TW201020289A - Hydrogenated block copolymer composition and molded body using the same - Google Patents

Abstract

This invention provides a hydrogenated block copolymer composition containing (I) a hydrogenated block copolymer that is a hydride of a copolymer of a vinyl aromatic compound and a conjugated diene and has the following features (1) to (4): 5 to 95 percent by mass; and (II) at least one olefin series resin: 5 to 95 percent by mass; (1) polymer block having at least one of the following (b), (c), in which (b) is a hydrogenated copolymer block containing a vinyl aromatic compound and a conjugated diene, (c) is a hydrogenated polymer block taking the conjugated diene as a main body, (2) the content of the vinyl aromatic compound in the foregoing (b) that is 40 to 80 percent by mass, (3) the content of the foregoing (c) in the above (I) that is 20 to 80 percent by mass, (4) in the viscoelasticity measured graph of the hydrogenated block copolymer (I), at least one peak of tan delta (loss tangent) existing at a temperature of above 0 degrees Celcius or below 60 degrees Celcius, and at least one peak of tan delta (loss tangent) existing at a temperature that does not reach 0 degrees Celcius.

Description

201020289 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a hydrogenated block copolymer composition and a shaped body using the same. [Prior Art] Since the hollow molded body such as the tube (10)e) or the soft f(ht)se has been required to have transparency and kink resistance, a soft ethylene-based resin is mainly used as the material.

However, since a soft vinyl chloride-based resin contains a large amount of a plasticizer, it is particularly useful as a medical use when it is dissolved in a chemical solution or blood, or an environmental load is caused by gas generated during incineration. Therefore, seeking alternative materials. In particular, various thermoplastic elastomer compositions have been proposed in recent years. In particular, styrene-based elastomer compositions having excellent flexibility have been proposed (for example, refer to Patent Documents 1 to 6). Patent Document 1 proposes a pipe comprising two hydrogenated copolymers, an olefin resin, and a softener for rubber. A composition comprising a hydrogenated segment copolymer and an olefin-based copolymer and a plasticizer is proposed. In the patent document 3, a composition comprising a hydrocarbon (four), a hydrogen & polymer, and a polymethylpentene resin is proposed. - In the tree, there is a hydrogenated dilute copolymer and a polysulfonate. In Patent Document 5, a composition comprising a hydrogenated dioxo copolymer and a thermoplastic poly 142282.doc 201020289 is obtained. Patent Document 6 proposes a pipe comprising two hydrogenated block copolymers and a polyolefin resin. Further, in particular, in the case of a hollow molded body such as a pipe or a hose, transparency and kink resistance are required in consideration of such practical use. Regarding the transparency, the compatibility of the composition becomes an important factor; regarding kink resistance, energy absorption and softness in a room temperature region are important factors. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 9-316287. [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. 2005-255856 (Patent Document 6) International Publication No. 2009/031625. [Solutions to be Solved] However, the hollow molded body such as a tube or a hose formed by using the styrene-based elastomer composition as described above has the following problems: the balance between transparency and kink resistance is not yet sufficient. Should be improved. Accordingly, an object of the present invention is to provide a composition which is excellent in flexibility and low rebound elasticity, that is, excellent in energy absorption in a room temperature region, and excellent in balance of transparency and kink resistance, and provides a tube using the composition, Soft 142282.doc 201020289 hollow shaped body such as tube. [Technical means for solving the problem] As a result of intensive research to solve the problems of the prior art described above, it has been found that the rebound elasticity and the softness are related to the kink resistance. In addition, the term "knot resistance" refers to the performance of the hollow molded body such as a tube or a hose, which satisfies the easing speed of the kinking moment and the performance of shortening the distance between the entangled tubes. Further, it has been found that a hydrogenated block copolymer composition using a hydrogenated block copolymer having a specific structure and having a peak of tans (loss tangent) in a viscoelasticity measurement chart in a specific temperature region is moderated in the above-described kink speed High sex. Further, a hydrogenated block copolymer composition having high flexibility has been found, and specifically, a hydrogenated block copolymer composition of a hydrogenated block copolymer having a remarkable effect of reducing the tensile modulus of elasticity is used, which shortens the above-mentioned kinked tube The effect of the inter-distance, that is, the bending diameter, is high, thereby completing the present invention. The present invention is as follows. [1] and 1 provide a hydrogenated block copolymer composition containing (I) a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene and having the following ("~ (hydrogenation of the character of the sentence) Block copolymer: 5 to 95% by mass; and (II) at least one olefin resin: 5 to 95 mass% of ruthenium; (1) a polymer block having at least one of the following (b) and (C), (b) a hydrogenated copolymer block comprising an ethylene-based aromatic compound and a co-rolled dilute, 142282.doc 201020289 (C) a hydrogenated polymer block mainly composed of a conjugated diene, (2) the above (b) The content of the vinyl aromatic compound in the range of 4 〇 to 8 〇 mass 0 / 〇, (3) the content of the above (c) in the above (I) is 2 〇 to 80% by mass, (4) hydrogenated block copolymerization The peak of tan § (loss tangent) in the viscoelasticity measurement chart of the object (1) is at least one above and below (6) 且 and at least one is present at less than 0 ° C. [2] Providing a hydrogenated block copolymer composition, A hydrogenated block containing (I) a hydride of a copolymer of a vinyl aromatic compound and a conjugated diene and having the following characteristics (1) to (4) Polymer: 2.5 to 92.5 mass%; (Π) at least one dilute-smoke resin: 5 to 95% by mass; and (III) a hydride of a copolymer of a vinyl aromatic compound and a common diuret and having the following (5) Hydrogenated block copolymer of the characteristics of (9): 2.5 to 92.5 mass. / 〇; (1) having at least one of the following (b), (c) polymer blocks, (b) containing B a hydrogenated polymer block in which a dilute aromatic compound and a common dilute hydrogenated polymer are embedded, (c) a hydrogenated polymer block mainly composed of a conjugated diene, and (2) a vinyl aromatic compound in the above (b) The content is 4 〇 to 8 〇 mass%, and (3) the content of the above (c) in the above (I) is 2 〇 to 8 〇 mass%, and (4) the point elasticity measurement chart of the hydrogenated block copolymer (1) The tan § (loss tangent) peak is above 0 ° C and 6 (at least one below TC, and at least one at 142282.doc -6 - 201020289 0 C, the hydrogenation polymerization of the host polymer (5) has At least two of the vinyl aromatic compound as the block (A), and at least one of the conjugated diene as the main block (B), (6) hydrogenated segment copolymerization The content of all the ethylene-based aromatic compounds in the material_ exceeds 10% by mass and does not exceed 25% by mass,

