680 (all Product name), Nippon Oil (former Nippon Oil) Komorix No. 2 process oil (trade name), ExxonMobil Co., Ltd., Esso Process Oil L-2, 765 (all trade names), Nippon Oil (Former Mitsubishi Petroleum) Co., Ltd. and Mitsubishi 20 Light Process Oil (trade name).

Further, as paraffin-based extender oils satisfying the above viscosity specific gravity constants, Diana Process Oil PW-90, PW-380, PS-32, PS-90, and PS-430 (manufactured by Idemitsu Kosan Co., Ltd.) (Trade name), FUKKOR PROCESS P-100, P-200, P-300, P-400, P-500 (all trade names) manufactured by Fujikosan Co., Ltd. , Kyoishi Process P-200, P-300, P-500, Kyoishi EPT750, 1000, Kyoishi Process S90 (all trade names), Lubrex 26, 100, and 100 460 (all trade names), ExxonMobil Esso Process Oil 815, 845, B-1 and Naplex 32 (all trade names), Nippon Oil (formerly Mitsubishi Oil) Mitsubishi 10 Rye Process oil (trade name), and the like.

The amount of the softener is 100 parts by mass or less, preferably 50 parts by mass or less, based on 100 parts by mass of the hydrogenated diene-based copolymer and the total amount of other thermoplastic resins blended as necessary. . If it exceeds 100 parts by mass, the strength of the obtained foam may be impaired, which is not preferable.

In addition, the foam composition of the present invention may contain bitumen, a flame retardant, an antioxidant, a lubricant, a coloring agent, a UV absorber, a heat stabilizer, an antiaging agent, as long as the purpose is not impaired. Other additives such as agents, processing aids, light-fast (weather) agents, and antibacterial agents can be added.

Examples of the bituminous substance that can be added to the composition for a foam of the present invention include straight asphalt or blown asphalt, which is frequently used in automobile vibration damping materials, or a compound of these and an inorganic substance. Examples of the flame retardant include a halogen-based flame retardant, a phosphorus-based flame retardant, and an inorganic flame retardant. In consideration of the dioxin problem, a halogen-free phosphorus-based flame retardant and an inorganic flame retardant are preferable.

Phosphorus-based flame retardants include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol-bis- (diphenyl phosphate), 2-ethylhexyl diphenyl phosphate, dimethyl methyl phosphate , Triallyl phosphate and the like, or a condensate thereof, ammonium phosphate or a condensate thereof, and diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate. Examples of the inorganic flame retardant include magnesium hydroxide, aluminum hydroxide, zinc borate, barium borate, kaolin clay, calcium carbonate, alunite, basic magnesium carbonate, calcium hydroxide and the like. The above-mentioned flame retardants include a so-called flame retardant auxiliary agent, which has a low effect of exhibiting its own flame retardancy but exhibits a synergistically superior effect when used in combination with another flame retardant.

Examples of the lubricant that can be added to the foam composition of the present invention include a paraffinic or hydrocarbon resin, a metal soap, a fatty acid, a fatty acid amide, a fatty acid ester, and a fatty acid that are generally used to impart molding stability. Group metal salts and the like. As the foaming agent, a known inorganic or organic foaming agent can be used. Specific examples of the foaming agent include sodium bicarbonate, ammonium bicarbonate, sodium carbonate, and ammonium carbonate as inorganic foaming agents, and azodicarbonamide, dinitrosopentamethylenetetramine, dinitrosoterephthalamide as organic foaming agents. And azobisisobutyronitrile, barium azodicarboxylate, and sulfonyl hydrazides such as toluenesulfonyl hydrazide. Among them, organic foaming agents such as azodicarbonamide are preferable because of their high expansion ratio. These foaming agents may be used in combination with known foaming aids such as urea and urea derivatives.

The blending amount of the foaming agent is 1 to 50 parts by mass, preferably 2 to 30 parts by mass, based on 100 parts by mass of the hydrogenated diene copolymer and the total amount of the thermoplastic resin blended if necessary. is there. If the amount of the foaming agent is less than 1 part by mass, only a foam having a low expansion ratio can be obtained. On the other hand, if the amount is more than 50 parts by mass, gas generated by decomposition of the foaming agent increases, and the gas pressure is abnormally high. Too much, and the resulting product may crack.

Examples of the cross-linking agent include at least one selected from the group consisting of sulfur, a compound that generates sulfur upon heating, an organic peroxide, a polyfunctional monomer, and a silanol compound. At the time of crosslinking, a combination of a polyfunctional monomer and electron beam irradiation, or a combination of a photosensitizer and ultraviolet irradiation may be used.

As the sulfur, powdered sulfur, sedimentable sulfur, colloidal sulfur, surface-treated sulfur and the like can be used. Compounds that generate sulfur by heating include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), dipenta Methylene thiuram tetrasulfide (DPTT) and the like can be used. Examples of the vulcanization accelerator used in combination with sulfur or a compound that generates sulfur by heating include tetramethylthiuram disulfide (TMTD) N-oxydiethylene-2-benzothiazolylsulfenamide (OBS), N-cyclohexyl-2- Benzothiazyl sulfenamide (CBS), dibenzothiazyl disulfide (MBTS), 2-mercaptobenzothiazole (MBT), zinc di-n-butyl dithiocarbide (ZnBDC), zinc dimethyl dithiocarbide (ZnMDC) and the like. Can be

In the case of organic peroxide crosslinking compounding, dicumyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, α, α′-di-t-butylperoxy-di-p-diisopropylbenzene , N-butyl-4,4-bis-t-butylperoxyvalerate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (t-butylperoxy) Oxy) hexane and the like can be used. In the case of organic peroxide crosslinking, various polyfunctional monomers may be added at the same time. Specific examples of the polyfunctional monomer include trimethylolpropane trimeacrylate, ethylene glycol dimethacrylate, triallyl isocyanate, diallyl phthalate and the like. The organic peroxide / polyfunctional monomer (molar ratio) in this case is usually 1/1 to 1/50, preferably 1/2 to 1/40.

The amount of the crosslinking agent component used is, for example, in terms of the mass of a compound such as sulfur or an organic peroxide, the total amount of the hydrogenated diene-based copolymer, and other thermoplastic resin blended if necessary 100 It is 0.001 to 50 parts by mass, preferably 0.01 to 20 parts by mass with respect to parts by mass. If the amount is less than 0.001 part by mass, crosslinking may be insufficient and a foam having satisfactory heat resistance and mechanical strength may not be obtained. On the other hand, if it exceeds 50 parts by mass, excessive crosslinking may occur and a required expansion ratio may not be obtained.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited by these Examples. In the Examples and Comparative Examples, “parts” and “%” are based on mass unless otherwise specified. Various components used in Examples and Comparative Examples and various measurements were performed according to the following methods.

(1) Method for measuring physical properties of hydrogenated diene copolymer The physical properties of the hydrogenated diene copolymer were measured by the following methods.

[Hydrogenation ratio]: The hydrogenation ratio of the conjugated diene was calculated from a ¹ H-NMR spectrum at 270 MHz using a carbon tetrachloride solution.

[Melt flow rate (MFR)]: Measured at 230 ° C. under a load of 21.2 N according to JIS K7210.

[Total styrene unit content (also referred to as “total bound styrene content”)]: Calculated from a 270 MHz, ¹ H-NMR spectrum using a carbon tetrachloride solution.

[Vinyl bond content (V)]: The vinyl bond (1,2-bond and 3,4-bond) content was calculated by the Hampton method using an infrared analysis method.

[BS ratio]: Calculated from the charged amount using the following equation.
BS ratio (%) = (total amount of vinyl aromatic compound charged in each (B) block of hydrogenated diene copolymer / total vinyl aromatic compound in the hydrogenated diene copolymer) Total amount) x 100

[LS ratio]: A solution prepared by dissolving 30 mg of a sample in 0.6 ml of carbon tetrachloride was integrated 50 times at 23 ° C. using ¹ H-NMR (270 MHz) using tetramethylsilane as a standard substance. It was calculated using the equation.
LS ratio (%) = [(area intensity of 6.8 to 6.0 ppm portion × 2.5) / (area intensity of 7.6 to 6.0 ppm portion)] × 100

[Melting viscosity]: Using a 20 mmΦ cone plate (cone angle: 2 °) with a viscoelasticity measuring device (“MR-500” manufactured by Rheology Co.) at a temperature of 230 ° C, a frequency of 0.1 Hz and a strain of 0.1. The melt viscosity η ^* (complex dynamic viscosity) was measured.