(7) The amount of the vinyl bond in the hydrogenated polymer block (b) having the conjugated diene as a main component is 62% by mass or more and less than 99% by mass, and (8) the weight average molecular weight of the hydrogenated block copolymer It is 30,000 to 10,000, and (9) % or more of the double bonds of the conjugated diene monomer unit in the hydrogenated block copolymer are hydrogenated. [3] The hydrogenated block copolymer composition according to the above [2], wherein the hydrogenated block copolymer of the above (III) contains at least a single terminal terminal of from 1 to 91% by mass of the above-mentioned total of the diene as a main component The hydrogenated polymer block (Β) β [4] The chlorinated block copolymer composition according to any one of the above (1), wherein the hydrogenated block copolymer of the above (1) contains at least a single terminal The above (c) is a hydrogenated polymer block mainly composed of a conjugated diene. [5] The hydrogenated block copolymer composition according to any one of the above [1] to [4] wherein the content of all the vinyl aromatic compounds in the hydrogenated block copolymer of the above (I) is 20~ 50% by mass. [6] The hydrogenated block copolymer composition according to any one of the above [1] to [5] wherein the (c) vinyl bond amount in the hydrogenated polymer block mainly composed of a conjugated diene It is 50% by mass or more. [7] The hydrogenated block copolymer group 142282.doc 201020289 compound according to any one of the above [1] to [6] wherein the above (b) in the hydrogenated block copolymer of the above (i) comprises ethylene The content of the hydrogenated copolymer block of the aromatic compound and the conjugated diene is 20 to 80% by mass. [8] The hydrogenated block copolymer composition according to any one of the above [1] to [7] wherein the hydrogenated block copolymer of the above (I) has at least one (a) as a vinyl aromatic compound The polymer block of the body. [9] The hydrogenated block copolymer composition according to the above [8], wherein the content of the polymer block having the vinyl aromatic compound as a main component in the hydrogenated block copolymer of the above (I) is 3~ 3 〇 Quality 0/〇. [10] The hydrogenated block copolymer composition according to any one of the above [1] to [7] wherein the hydrogenated block copolymer of the above (I) has at least one (d) vinyl bond amount of 25 mass The following is a polymer block with a total of a diene as a main component. [11] The hydrogenated block copolymer composition according to the above [10], wherein the (d) vinyl bond amount in the hydrogenated block copolymer of the above (1) is 25 mass 〇 / 〇 or less to conjugated diene The content of the polymer block as a main component is 3 to 3 % by mass. [12] The hydrogenated block copolymer composition according to any one of the above [1] to [π], wherein the hydrogenated block copolymer of the above (1) has a weight average molecular weight of 50,000 to 600,000. [13] The hydrogenated block copolymer composition according to any one of [1] to [12] wherein the double bond of the conjugated dilute monomer unit in the hydrogenated block copolymer of the above (1) is 75% The above is hydrogenated. [14] The hydrogenated funnel copolymer according to any one of the above [1] to [13], wherein the olefin-based resin of the above (II) comprises at least one polyacrylic resin. [15] A molded body is provided which is formed by using the hydrogenated block copolymer composition according to any one of the above [" to 々]. [16] A hollow molded body is provided which is used as described above (1) The hydrogenated block copolymer composition of any one of [14] is formed. [Effect of the Invention] According to the present invention, it is excellent in flexibility and low rebound elasticity, and excellent in balance of transparency and kink resistance. A hydrogenated block copolymer composition containing a hydrogenated block copolymer and an olefin resin; and a molded article using the same. [Embodiment] The following is a mode for carrying out the present invention (hereinafter referred to as "this embodiment") ) to explain in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention. [Hydrogenated Scatter Copolymer Composition] As described later, the hydrogenated block copolymer composition of the present embodiment is roughly classified into the hydrogenated block copolymer composition of the first embodiment and the hydrogenated block copolymer of the second embodiment. Composition. The hydrogenated block copolymer composition of the first embodiment contains: (I) a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene and having hydrogenation characteristics of the following (1) to (4) Block copolymer: 5 to 95% by mass; and (II) at least one olefin-based resin: 5 to 95% by mass. 142282.doc 201020289 (1) A polymer money segment having at least one of the following (b), (c). (b) a hydrogenated copolymer block comprising a vinyl aromatic compound and a conjugated diene. (c) a hydrogenated polymer block having a conjugated diene as a main component. (2) The content of the vinyl aromatic compound in the above (b) is from 4 〇 to 8 〇 by mass. (3) The content of the above (c) in the above (I) is -% by mass. (4) The wave loss bee of the nitriding block copolymer (1) in the viscoelasticity measurement chart is above 0 ° C and 6 (at least one below rc and at least one less than 0 C). The hydrogenated block copolymer composition of the second embodiment contains: (I) a hydrogenated block copolymer having the following characteristics of (1), which is a nitride of a copolymer of an ethylene compound and a decadiene: ~ 925 mass%; (π) at least one dilute hydrocarbon resin: 5 to 95 mass and