[Weight average molecular weight (Mw) of hydrogenated diene copolymer]: Determined in terms of polystyrene using gel permeation chromatography (room temperature GPC, column: GMH-XL, manufactured by Tosoh Corporation).

(2) Production example of hydrogenated diene copolymer (Production Example 1: Production of hydrogenated diene copolymer (H-1))
After 25 kg of degassed and dehydrated cyclohexane and 400 g of styrene were charged into an autoclave having an internal volume of 50 liters, 300 g of tetrahydrofuran and 3.5 g of n-butyllithium were added, and adiabatic polymerization from 50 ° C. was performed for 20 minutes. After the temperature of the reaction solution was set to 20 ° C., 3,500 g of 1,3-butadiene and 700 g of styrene were added, and adiabatic polymerization was performed. After the conversion reached almost 100%, 400 g of styrene was further added to carry out polymerization.

After the polymerization was completed, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and the mixture was stirred for 20 minutes to react with living terminal lithium as a living anion to obtain lithium hydride. The reaction solution was heated to 90 ° C., tetrachlorosilane (1.5 g) was added, and the mixture was stirred for about 20 minutes. Then, a hydrogenation reaction was performed using a titanocene compound described in JP-A-2000-37632.

The hydrogenated diene copolymer (H-1) obtained had a hydrogenation ratio of 98%, a weight average molecular weight of 120,000, a bound styrene content of 30% by mass, a BS ratio of 47%, and an LS ratio of 48%. The B block had a vinyl bond content of 73%, an MFR of 20 g / 10 min, and a melt viscosity of 450 Pa · s. Table 1 shows the measurement results of the physical properties.

Hereinafter, by the same method, the amount of monomer, the amount of tetrahydrofuran added, the amount of catalyst, the polymerization temperature, the polymerization time and the like are varied, so that H-2 to H5, H-8 to H-13 shown in Table 1 and Table 2, A hydrogenated diene copolymer of H-16 and R-1 to R10 was produced. Tables 1 and 2 show the measurement results of the physical properties of these hydrogenated diene copolymers. In addition, the hydrogenated diene copolymer of H-7 and H-15 uses tetrachlorosilane as a coupling agent.

(Production Example 2: Production of hydrogenated diene copolymer (H-6))
After 25 kg of degassed and dehydrated cyclohexane and 400 g of styrene were charged into an autoclave having an internal volume of 50 liters, 150 g of tetrahydrofuran and 3.2 g of n-butyllithium were added, and adiabatic polymerization from 50 ° C. was performed for 20 minutes. After the temperature of the reaction solution was adjusted to 20 ° C., 2,950 g of 1,3-butadiene and 1200 g of styrene were added, and adiabatic polymerization was performed. After the conversion reached almost 100%, 400 g of styrene was further added and adiabatic polymerization was performed for 20 minutes, and then 50 g of 1,3-butadiene was added to perform adiabatic polymerization.

After the polymerization was completed, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and the mixture was stirred for 20 minutes to react with living terminal lithium as a living anion to obtain lithium hydride. The reaction solution was heated to 90 ° C., tetrachlorosilane (1.5 g) was added, and the mixture was stirred for about 20 minutes. Then, a hydrogenation reaction was performed using a titanocene compound described in JP-A-2000-37632.

The hydrogenated diene copolymer (H-6) obtained had a hydrogenation ratio of 98%, a weight average molecular weight of 130,000, a bound styrene content of 40% by mass, a BS ratio of 60%, and an LS ratio of 36%. The B block had a vinyl bond content of 56%, an MFR of 18 g / 10 min, and a melt viscosity of 520 Pa · s. Table 1 shows the measurement results of the physical properties. “C” in Structure 2 of the hydrogenated block copolymer (H-6) shown in Table 1 represents a hydrogenated polybutadiene block.