Σπ) is a hydrogenated segment copolymer having a characteristic of the following (5) to (9) which is nitrided with a copolymer of a vinyl aromatic compound and a common diuret: 2.5 to 92.5 mass%. (1) having at least one (b) comprising an ethyl block. The polymer blocks of the following (b), (e). Hydrogenation copolymerization of an alkenyl aromatic compound with a conjugated diene (c) in a total of two rare &amp; (2) %. The hydrogenated polymer block of the von main body. In the above (b), the content of the arsenic------------------------- (4) The peak of taM (loss tangent) in the viscoelasticity measurement chart of the hydrogenated block copolymer (I) is at least one above 〇 ° C and below 60 ° C, and at least one is present at less than 0 ° C. (5) A polymer block (A) having at least two vinyl aromatic compounds as a main component, and at least one hydrogenated polymer block (B) mainly composed of a conjugated diene. (6) The content of all the vinyl aromatic compounds in the hydrogenated block copolymer (III) exceeds 10% by mass and does not exceed 25% by mass. (7) The amount of the vinyl bond in the hydrogenated polymer block (B) mainly composed of the conjugated diene is 62% by mass or more and less than 99% by mass. (8) The hydrogenated block copolymer has a weight average molecular weight of 30,000 to 300,000. (9) 75% or more of the double bonds of the conjugated diene monomer unit in the hydrogenated block copolymer are hydrogenated. The constituent elements of the hydrogenated block copolymer composition of the present embodiment will be described in detail as φ. &lt;(1) a hydrogenated block copolymer of a hydride of a copolymer of a vinyl aromatic compound and a conjugated diene; and (III) a hydride of a copolymer of a vinyl aromatic compound and a common diterpene Hydrogenated segment copolymer&gt; • Hereinafter, the hydrogenated block copolymer of (I) and the hydrogenated block copolymer of (III) are simply referred to as hydrogenated block copolymer (I), hydrogenated block copolymer (III) ). (Vinyl aromatic compound) Examples of the vinyl aromatic compound constituting the hydrogenated block copolymer (1) and the hydrogenated block copolymer (III) include styrene and α-mercaptophenylethyl 142282.doc 201020289. P-methylstyrene, divinylbenzene, 1,1-dipyridylethylene, N,N-monodecyl-p-aminoethylphenidene, N,N-diethyl-p-aminoethylbenzene Ethylene and the like. Particularly, from the viewpoint of the balance between the price and the mechanical strength, styrene is preferred. These may be used singly or in combination of two or more. The content of all the vinyl aromatic compounds in the hydrogenated block copolymer (I) is preferably from 20% by mass to 50% by mass, more preferably from 23% by mass to 48% by mass, and further preferably 25% by mass. ~46 mass ° / 〇. When the content of the vinyl aromatic compound in the hydrogenated block copolymer (I) exceeds 50% by mass, the transparency of the final hydrogenated block copolymer composition is likely to be impaired, if it is less than 20% by mass. There is a tendency for low rebound resilience and kink resistance to deteriorate. The content of all the vinyl aromatic compounds in the hydrogenated segment copolymer (m) is more than 10% by mass and less than 25% by mass, preferably from 9% by mass to 24% by mass, more preferably from 12% by mass to 23% by mass. quality%. When the content of the ethylene-based aromatic compound in the hydrogenated money copolymer (III) is at least 25% by mass, the transparency and flexibility of the finally-oriented gasified block-tanomer composition tend to be impaired. If it is ι〇% by mass or less, there is a tendency that the strength is lowered or the adhesiveness is deteriorated. The content of all the ethylene-based aromatic compounds in the weathered drum section copolymers (I) and (ΙΠ) can be measured by using an ultraviolet spectrophotometer using a copolymer before hydrogenation or a copolymer obtained by hydrogenation as a sample. (Conjugated diene) 142282.doc -12- 201020289 The conjugated diene constituting the chlorinated block copolymer (1) and the hydrogenated block copolymer (ΠΙ) means a diene having a pair of conjugated double bonds. For example, L3·butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-I,butadiene, and iota-3pentadiene 2, methyl hydrazine, pentyl-female, 1'3-hexadiene, and the like. Particularly, from the viewpoint of a good balance between moldability and mechanical strength, bismuth, % butadiene and isoprene are preferred. These may be used singly or in combination of two or more. In the configuration of the hydrogenated block copolymer composition of the present embodiment, the term "as a main component" means that the ratio in the predetermined copolymer or the copolymer block is 70% by mass or more. It is 8 〇 mass% or more, more preferably 90 mass% or more. (Hydrogenated Copolymer Block (b)) The hydrogenated copolymer block (b) contains a vinyl aromatic compound and a co-labeled diene. The content of the vinyl aromatic compound in the hydrogenated copolymer block (b) is φ 40 mass. /❶~80% by mass, preferably 45% by mass to 755% by mass. More preferably 50% by mass to 70% by mass. /〇. When the content of the vinyl aromatic compound in the hydrogenated copolymer block (b) exceeds 80% by mass, the softness and transparency of the finally obtained hydrogenated block copolymer composition tend to be impaired. On the other hand, if it is less than 4% by mass, there is a tendency that the low rebound elasticity and the kink resistance are deteriorated. The hydrogenated copolymer block (b) in the hydrogenated block copolymer (I) from the viewpoint of obtaining a good balance between low rebound resilience, kink resistance and transparency of the finally obtained deuterated block copolymer composition The content of 2 〇 is preferably 142282.doc -13 - 201020289 % ~ 8 〇 mass%, more preferably 25% by mass to 70% by mass, still more preferably 30% by mass to 60% by mass. Further, the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (1) can be measured by a nuclear magnetic resonance (NMR) or the like. The amount of the vinyl bond of the conjugated diene oxime in the copolymer block before hydrogenation of the nitriding copolymer block (b) can be controlled by using a regulator such as a tertiary amine compound or a compound which will be described later. When 1,3-butadiene is used as the conjugated diene, hydrogenation is finally obtained from the viewpoint of obtaining a good balance of transparency, low rebound elasticity, and kink resistance as the intended hydrogenated 10-block copolymer composition. The ruthenium of the conjugated diene moiety in the copolymer block before hydrogenation of the copolymer block (b) is preferably from 5 to 60%, more preferably from 10 to 50%. When isoprene is used as the conjugated diene, or when 1,3-butadiene and isoprene are used in combination as the conjugated diene, the total of the 2-vinyl bond and the 3,4-vinyl bond The amount is preferably from 3 to 75%, more preferably from 5 to 6 %. Further, in the present embodiment, the total amount of the i, 2_vinyl bond and the 3,4_ethoxylated bond © (in the case where L3-butadiene is used as a common dilute, the H vinyl bond) The amount) is called the ethylene base bond amount. The amount of vinyl bond can be determined by measurement of an infrared spectrophotometer (e.g., the Hampton method) using a copolymer before hydrogenation as a sample. (Hydrogenated polymer block (c) mainly composed of a conjugated diene) The hydrogenated polymer block (c) is mainly composed of a conjugated diene. The hydrogenated polymer block (C) in the above hydrogenated block copolymer (1) from the viewpoint of the transparency and softness of the hydrogenated block copolymer composition obtained by the most &quot;ς; 142282.doc -14·201020289 The content is 20% by mass to 8% by mass, preferably 25 mass% / ❶', more preferably 30 mass%. /. ~60% by mass. The amount of the vinyl bond of the conjugated diene before hydrogenation in the hydrogenated polymer block (c) is affected by the compatibility with the olefin-based resin (π) described later, in order to promote the inter-column The flowability of the finally obtained hydrogenated block copolymer composition is good, and the amount of the above-mentioned ethylene-based bond is preferably 55% by mass or more, more preferably 55% by mass or more. It is preferred that the hydrogenated block copolymer (1) is 60% by mass or less (&gt; the polymer block (4) mainly composed of an ethyl group-based aromatic compound), and preferably has at least one polymer having a vinyl aromatic compound as a main component. In the hydrogenated block copolymer (1), the content of the polymer block (4) mainly composed of the aromatic compound of the B county is preferably 3 to 3 Gf%, more preferably 5 to 28% by mass. Further, it is preferably 7 to 25 mass% 〇/〇. If the content of the polymer block (4) having a vinyl aromatic compound as a main component in the hydrogenated copolymer (1) is less than 3% by mass, the final hydrogenation is targeted. Block copolymer composition has reduced strength and deteriorated heat resistance When the content is more than 30% by mass, the flexibility and transparency tend to be impaired. The content of the polymerization (4) segment (4) using a vinyl aromatic compound as a main component can be obtained by using iron oxide as a ruthenium. A method for oxidative decomposition of hydride by oxidation of tert-butanol (described in tmk〇lth(10) etal., P〇lym. ^15429(1946)^^^ ;^#^^ 142282.doc -15- 201020289 cerium oxide method) The measurement was carried out. Further, the content of the polymer block (a) mainly composed of a vinyl aromatic compound may be a sample obtained by hydrogenation or a copolymer obtained after hydrogenation, and a nuclear magnetic resonance apparatus (NMR) may be used (described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981), hereinafter referred to as "NMR method". Further, in this case, the content (as Os) of the polymer block (a) mainly composed of a vinyl aromatic compound measured by a perylene oxide method and using a copolymer before hydrogenation is used and utilized. There is a correlation between the content of the polymer block (a) having a vinyl aromatic compound as a main component (set to Ns) measured by the NMR method and using the hydrogenated copolymer. (Os) = -0.012 (Ns) 2+1.8 (Ns) -13.0 (F) Therefore, in the present embodiment, a polymer having a vinyl aromatic compound as a main component of the hydrogenated copolymer is obtained by an NMR