Further, these hydrogenated diene-based copolymers were molded using an electrothermal press molding machine (manufactured by Kansai Roll Co., Ltd.) at a mold temperature of 190 ° C., a pressurization heating time of 10 minutes, and a pressurization cooling time of 5 Then, a sheet (molded body) for evaluation of physical properties having a thickness of 2 mm, a vertical width of 120 mm, and a horizontal width of 120 mm was prepared by press molding under the conditions of minutes, and evaluated as described later. The results are shown in Tables 1 and 2.

Here, H-1 to H-16 are hydrogenated diene copolymers within the scope of the present invention, and R-1 to R-8 are hydrogenated diene copolymers outside the scope of the present invention. It is. R-1 is an example in which the vinyl aromatic compound is not copolymerized in the block (B). R-2 and R-3 are those whose BS ratio and LS ratio are out of the range of the present invention. R-4, R-5, and R-8 have a vinyl bond content outside the scope of the present invention. R-6 has a total vinyl aromatic compound unit content outside the range of the present invention. R-7 is such that the conjugated diene compound unit is contained in the (A) block in an amount of 50% by mass.

(3) Various components (a) The component is a hydrogenated diene copolymer having the structure shown in Table 1 and Table 2, and (b) the component is polypropylene (olefin-based resin) manufactured by Sun Allomer (PM940M, MFR = 30 g / 10 min (230 ° C., 21.2 N load). The component (c) is an olefin-based thermoplastic elastomer (TPO) and was produced by the following method.

Ethylene / propylene / 5-ethylidene-2-norbornene terpolymer (ethylene content 66% by mass, 5-ethylidene-2-norbornene content 4.5% by mass, intrinsic viscosity measured at 135 ° C. in a decalin solvent [ η] = 4.7, 70 parts of paraffinic mineral oil-based softener (product name “Diana Process Oil PW380”, manufactured by Idemitsu Kosan Co., Ltd., content: 50% by mass), propylene / ethylene random copolymer (MFR (temperature 230 ° C, load 21.2N) 23g / 10min, 25 parts of product name “Novatech PPFL25R” manufactured by Nippon Polychem Co., Ltd., and a propylene / 1-butene amorphous copolymer (propylene content 71 mol%, melt viscosity 8000 cSt, density 0) .87g / cm ^3, Mn6500, manufactured by Ube Industries, Ltd., product name "APAO UT2780") 5 parts, anti-aging agent (Chibasu 0.1 parts of "Irganox 1010" manufactured by Charty Chemicals and 0.2 parts of silicone oil ("SH-200 (100 cSt)" manufactured by Dow Corning Toray Silicone Co., Ltd.) were heated to 150 ° C. The mixture was put into a liter double-arm type pressure kneader (manufactured by Moriyama), kneaded at 40 rpm for 20 minutes, and then pelletized by a feeder ruder (manufactured by Moriyama) set at 180 ° C. and 40 rpm. Further, 1 part of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (manufactured by NOF CORPORATION, product name “Perhexa 25B-40”) and 1 part of N, N ′ were added to the obtained pellets. 0.5 part of m-phenylene bismaleimide (Ouchi Shinko Chemical Co., Ltd., product name "Barnock PM") is blended and mixed with a Henschel mixer for 30 seconds. Then, a twin-screw extruder (manufactured by Ikegai Co., Ltd., model “PCM-45”, a fully meshing screw in the same direction, and L / D which is the ratio of the length L of the screw flight portion to the screw diameter D is 33. 5) and extruded while performing dynamic heat treatment under the condition of staying at 230 ° C. and 300 rpm for 2 minutes to obtain a pellet-shaped dynamically crosslinked TPO.

(4) Evaluation of Powder Shape Physical properties indicating the shape of the powder were measured by the methods described below, and the shape of the powder was evaluated.

[Powder bulk specific gravity]: 100 ml of powder was collected and weighed in accordance with JIS K6721, and the bulk specific gravity was calculated.

[Powder spherical average particle diameter]: 100 powder particles are arbitrarily sampled, the mass thereof is determined, the average volume of the particles is calculated from the mass and the specific gravity of the polymer composition, and the same as the average volume. The diameter of the volume sphere was calculated and defined as a sphere-converted average particle size.

(5) Evaluation of physical properties of molded articles Physical properties of various molded articles were measured and evaluated by the following methods.

[Tensile properties (mechanical strength)]: According to JIS K6301, the tensile strength and elongation of the molded body were measured.