method. In the case of the content of the block (a), the value of (Os) obtained by the above formula (F) is used as the polymer block (a) mainly composed of a vinyl aromatic compound as defined in the present embodiment. content. (Polymer bond amount: 25% by mass or less of the polymer block (d) mainly composed of a conjugated diene) The hydrogenated block copolymer (I) preferably has at least one vinyl bond amount of 25% by mass. The following polymer block (d) having a conjugated diene as a main component. The amount of the vinyl bond of the polymer block (d) having a conjugated diene as a main component is preferably 25% by mass or less, more preferably 23% by mass or less, still more preferably 20% by mass or less. 142282.doc -16- 201020289 If the amount of the vinyl bond of the polymer block (d) mainly composed of the co-diene is more than 25% by mass, the hydrogenated block copolymer composition finally has a strength reduction, and The tendency to deteriorate heat resistance. The content of the polymer block (d) having a conjugated diene as a main component in the hydrogenated block copolymer (I) in an amount of 25% by mass or less is preferably 3 to 30% by mass, more preferably It is 5 to 28% by mass, and more preferably 7 to 25% by mass. If the amount of the vinyl bond in the hydrogenated block copolymer (I) is 25% by mass or less, and the content of the polymer block (d) mainly composed of the total of the diene is less than 3% by mass, the final target is The hydrogenated block copolymer composition tends to have a decrease in strength and a deterioration in heat resistance, and when it exceeds 30% by mass, the flexibility tends to be impaired. (Polymer block (A) mainly composed of a vinyl aromatic compound) The hydrogenated block copolymer (III) has at least two polymer blocks (A) mainly composed of a vinyl aromatic compound. φ In terms of obtaining a material having good mechanical strength, the proportion of the polymer block (A) in all the vinyl aromatic compounds in the hydrogenated block copolymer (III) is preferably 80% by weight or more, more preferably It is preferably 85% by weight or more, and more preferably 90% by weight or more. When the proportion of the polymer block (A) is less than 80%, the hydrogenated block copolymer composition which is finally targeted has a tendency to lower in strength and deteriorate in heat resistance. (Hydrogenated polymer block (B) having a conjugated diene as a main component) The hydrogenated block copolymer (III) has at least one hydrogenated polymer block (Β) β having a conjugated diene as a host 142282.doc 201020289 The hydrogenated copolymer block (Β) which is the main body of the hydrogenated I-segment copolymer (111) as a main component in terms of transparency and flexibility of the hydrogenated block copolymer composition finally obtained The content is preferably more than 9% by mass and less than 90% by mass. More preferably, it is 76% by mass to 89% by mass, and further preferably 77% by mass to 88% by mass. The amount of the vinyl bond in the hydrogenated polymer block (Β) having a conjugated diene as a main component affects the compatibility with the olefin-based resin (11) described later, and in order to improve the compatibility, the final obtained is obtained. The hydrogenated block copolymer composition is excellent in transparency, flexibility, and fluidity, and the amount of the vinyl bond is 62% by mass or more and less than 99% by mass, preferably 65% by mass to 95% by mass. More preferably, it is 68% by mass to 90% by mass. /〇. &lt;tan§ (loss tangent) in the viscoelasticity measurement chart of the hydrogenated block copolymer (1)&gt; Hydrogenated block copolymer (1) In the viscoelasticity measurement chart, the peak of tanS (loss tangent) is 〇60. 〇, preferably 2~5〇t, more preferably 4~4〇 Art exists at least one. The peak of the taM is a peak caused by the hydrogenated copolymer block (b) in the hydrogenated block copolymer (1). In order for the final target hydrogenated block copolymer composition to obtain low rebound elasticity and kink resistance, the peak must be present in at least one of 0 to 60 °C. Further, in the hydrogenated block copolymer (I), in the viscoelasticity measurement chart, the peak of tanS (loss tangent) was not reached except for the above 〇~60 °C. Preferably, it is -60 to -5 eC, more preferably _5 〇 ~ -l 〇 ° C exists in at least one. 142282.doc -18- 201020289 The peak of tan5 is the peak caused by the hydrogenated copolymer block (c) in the hydrogenated block copolymer (I). In order for the final intended hydrogenated block copolymer composition to achieve practically sufficient flexibility and transparency at low temperatures, the peak must be present in at least one of the range below 〇 °C. Further, tan3 can be measured using a viscoelasticity measuring apparatus (manufactured by TA Instruments Co., Ltd., ARES) under the conditions of a strain of 0.5%, a frequency of 1 Hz, and a temperature rising rate of 3 ° C /min. &lt;Weight-average molecular weight of the hydrogenated block copolymer (I)&gt; From the viewpoint of obtaining a good balance between heat resistance, mechanical strength, and fluidity (forming processability) of the hydrogenated block copolymer composition as a target The weight average molecular weight of the hydrogenated block copolymer (I) is preferably from 50,000 to 600,000, more preferably from 70,000 to 500,000, and still more preferably from 100,000 to 400,000. &lt;Weight-average molecular weight of the hydrogenated block copolymer (III)&gt; From the viewpoint of obtaining a good balance between heat resistance, mechanical strength, and fluidity (forming processability) of the hydrogenated block copolymer composition as a target The weight average molecular weight of the hydrogenated block copolymer (III) is 30,000 to 300,000, preferably 40,000 to 250,000, more preferably 50,000 to 200,000. Here, the weight average molecular weight of the hydrogenated block copolymers (I) and (III) is measured by gel permeation chromatography (GPC) using a commercially available standard polystyrene. The obtained calibration curve (made using the peak molecular weight of standard polystyrene) was obtained. &lt;Molecular weight distribution of hydrogenated block copolymers (I) and (III)&gt; The molecular weight distribution of the above hydrogenated block copolymers (I) and (III) can be determined by measurement by GPC, based on weight average molecular weight. Calculated by the ratio of the number of average molecules 142282.doc -19- 201020289. The molecular weight distribution of the hydrogenated block copolymers (I) and (III) is preferably 10 or less, more preferably 8 or less, and further preferably 5 or less. &lt;Hydrogenation rate of double bond of conjugated diene monomer unit in hydrogenated block copolymer (I)&gt; From the viewpoint of obtaining excellent heat resistance and weather resistance of the finally-oriented hydrogenated block copolymer composition The hydrogenation ratio of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (I) is preferably 75% or more, more preferably 80% or more, and still more preferably 85% or more. &lt;Hydrogenation rate of double bond of a unitary diene monomer unit in the hydrogenated block copolymer (III)&gt; From the viewpoint of obtaining a good heat resistance and weather resistance of the finally-oriented hydrogenated block copolymer composition The hydrogenation ratio of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (III) is set to 75% or more, preferably 80% or more, more preferably 85% or more. <Hydrogenation Rate of Aromatic Double Bond of Vinyl Aromatic Compound Unit in Hydrogenated Block Copolymers (I) and (III)&gt; Aromaticity of Vinyl Aromatic Compound Unit of Hydrogenated Block Copolymers (1) and (III) The hydrogenation rate of the double bond of the group is not particularly limited, but is preferably 50% or less, more preferably 30% or less, still more preferably 20% or less. Here, the hydrogenation ratio of the hydrogenated block copolymers (I) and (III) can be measured by a nuclear magnetic resonance apparatus (NMR) or the like. &lt;Crystalization peak of hydrogenated block copolymer (I)&gt; The hydrogenated block copolymer (I) is preferably in the differential scanning calorimetry 142282.doc -20- 201020289 (DSC, differential scanning caI〇rimeter) chart In the range of _2 〇 8 (the range of TC, there is substantially no hydride 0 of the crystallization peak caused by the above-mentioned hydrogenated copolymer block (b) containing an ethyl aromatic group and a conjugated diene. Here, "there is substantially no crystallization peak caused by the hydrogenated copolymer block (b) containing a vinyl aromatic group and a conjugated diene in the range of -20 to 80", which means In the temperature range, the peak caused by the crystallization of the hydrogenated copolymer block (b) containing the ethyl b-alkenyl aromatic group and the co-diene is not exhibited, or even if it is confirmed by crystallization. In the case of a crest, the heat of crystallization peak caused by the crystallization is less than 3 j/g, preferably less than 2 J/g, more preferably less than i J/g, and more preferably no Crystallization of the peak heat. As shown above, if it is in the range of ·20~8 (Γ(:) The hydrogenated block copolymer (1) obtained a good crystallization peak caused by the hydrogenated copolymer of the ethylene-containing aromatic group and the common diene, and the hydrogenated block copolymer (1) obtained good softness and properties, and finally achieved the desired hydrogenated block copolymer. The softening of the composition is preferred. In order to obtain substantially no crystallization peaks caused by the hydrogenated copolymer block (8) comprising an ethyl aromatic group and a common dilute in the range of -20 to 8 CTC. The hydrogenated block copolymer (1) is polymerized under the conditions described below by using a specific modifier which adjusts the amount of the vinyl bond or the copolymerization of the vinyl aromatic compound and the conjugated diene. The copolymer obtained by the reaction may be subjected to hydrogenation reaction. <Structure of hydrogenated block copolymers (I) and (III) &gt; 142282.doc -21 - 201020289 For example, the structure of the hydrogenated block copolymer (1) may be listed. There is no particular limitation, and those having the structure represented by the following formula: (bc)n, c-(bc)n, b-(cb)n, (bc)mX, (cb)m_x, c-(b- a) n , c-(ab)n , c-(aba)n , c-(bab)n , c-(bca, ' a~(cb- ca n, a-c-(b-a)n, a-c-(a-b)n, a-c-(b-a)n-b, ,