[Hardness (flexibility)]: Shore A hardness was measured according to ASTM D-2240. The hardness of the molded body was evaluated according to the following criteria.
：: excellent in flexibility (hardness is less than 90)
×: Inferior in flexibility (hardness exceeds 90)

[Mold appearance]: The molded body was visually evaluated for appearance according to the following criteria.
：: No pinholes, good grain transferability ×: Poor appearance phenomena such as pinholes or underfill, poor grain transferability, uneven gloss, etc.

[Scratch resistance]: Using a Tabers clutch tester manufactured by Toyo Seiki Seisaku-Sho, Ltd., a scratch test was performed using each molded product as a sample while changing the load by 50 g. The presence or absence of scratches on the sample surface after the test was visually observed.
：: Excellent scratch resistance (scratch load exceeds 200 g)
×: poor scratch resistance (scratch load is less than 200 g)

[Heat resistance]: The molded body was left at 110 ° C. for 24 hours, and the change in gloss value (gloss) before and after heating was evaluated according to the following criteria. The gloss value was measured by a digital photometer (GM-26D, manufactured by Murakami Color Research Laboratory, reflection angle: 60 degrees).
：: excellent heat resistance (gloss value difference is less than 1.0)
×: Inferior in heat resistance (gloss value difference exceeds 1.0)

[Weather resistance]: Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), the molded body was allowed to stand at a black panel temperature of 83 ° C. (without rain) for 50 hours, and a retention ratio of tensile strength before and after that was determined. evaluated.
：: Excellent weather resistance (retention rate exceeds 90%)
×: Poor weather resistance (retention rate is less than 90%)

(Example 1 (powder production and powder molding))
70 parts by mass of the hydrogenated diene copolymer (H-1) obtained in the above production example and 30 parts by mass of the olefin resin (PM940M) are put into a 30 mmφ extruder (manufactured by Tanabe Plastic Co., Ltd.) and heated and kneaded at 190 ° C. Thereafter, the mixture was discharged from a die having a discharge opening diameter of 1.0 mm (temperature: 190 ° C.) at a discharge speed of 1 kg / hour / hole, was taken out at a take-up speed of 32 m / min, and was returned to room temperature to obtain a strand having a diameter of 0.8 mm. . Next, this was cut with a pelletizer to obtain a powder composed of the polymer composition having a bulk specific gravity of 0.42 and a sphere-converted average particle diameter of 0.65 mm. The powder was press-molded using an electric heat press machine under the conditions of a mold temperature of 190 ° C., a heating time of 10 minutes and a cooling time of 5 minutes to produce a 2 mm thick sheet. The tensile properties, hardness, and weather resistance of this sheet were measured and evaluated.

Next, the powder composed of the above polymer composition is charged into an electroformed mold (length: 1200 mm × width: 500 mm) at a temperature of 250 ° C. and left for 5 seconds. Was left for 60 seconds. Thereafter, the molded product was cooled and removed from the mold to obtain a molded article with a grain having a thickness of 1 mm. The molded appearance, scratch resistance, and heat resistance of the molded body with the grain were evaluated. Table 3 shows the evaluation results of these physical properties.

(Examples 2 to 10)
According to the formulation shown in Table 3, a powder composed of the polymer composition was obtained in the same manner as in Example 1, and a sheet and a molded article with a grain were produced using the powder, and the physical properties were evaluated. Table 3 shows the results.

(Comparative Examples 1 to 8)
According to the formulation shown in Table 4, a powder composed of the polymer composition was obtained in the same manner as in Example 1, and a sheet and a molded body with a grain were produced using the powder, and the physical properties were evaluated. Table 4 shows the results.

(Example 11 (extrusion molding))
2100 g of hydrogenated diene-based copolymer (H-9) and 900 g of olefin-based resin (PM940M) were melt-kneaded at 190 ° C. and pelletized using a 40 mmφ extruder (FS-40, manufactured by Ikegai Co., Ltd.). 1500 g of pellets were obtained. A T-die (200 mm width, lip interval 0.7 mm) was attached to the tip of a 20 mmφ extruder (manufactured by Toyo Seiki Co., Ltd.), and the cylinder temperature of the extruder was 190 ° C., the temperature of the T-die was 200 ° C. Extruded under the conditions of a roll temperature of 30 ° C. and a take-up speed of 10 m / min, taken out by a take-off machine to produce a 1 mm-thick sheet-like extruded body for physical property evaluation, and measured the tensile properties, hardness and weather resistance of the formed body ·evaluated. Further, the pellets were press-molded using an electro-thermal press molding machine (manufactured by Kansai Roll Co., Ltd.) under the conditions of a mold temperature of 190 ° C., a heating time of 10 minutes, and a cooling time of 5 minutes, A sheet-like molded article with a grain having a thickness of 1 mm was produced, and the molded article was evaluated for scratch resistance. Table 5 shows the results.

(Examples 12 to 20)
According to the formulation shown in Table 5, a sheet-like extruded product for evaluating physical properties was produced in the same manner as in Example 11, and the physical properties were evaluated. Table 5 shows the results.

(Comparative Examples 9 to 17)
According to the formulation shown in Table 6, a sheet-like extruded product for evaluating physical properties was prepared in the same manner as in Example 11, and the physical properties were evaluated. Table 6 shows the results.

(Examples 21 to 25, Comparative Examples 18 to 20)
After using the hydrogenated diene copolymer (H-1 to H-5, R-1, R-9, R-10) described above and forming a sheet at 160 ° C. with a 6-inch open two-roll, Using a press, a 2 mm thick sheet was formed at 190 ° C. and a gauge pressure of 150 kg, and the physical properties were evaluated. Similarly, a sheet having a thickness of 1 mm was formed, and dynamic viscoelasticity (loss tangent peak temperature, loss tangent peak height) was measured. The physical properties shown in Table 7 were evaluated for these compacts (2 mm thick sheets). Table 7 shows the results. The methods for measuring and evaluating “loss tangent peak temperature (° C.)”, “loss tangent peak height”, and “weatherability (stickiness)” shown in Table 7 are shown below.

[Loss tangent peak temperature, loss tangent peak height]: Using RSAII manufactured by Rheometric Co., Ltd., under the conditions of a tensile mode, a measurement frequency = 1 Hz, a heating rate = 3 ° C./min, and an initial strain = 0.05%. The loss tangent peak temperature (° C.) and the loss tangent peak height were measured.

[Weather resistance (stickiness)]:
Using a Daipla Metal Weather (super-accelerated weathering tester) manufactured by Daipla Wintes Co., Ltd., the stickiness of the sample surface after 5 cycles of irradiation under the following test conditions (1) to (3) was evaluated according to the following evaluation criteria ( (Contact confirmation). In addition, under the following test conditions, (1) and (2) were each performed once, for a total of 8 hours, which was defined as one cycle.
(1) Irradiation mode: black panel temperature = 63 ° C., humidity = 50% RH, time = 4 hours (2) Non-irradiation mode: temperature = 30 ° C., humidity = 98% RH, time = 4 hours (3) Rainfall: The sample is showered for 20 seconds each before and after the non-irradiation mode.
：: No or almost no sticky △: Sticky ×: Severe sticky

(Example 26, Comparative example 21)
Under the same conditions as in Example 21, they were blended with a roll according to the blending recipe shown in Table 7 to prepare each measurement sheet (molded body for evaluating physical properties). This molded article was evaluated for physical properties shown in Table 7. Table 7 shows the results.

(Comparative Example 22)
Hydrogenated styrene-isoprene-styrene block copolymer (SEPS) shown in Table 7 (the ratio of 1,2- and 3,4-bonds to all isoprene bonds in the isoprene block: 50%, styrene content: 20) %, Molecular weight: 116,000), and a molded article for evaluating physical properties was produced in the same manner as in Example 21. This molded article was evaluated for physical properties shown in Table 7. Table 7 shows the results.

(Examples 27 to 31, Comparative Example 23)
According to the composition shown in Table 8, a foam composition was obtained at 125 ° C. using two open rolls. Thereafter, using a mold having a thickness of 12 mm, the composition was crosslinked at 165 ° C. for 12 minutes, and then opened to atmospheric pressure to obtain a foam. The surface layer of the obtained foam was scraped to obtain a foam sample having a predetermined thickness without a skin layer. The physical properties shown in Table 8 were evaluated for the obtained foam sample. Table 8 shows the results. In addition, the measuring method of "density (g / cm < ³ >)", "hardness (Type-C) (degree)", and "rebound resilience (%)" shown in Table 8 is shown below.