Ua-b-c)nl X, [a-(b-c)n]m-X, [(a-b)nc]m-X, [(a-b-a)n-c]m_x, m [(b-a-

b) ne]mX, [(cba)n]mX, [e_(ba)n]mX, "c L va-ba)n]m_ X, [c-(bab)n]mX.c_(bd)n , c-(db)n, c-(dbd, ~u^n ' c-(b- db)n , c-(bcd)n , d-(cbcd)n , dc-(bd)n , d_c u , win dC-(bd)nb, [(dbC)n]mX, [d_(b_c)n]m_X, η

Ud'b)nC]m-X, [(dbd)nc]mX, [(bdb)nc]mX, [(cbd)n]m_x, [c ^ d)n]mX, [c-(dbd)n ]mx, [c_(b_d_b)ijm_x. Further, in the above various formulae, a represents a polymer block (a) mainly composed of a vinyl aromatic compound, and b represents a hydrogenated copolymer block sand containing a vinyl aromatic character and a conjugated diene. And c represents a hydrogenated copolymer block (c) having a conjugated diene as a main component, and d represents a vinyl bond amount of Μ 'mass?

The following polymer block (d) having a decadiene as a main component. Q η is an integer of 1 or more, preferably an integer of 5 . m is an integer of 2 or more. What is preferable is an integer of divination. X represents the residue of the coupling agent or the residue of the polyfunctional starter. The structure of the hydrogenated block copolymer (ΙΠ) is not particularly limited, and for example, η is a structure having a structure represented by the following formula. A-(BA)n, B-(AB)m, (Α·Β)η, (Α_Β)πι·χ, (Βυ Furthermore, in the above various formulae, the lanthanide is a vinyl aromatic compound as 142282 .doc •22· 201020289 B is a total of 1 or more of the total η of the total light diene compound, and is preferably an integer of 丨~5. m is an integer of 2 or more, preferably 2 to 8. X. The residue of the coupling agent or the residue of the polyfunctional initiator. The hydrogenated apron copolymer (1) is present in a plurality of blocks (4), embedded

In the case of the segment (8), the segment (4), and the block (d), the structures of the molecular weights, compositions, and the like may be the same or different. Moreover, the boundaries of the blocks do not necessarily need to be clearly distinguished. The distribution of the nitriding block copolymer (1) and the ethylene-based aromatic compound in the _ is not particularly limited as long as it satisfies the range of the content of the vinyl aromatic compound in the present embodiment, and may be uniformly distributed or may be distributed as a wedge. Shape, stepped, convex, concave. Further, the distribution form of the vinyl aromatic compound may coexist in plural.

The polymer block block of the host. Further, in the hydrogenated block copolymers (1) and (III), a plurality of segments having different contents of the ethylenic aromatic compound may be coexisted. Further, the distribution of the vinyl bond units in the blocks (a) to (sentences and (A) and (B) in the hydrogenated block copolymers (1) and (III) is not particularly limited, and may have a knife cloth. The distribution of the vinyl bond can be controlled by adding a later-mentioned adjusting agent to the polymerization or changing the temperature in the polymerization. Further, the conjugated diene monomer unit in the hydrogenated block copolymers (1) and (III) The gasification rate may also have a distribution. The distribution of the hydrogenation rate may be controlled by changing the distribution of the vinyl bond unit or by copolymerizing isoprene with 142282.doc -23- 201020289 butadiene. Hydrogenation using a hydrogenation catalyst described later, using a difference in hydrogenation rate between the isoprene unit and the butyl unit. The hydrogenated block copolymer (1) has a polymer block at least at one end (the structure of the hook is finally The hydrogenated block copolymer composition is preferably a viewpoint of obtaining good heat resistance and mechanical strength. Further, the hydrogenated block copolymer (1) has at least a single terminal (c) having a conjugated diene as a main component. The structure of the hydrogenated polymer block, The improvement of the compatibility with the olefin-based resin (II) to be described later is preferable from the viewpoint of obtaining good transparency and flexibility as the intended hydrogenated block copolymer composition. Specifically, the above-mentioned hydrogenation is indicated. In the formula of the structure of the block copolymer (1), preferred are c-(ba)n, c-(aba)n, ac-(ba)n, more preferably c_(ba)n, c-( The aba)n hydrazine-hydrogenated block copolymer (I) may also be any mixture of copolymers having the structure represented by the above formula. The hydrogenated block copolymer (III) is at least two or more polymer blocks (A) More than one of the structures present at the end is preferable from the viewpoint of obtaining good heat resistance and mechanical strength as the target argon-forming segment copolymer composition. Specifically, 'the above structure is preferably A_ (B_A)n, (A_B)n. The nitrided block copolymer (ΠΙ) may also be any mixture of copolymers having the structure represented by the above formula. Further, the hydrogenated block copolymer (III) is at least in a single The terminal contains 〇丨~91% by mass of the above (B) hydrogenated polymer with conjugated diene as a main component 142282.doc -24- 201020289 It is preferable from the viewpoint that the hydrogenated block copolymer composition finally obtains good workability. <Other examples of the structure of the hydrogenated block copolymers (I) and (III) &gt; The hydrogenated block copolymers (1) and (III) may also be modified block copolymers in which an atomic group having a specific functional group is bonded. Further, the modified block copolymer may also be a secondary modified block. Copolymer. <Method for producing hydrogenated block copolymer (I), (ΙΠ)>