[Density]: Measured at 23 ° C. by an underwater displacement method (buoyancy method).

[Hardness (Type-C)]: Measured using a sponge hardness meter (Type-C) manufactured by Kobunshi Keiki Co., Ltd.

[Rebound resilience]: Measured at a sample thickness of 12.6 to 12.8 mm according to JIS K6255, and the value of the fourth impact was used as the measured value.

From the results shown in Tables 1 to 6, the hydrogenated diene copolymer of the present invention is excellent in flexibility and mechanical properties, and a fine powder can be obtained by using the composition (polymer composition). In addition, the molded product obtained by forming the powder into a powder, and the sheet-shaped molded product of the composition are rich in flexibility, excellent in mechanical properties, molded appearance, scratch resistance, heat resistance, and weather resistance. I understand. On the other hand, when the hydrogenated diene copolymer in which the vinyl aromatic compound was not copolymerized in the block (B) was used (Comparative Example 1), fine powder was not obtained, and the hydrogenated diene copolymer was not obtained. The sheet-shaped molded article using the diene copolymer was inferior in flexibility (hardness), molded appearance, and scratch resistance.

Moreover, the sheet-shaped molded product of Comparative Example 9 was inferior in mechanical strength, flexibility (hardness), and scratch resistance. The sheet-shaped molded articles of Comparative Examples 2 and 10 using a hydrogenated diene copolymer having a BS ratio of more than 80% and an LS ratio of less than 10% have insufficient mechanical strength and scratch resistance. Was. When a hydrogenated diene copolymer having a BS ratio of less than 10% and an LS ratio of more than 80% was used (Comparative Example 3), and a hydrogenated diene copolymer having a vinyl bond content of less than 30% was used. When used (Comparative Example 4), fine powder was not obtained, and the sheet-like molded article using these hydrogenated diene copolymers had mechanical strength, flexibility, molded appearance, and scratch resistance. It was inferior in sex. Further, it can be seen that the sheet-shaped molded bodies of Comparative Examples 11 and 12 are not sufficient in mechanical strength, flexibility, and scratch resistance.

The sheet-like molded article of Comparative Example 5 using a hydrogenated diene copolymer having a vinyl bond content of more than 75% has heat resistance and scratch resistance, and the sheet-shaped molded article of Comparative Example 13 has scratch resistance. But each was not enough. The sheet-like molded articles of Comparative Examples 6 and 14 using the hydrogenated diene copolymer having a total bound styrene content outside the range of the present invention were all inferior in scratch resistance. In Comparative Example 7 in which the conjugated diene compound was copolymerized in the block (A), heat resistance and scratch resistance were poor, and in Comparative Example 15, scratch resistance was poor. Moreover, the sheet-shaped molded articles of Comparative Examples 8 and 16 using TPO were inferior in scratch resistance. Further, the sheet-like molded product of Comparative Example 17 using a hydrogenated diene-based copolymer having a vinyl bond content of less than 30% was inferior in flexibility.

From Table 7, it was found that the hydrogenated diene copolymer of the present invention had a higher loss tangent peak temperature than the comparative example, and was excellent in vibration damping properties at a temperature closer to normal temperature. In addition, Examples 21 to 26 shown in Table 7 have no stickiness in the weather resistance test, whereas Comparative Example 22 has a high loss tangent peak temperature, but it is not preferable that stickiness occurs in the weather resistance test. Further, from Table 8, it can be seen that the foams of Examples 27 to 31 of the present invention have lower rebound resilience and are superior in vibration damping property and shock absorption as compared with Comparative Example 23 having the same density and the same hardness.

The hydrogenated diene copolymer having a specific structure of the present invention, particularly a molded article of a composition obtained by blending the olefin polymer with the copolymer is rich in flexibility, excellent in mechanical properties, heat resistance, and weather resistance. Bumpers, exterior moldings, gaskets for wind seals, gaskets for door seals, gaskets for trunk seals, roof side rails, emblems, inner and outer skin materials such as inner panels, door trims, console boxes, weather strips, etc. Such as leather seats, seal materials for aircraft and ships, and interior and exterior skin materials, etc., civil and architectural seal materials, interior and exterior skin materials, waterproof sheet materials, etc., seal materials for general machinery and equipment, etc. Rolls for information equipment, cleaning blades, films for electronic components, semi-conductive parts Protective films, sealing materials, image protective films for photographs, etc., cosmetic films for construction materials, medical equipment parts, electric wires, daily necessities, sports goods, It can be widely used in general processed products such as shock absorbing sponges for shoe soles, shock absorbing sponges for insoles, cup insoles, packaging materials for shock absorption, and cushioning materials.

¹ is a ¹ H-NMR spectrum (frequency: 270 MHz, region: 7.6 to 6.0 ppm) of a hydrogenated diene copolymer (H-2).

Claims (16)

At least two vinyl aromatic compound-based polymer blocks (A);
At least one block copolymer containing a copolymer block of a vinyl aromatic compound and a conjugated diene compound (B) is hydrogenated, and satisfies all of the following conditions (1) to (3): Hydrogenated diene copolymer.
(1): The total content of the vinyl aromatic compound units in the hydrogenated diene copolymer is 20 to 70% by mass.
(2): The ratio (BS) of the vinyl aromatic compound unit content contained in the block (B) to the total vinyl aromatic compound unit content in the hydrogenated diene copolymer is 10 to 80%. It is.
(3): The content of the vinyl bond derived from the conjugated diene compound in the hydrogenated diene-based copolymer is 30 to 75%. At least two vinyl aromatic compound-based polymer blocks (A);
At least one block copolymer containing a copolymer block of a vinyl aromatic compound and a conjugated diene compound (B) is hydrogenated, and satisfies all of the following conditions (1) to (3): Hydrogenated diene copolymer.
(1): The total content of the vinyl aromatic compound units in the hydrogenated diene copolymer is 20 to 70% by mass.
(2): The ratio (LS) of the long-chain vinyl aromatic compound unit content to the total vinyl aromatic compound unit content in the hydrogenated diene copolymer is 10 to 80%.
(3): The content of the vinyl bond derived from the conjugated diene compound in the hydrogenated diene copolymer is 30 to 75%. The hydrogenated diene-based copolymer according to claim 1 or 2, wherein 90% or more of double bonds derived from the conjugated diene compound are hydrogenated. The hydrogenated diene-based copolymer according to any one of claims 1 to 3, wherein a melt flow rate (MFR) measured at 230 ° C and a load of 21.2N is 10 to 200 g / 10 minutes. The hydrogenated diene-based copolymer according to any one of claims 1 to 3, wherein a melt flow rate (MFR) measured at 230 ° C and a load of 21.2N is 0.01 to 100 g / 10 minutes. The hydrogenated diene copolymer according to claim 1, wherein the melt viscosity at 230 ° C. and 0.1 Hz is 2000 Pa · s or less. The hydrogenated diene-based copolymer (a) according to any one of claims 1 to 6 and a thermoplastic polymer (b) other than the hydrogenated diene-based copolymer (a) are represented by a mass ratio of ( A) / (b) = a polymer composition containing 99/1 to 1/99. The polymer composition according to claim 7, wherein the thermoplastic polymer (b) is a propylene-based polymer. A powder obtained by subjecting the polymer composition according to claim 8 to mechanical pulverization, die face cutting, or strand cutting. The powder according to claim 9, having a bulk specific gravity of 0.38 or more and a sphere-converted average particle size of 1.2 mm or less. A molded product obtained by powder molding the powder according to claim 9. A molded article obtained by extruding the hydrogenated diene copolymer according to claim 5. The hydrogenated diene copolymer (a) according to claim 5 and the thermoplastic polymer (b) are contained at a mass ratio of (a) / (b) = 99/1 to 1/99. A molded article obtained by extruding the resulting polymer composition. A foam composition comprising the hydrogenated diene copolymer according to any one of claims 1 to 6 and a foaming agent. The composition for a foam according to claim 14, further comprising a thermoplastic polymer other than the hydrogenated diene-based copolymer. A foam obtained by foaming the foam composition according to claim 14.

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