The block copolymer of the hydrogenated copolymers (I) and (III) in a state before hydrogenation, for example, a vinyl aromatic compound by using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent. Obtained by living anionic polymerization with a conjugated diene compound. (Solvent) Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane, and cyclohexane and cycloheptanemethylcycloheptane. An alicyclic hydrocarbon such as an alkane, an aromatic hydrocarbon such as benzene, toluene, xylene or ethyl. (Polymerization initiator) 2 is a polymerization initiator, generally applicable: aliphatic (IV) metallization which is known to have anionic polymerization activity for ethylene aromaticization 2 and conjugated diene: machine test 2 = metal compound , an organic amine-based metal compound, etc. (4) a metal compound is preferably a carbon number of 1 to a paper compound, and is applicable to include a lithium compound in one molecule and a plurality of compounds in one molecule, three Zhonghua 142282.doc -25. 201020289 Compound, four-clock compound. Specifically, it may be mentioned: n-propyl lithium, n-butyl chain, second butyl group, third butyl group, n-pentyl group 'n-hexyl group, nodal chain, phenyl group, tolyl group, diisopropyl The reaction product of benzene and the second lithium, the reaction product of diethylbenzene, the second butyl group and a small amount of π butadiene. Further, the organic alkali metal compound disclosed in the specification of U.S. Patent No. 5,7,8, No. 92, the specification of U.S. Patent No. 2,241,239, and the specification of U.S. Patent No. 5,527,753. (Adjusting agent) An organic group metal compound is used as a polymerization (4) to aromatize the ethyl group. When the copolymer is co-polymerized with a olefin, the specific modifier can be used to adjust the content of the ethylene bond (12 or 3, 4 bond) caused by the total lighter in the polymer of the group, ethylene. Random copolymerization of a base aromatic compound and a conjugated diene. As such a regulator, for example, a tertiary amine compound, an ether compound, or a metal alkoxide compound may be added. The regulators may be used singly or in combination of two or more. As the tertiary amine compound, a compound represented by the formula RiR2R3N (wherein, R1, R2, and R3 represent a hydrocarbon group having 1 to 2 carbon atoms or a hydrocarbon group having a tertiary amino group) can be used. For example, trimethylamine, triethylamine, tributylamine, hydrazine, hydrazine-diamine basic amine, hydrazine-ethyl brigade bite, Ν-methyl hydrazine bite, ν, Ν, Ν, ,Ν,-tetramethylethylenediamine, hydrazine, hydrazine, hydrazine, hydrazine, -tetraethylethylenediamine, 1,2-dipiperidylethane, dimethylaminoethylpiperazine, ν , ν, ν', ν", ν &quot; - pentamethylethylenetriamine, 142282.doc • 26 - 201020289 N, N'-dioctyl p-phenylenediamine, etc. The direct-bonding compound and the cyclic ether compound are used as the direct-bonding hydrazine compound, and examples thereof include diphenyl ether, ethylene glycol dimethyl ether, ethyl methyl ether, diethyl ether, ethylene glycol, and diethyl ether. An alkyl ether compound such as alcohol diethyl ether or ethylene glycol dibutyl ether, a dialkyl ether compound of diethylene glycol such as diethylene glycol dimethyl ether or diethylene glycol ethylene glycol monobutyl ether; Compounds, for example, can be oxime and 歹J. tetrahydroanthracene, dioxanoxane, dimethyloxocyclic, 2,2,5,5-tetra-f-yloxyxanthene, 2,2_ double (2-oxocyclopentanyl) propyl hospital &quot; Fu nam methanol burning shouting etc. as gold The alcohol compound may be, for example, a third sodium laurylate, a sodium third butoxide, a potassium third potassium pentoxide, a potassium third potassium hydride or the like. (Polymerization method) As an organic metal test compound, the above is used. A method for polymerizing an initiator and a co-consumption: a compound can be applied by a previously known method, for example, it can be a batch polymerization, a deterrent, or the like. Any one of the combinations, especially in order to obtain a copolymer having excellent heat resistance, is preferably a batch polymerization. The polymerization temperature is preferably 〇〇c 18 (rr ' is more preferably 3 〇 t &gt; c~15〇ec. The polymerization time varies depending on the conditions, and J is usually within 48 hours, preferably 0.1 to 1 hour. As the gas environment of the polymerization system, it is preferably an inert gas such as nitrogen 142282.doc 27· 201020289 Body environment A pressure is determined to be a pressure range in which the monomer and the solvent can be maintained in the liquid phase within the above temperature range, and is not particularly limited. Further, care must be taken to prevent the deuterium compound from being inactivated. Impurities, such as water Γ The living polymerization is followed by oxygen, carbon dioxide, etc. At the end of the above polymerization step, a coupling amount of a bifunctional or higher coupling agent may be added to carry out the coupling reaction. The bifunctional coupling agent may be used as a conventionally known one, and is not particularly limited. And exemplified by: = methoxy decane, triethoxy decane, tetramethane, tetraethoxy, dimethyl dimethyloxy, and dimethyl oxo; , two gas diethoxy stone Xizhu, three gas methoxy Xi Xi, three gas ethoxy money and other hospital oxygen stone smelting compound, two gas acetyl, two desert acetyl, dimethyl two gas, = A difunctional compound such as methyl dibromide, such as methyl benzoate, ethyl benzoate, benzoic acid benzoate or phthalate. Further, as a trifunctional or higher polyfunctional coupling agent, a conventionally known one can be used without particular limitation. For example, polyhydric alcohols of more than 3 yuan; polyepoxides such as epoxidized ugly oil, diglycidyl double A, U•bis diglycidylaminomethyl) cyclohexane, etc. "SiXn (here, R represents a hydrocarbon group having a carbon number of U0, χ represents a south, and η represents an integer of Μ&quot;), such as a methyl trigastone, a third butyl three gas , four gas cuts and the like bromide; general formula R4-nSnXn (where R represents a hydrocarbon group having a carbon number of 1 to 20, X represents a halogen, and 11 is 142282.doc -28- 201020289 shows 3 to 4 The tin halide compound represented by an integer), for example, a polydentate compound such as a mercaptotriazine, a tributyltin trioxide, or a tetralithium tin. Further, dinonyl carbonate or diethyl carbonate may also be used. (Modification step) As described above, the hydrogenated block copolymers (1) and (111) may also be modified block copolymers to which a functional group having a functional group is bonded. The atomic group having a functional group is preferably Bonding is carried out as a step before the hydrogenation step described later. φ is the above-mentioned "atomic group having a target group", for example An atomic group having at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, a carbonyl group, a thiocarbonyl group, a decyl group, an acid anhydride group, a carboxylic acid group, a sulfur carboxylic acid aldehyde group, a thioaldehyde group, a carboxylic acid Ester group, decylamino group, sulfonic acid group, sulfonate group, squary acid group, linoleic acid group, amine group, imido group, nitrile group, acridinyl group, (tetra) group, epoxy group, thioepoxy group Base, sulfur test group, isogastric acid vinegar group, isothiocyanate vine group, functional fossil decyl group, Shixi smelting alcohol group, alkoxylated oxetyl group, tin-tin-based group, octanoic acid group, butterfly-containing group, A sulfonate group, an alkoxy tin group, a phenyl tin φ group, or the like. Particularly preferred are atomic groups having at least one functional group selected from the group consisting of a trans group, an epoxy group, an amine group, a linalool group, and an alkoxyalkyl group. The above-mentioned atomic group having a g-energy group is bonded by a modifier. Examples of the modifier include tetraglycidyl meta-xylylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexanin, ebhexine, bupentane vinegar, and 4-methoxyl. Bis-benzoate, γ-glycidoxyethyltrimethoxy sulphur, γ-glycidoxypropyltrimethoxy hard, γ-glycidoxypropyl monomethyl phenoxy , bis &amp; glycidoxypropyl) methyl propyl 142282.doc -29· 201020289 oxydecane, i,3-dimethyl-2.imidazolidinium, Μ-diethyl-2-imidazolidinone , N, Nkf-based propylene-based gland, (four) class, and the like. The modified post-stage copolymer can be polymerized, for example, by anionic living polymerization, using a polymerization initiator having a functional group or having a functional group and a monomer, or a reforming sword which forms or contains a functional group at the active end. Obtained by an addition reaction. As another method, a modifying agent having a functional group and a block polymer to which an organic metal is added can be carried out by reacting an organic metal compound such as an organic clock compound with a segmented copolymer (metallization reaction). The addition reaction is obtained by β. In the case of the latter method, the modified hydrogenated block copolymer can also be produced by subjecting the hydrogenated block copolymers (1) and (4) to metallization and reacting the modifier directly. The temperature at which the upgrading reaction is carried out is preferably 0 to 15 (rc, more preferably 20 to 120 ° (:. The time required for the modification reaction varies depending on other conditions, preferably within 24 hours) More preferably, it is 1 to 1 hour. Depending on the type of modification (4) used, in the stage of reacting the modifier, there is also a case where an amine group or the like is formed to form an organic metal salt. In this case, It can be converted into an amine group by treatment with a compound having active hydrogen such as water or alcohol, and a modified copolymer can be mixed with a part of the copolymer which has not been modified in the modified copolymer. The modified block copolymer may also be a secondary modified block copolymer. The secondary modified block copolymer may have a modified block copolymer and a functional group with the modified block copolymer The reactive secondary modifier is obtained by the reverse 142282.doc -30· 201020289. As a secondary modifier, for example, isocyanate acrylate, epoxy group, money = thiol group, _ group, A ^ ^ Shen Zhiji, alkoxyalkylene group in the official = the modifier "has at least two selected from the official Functionality in the base: Liver: When the functional group is an acid-hepatic group, it may be an acid as shown above, in the case where the secondary modifier and the modified #&amp; In the case of the amount of the modifier, the amount of the modifier is preferably used in the amount of the modifier of the (four)-stage copolymer. 〇莫耳, better 疋·~5 mol, and more preferably 〇5 to 4 mol. Regarding the method of reacting the modified block copolymer with the secondary modifier, a known method can be applied' There is no particular limitation, and examples thereof include a melting/strengthening method to be described later, a method of dissolving or dispersing each component in a solvent, and the like, and a subsequent method, etc. Further, the second modification is preferably chlorine. The bis-(3-tris-β-unsaturated oxime imidization as a secondary modifier) is particularly suitable: cis-butyl dibenzoate tetracarboxylic dianhydride, j'2'4' 5-Phenyltetracarboxylic acid di-hepatic, toluene diisocyanate, tetraglycidyl #diaminomethylcyclohexaneethoxy decyl propyl)-tetrasulfide, etc. Further, hydrogenated block copolymerization (1) and (ΙΠ) can be prepared as a modified block copolymer obtained by graft-modifying α, a carboxylic acid or a derivative thereof such as an anhydride, an esterified product, a guanamine or a compound thereof. Specific examples of the saturated carboxylic acid or a derivative thereof include: 142282.doc -31 - 201020289 Maleic anhydride, maleic anhydride quinone imine, acrylic acid or its ester, methacrylic acid or its ester, and internal Bicyclo[2,2,1]-5·heptene·2,3-dicarboxylic acid or its anhydride, etc. The addition amount of α,β-unsaturated carboxylic acid or a derivative thereof is relative to each part by mass The hydrogenated block copolymers (1) and (III) are usually 〇〇1 to 2 parts by mass, preferably 0.1 to 10 parts by mass. The reaction temperature at the time of graft reforming is preferably from 1 〇〇 to 3 〇〇〇c, more preferably from 120 to 280 〇C. As a specific method of the graft modification, for example, the method described in JP-A-62-7921 1 can be applied. (Hydrogenation Reaction Step) The hydrogenated oxime copolymers (I) and (IH) are supplied to the hydrogenation reaction by using an unhydrogenated unmodified or modified block copolymer as described above by using a hydrogenation catalyst. Obtained in the middle. The hydrogenation catalyst is not particularly limited, and a known catalyst can be used: (1) a metal such as Ni pt, Pd or Ru is supported on carbon, a magnet dioxide, an oxidized smelt, a shi shi sho Type heterogeneous hydrogenation catalyst; (2) use,

a so-called Ziegler type nitride catalyst of an organic acid salt of Co, Fe, Cr or the like, or a transition metal salt such as ethylene (IV), and a reducing agent such as an organic solvent; (3) Ti,

A homogeneous hydrogenation catalyst such as an organometallic compound such as an organic metal compound such as Ru Rh or Zr. Specifically, Japanese Patent Publication No. Sho 42-8704, Japanese Patent No. A-43-6636, Japanese Patent Publication No. Sho 63-4841, Japanese Patent Special Fair No. 1.3 797G, and Japanese Patent Special Fair 142282.doc 201020289

Japanese Patent No. 5385 No. 1 and Japanese Patent Special Fair 2_Riding No. L is a preferred hydrogenation catalyst, and examples thereof include a titanocene compound, a reducing organometallic compound, or a mixture thereof. As the titanocene compound, a compound of the Japanese Patent Application Laid-Open No. Hei No. 219, No. 219, No. 219, may be used. Specifically, it may be exemplified by dicyclopentadiene: gasification, monopentamethylcyclopentadienyl, and trigas. A compound having at least one or more ligands of a (substituted) cyclopentadienyl skeleton, a nodal group skeleton, or a base skeleton, etc. as the reducing organometallic compound: an organic alkali metal compound such as organolithium The organic compound, the organic compound, the organoboron compound, or the organozinc compound, etc. The hydrogenation reaction will be described. The reaction temperature is usually set to 0 to 200 ° C, preferably 3 to 15 ° (the temperature range of TC). The pressure of the hydrogen used in the hydrogenation reaction is set to 〇1 to 15 servings, preferably 疋0.2 to 10 MPa', and more preferably 〇.3 to 5 MPa. The hydrogenation reaction time is usually set to 3 minutes to 1 hour. Preferably, the hydrogenation reaction can be either a batch process, a continuous process, or a combination of the above. The solution of the hydrogenated block copolymer obtained by the hydrogenation reaction is optionally Remove For the separation method, the hydrogenated block copolymer is separated from the solution. As the separation method, for example, 142282.doc -33·201020289 is added to the reaction liquid after hydrogenation to form a hydrogenated modified copolymer. a polar solvent of a poor solvent, a method of precipitating and recovering a polymer; and a method of recovering the reaction liquid by adding it to the hot water by stirring, by steaming, removing the solvent, and recovering the solution; directly polymerizing A method in which the solvent is heated to remove the solvent, etc. Further, various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers may be added to the hydrogenated block copolymers (1) and (111). (Standard olefin resin) The olefin resin (II) constituting the hydrogenated block copolymer composition of the present embodiment will be described. Examples of the hydrocarbon resin (II) include · Polyethylene (PE, polyethylene), polypropylene (pp, p〇iypr〇pyiene), i-butene, i_pinene, 1-hexene, 3-mercapto-1-butene, 4_fluorenyl Pentene, fluorene-octene, etc. a homopolymer of olefins. A random copolymer or a block copolymer comprising a combination of olefins selected from the group consisting of ethylene, propylene, butene, pentene, hexene, octene, etc., for example, an ethylene-propylene copolymer, ethylene_丨_ Butene copolymer, ethylene-3-mercapto-1-butene copolymer, ethylene·4_mercapto-4·pentene copolymer, ethylene-1·hexene copolymer, ethylene octene copolymer, ethylene oxime Ene copolymer, propylene-1·butene copolymer, propylene hexene copolymer, propylene octene copolymer, propylene_4_mercapto-1-pentene copolymer, ethylene propylene propylene copolymer, propylene An ethylene and/or propylene/α-olefin copolymer such as a 1-hexene-ethylene copolymer or a propylene/non-octene ethylene copolymer. 142282.doc -34- 201020289 Further, as a copolymer with ethylene and/or propylene, a copolymer with other unsaturated monomers shown below is also included. For example, ethylene and/or propylene with acrylic acid, methacrylic acid, maleic acid, decylene succinic acid, decyl acrylate, methyl methacrylate, maleic anhydride, aryl butene a copolymer of an unsaturated organic acid such as a diimine, an alkyl maleimide or a derivative thereof, a copolymer of ethylene and/or a vinyl ester such as propylene and vinyl acetate, and further an ethylene and/or a ru Non-conjugated diene such as propylene and cyclopentene, 4-ethylidene-2-norbornene, 4-methyl-1,4-hexene, 5-methyl-ι, 4-hexadiene Copolymer. The (1) olefin-based resin preferably contains at least one type of polypropylene resin. The thin-type smear-type resin (II) may be modified by a specific functional group. Examples of the functional group include, for example, a functional group: The epoxy group, the carboxyl group, the acid anhydride, the hydroxyl group, etc. # As a functional group-containing compound or a modifier for modifying the olefin-based resin (II), the following compounds may be mentioned. For example, glycidyl methacrylate may be mentioned. Unsaturated epoxidized dibutyl acid, antibutanic acid, sulfhydryl succinic acid, methyl maleic acid, such as ester, glycidyl ethoxide, glycidyl hydrazine, and propyl glycerol An unsaturated organic acid such as allyl succinic acid, maleic anhydride or fumaric acid methylene succinic anhydride, etc. Further, an ionic polymer, a vaporized polyolefin, etc. may be mentioned. π), in terms of economy and high transparency in the hydrogenated block copolymer composition of the embodiment 142282.doc • 35· 201020289, it is preferred to obtain a high transparency. Propylene homopolymer, ethylene and propylene random or funeral Polypropylene waxes, etc. Especially preferred from the viewpoint of transparency and flexibility, an ethylene-propylene random copolymer. The olefin resin (π) may be composed of a single material, or may be used in combination. [Hydrogenated block copolymer composition] The hydrogenated block copolymer composition of the present embodiment contains the hydrogenated block copolymer (1) and at least one of the first embodiment as described above. In the second embodiment, the hydrogenated block copolymer (I), at least one olefin resin (11), and hydrogenated block copolymer (III) are contained in the second embodiment. In the hydrogenated block copolymer composition, the content of the hydrogenated block copolymer (I) is preferably from 5% by mass to 95% by mass, more preferably from 10% by mass to 90% by mass, even more preferably 15% by mass. When the content of the hydrogenated block copolymer (I) is less than 5% by mass, the flexibility of the hydrogenated block copolymer composition tends to be deteriorated. On the other hand, if it exceeds 95% by mass, Then there is a hydrogenated block copolymer composition In the hydrogenated block copolymer composition of the second embodiment, the content of the hydrogenated block copolymers (1) and (in) is preferably from 25 to 92% by mass, respectively. More preferably, it is 5 mass% to 85% by mass, and further preferably 75% by mass to 77.5 mass%. 142282.doc -36- 201020289 If the contents of the hydrogenated block copolymers (i) and (ΙΠ) are respectively less than When the amount is 25% by mass, the flexibility of the hydrogenated block copolymer composition tends to be deteriorated. On the other hand, when it exceeds 92.5 mass%, the strength and heat resistance of the hydrogenated block copolymer composition tend to deteriorate. In addition to the hydrogenated block copolymers (I) and (III) and the polyolefin-based resin, the hydrogenated block copolymer composition of the present embodiment may be blended with any rubber softener or modifier, for example. Additives, etc. The φ rubber softener softens the intended hydrogenated block copolymer composition and imparts fluidity (forming processability). As the rubber softener, for example, a mineral oil, a liquid or a low molecular weight synthetic softener can be applied, and a naphthenic and/or paraffin-processed treatment oil or extender oil is particularly preferable. The mineral oil-based rubber softener is a mixture of an aromatic ring, a naphthene ring, and a paraffin chain, and the carbon number of the paraffin chain accounts for 5% or more of the total carbon, and is called a paraffin system, and the carbon number of the naphthenic ring is 3 〇~45% is called a naphthenic system, and an aromatic carbon number of more than 30% is called an aromatic system. As the synthetic softener, Lu may be a polybutene, a low molecular weight polybutadiene, a flowing paraffin or the like, and more preferably a softener for the above mineral oil-based rubber. In the case where the target hydrogenated block copolymer composition is required to have high heat resistance and mechanical properties, the dynamic viscosity of the mineral oil-based rubber softener applied at 40 C is 60 cst or more, preferably It is 120 cst or more. The softener for rubber may be used singly or in combination of two or more. The modifier is a function which has a function of improving the scratch resistance of the target hydrogenated block copolymer composition or improving the adhesion. As the modifier, an organopolyoxane can be used. This exhibits the surface modification effect of the hydrogenated block copolymer composition 142282.doc -37· 201020289' and functions as an abrasion resistance improving aid. The form of the modifier can be either a low viscosity liquid to a high viscosity liquid or a solid, from the viewpoint of ensuring good dispersibility in the hydrogenation segment copolymer composition. Suitable liquids, ie eucalyptus oils. Further, from the viewpoint of suppressing the permeation of the polyoxyalkylene by the dynamic viscosity, a preferable 疋90 cst or more is more preferably 1 〇〇〇(3) or more. Specific examples of the poly-stone-oxygen-burning include a general-purpose material such as dimethyl polyphosphorus, f-phenyl polysulfide, and a base modification, a polyether modification, a fluorine modification, and the like. Alcohol modification, soil quality epoxy modification and other modified stone oil. There is no particular limitation, and in view of the higher effect of the wear resistance improving aid, it is more suitable for the dimethyl group. These organic poly-stones can be used alone or in combination as an additive, if it is a filler, a slip agent, a mold release agent, a plasticizer, a stabilizer, a light stabilizer, or an ultraviolet absorber. Agent, flame retardant ❹ = antistatic agent, reinforcing agent, colorant, thermoplastic resin or rubber-like polymer in the preparation of the user, there is no particular limitation. Examples of the filler include, for example, dioxane, talc, mica, calcium, hydrotalcite, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, strontium oxide, sulfuric acid 26, barium sulfate, and the like. Inorganic filler 'organic filler such as carbon black. The lubricant may, for example, be stearic acid, behenic acid, calcium stearate, magnesium stearate or bis-stearate. Examples of the plasticizer include organic polyoxoxime, mineral oil, and the like. As the antioxidant, a hindered antioxidant is exemplified. 142282.doc •38- 201020289 Examples of the heat stabilizer include phosphorus-based, sulfur-based, and amine-based heat stabilizers. As a light stabilizer, a hindered amine light stabilizer is mentioned. As a ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned. Examples of the reinforcing agent include organic fibers, glass fibers, carbon fibers, and metal whiskers. Examples of the coloring agent include titanium oxide, iron oxide, carbon black, and the like. In addition, it can be listed as "Rubber and plastic compounding medicine" (edited by Rubber Digest ^ company). The hydrogenated block copolymer composition of the present embodiment can be produced by a conventionally known method. For example, the following method can be used, etc., using a mixer such as a Banbury mixer, a single-axis screw extruder, a twin-screw extruder, a two-way kneader, or a multi-axis screw extruder, and the respective components (the above hydrogenation) A method in which the block copolymers (1) and (ΠΙ) and a polyolefin resin (II) and other additives are kneaded and kneaded; and the components are dissolved or dispersed, and then the solvent is heated and removed. In particular, from the viewpoint of productivity and good kneading, it is preferred to use a melt kneading method of an extruder. The shape of the hydrogenated block copolymer composition is not particularly limited, and may be any shape such as a pellet, a sheet, a rope, or a wafer. Further, it is also possible to directly produce a molded article after melt-kneading. [Molded product using hydrogenated block copolymer composition] The hydrogenated block copolymer composition can be, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, or the like. Rotary forming, powder forming, and foam forming 142282.doc -39- 201020289 The layered wire 1 is formed into a shape, a wire, or the like, and is shaped. For example, it can be used as a sheet, a thin molded article, an air-molded article, a vacuum-formed product, a molded article, a hollow product, a non-woven fabric, or a fibrous molded article. Soaked into a molded article. σ into leather and a variety of such special molded products such as usable, occupational appliances, home appliances, fly parts, food packaging materials, medical components, electronic components, household items, toys; construction materials, industrial materials Wait. Raw materials and fiber raw materials Specific examples of automotive parts include: gear shifting heads, weatherproof linings, window frames and their sealing materials, and handrails: mats, spoilers, and airbag covers. The instrument panel, the bumper, and the medical device include, for example, a medical tube, a sputum, a soft tissue liquid S for a side treatment, a blood collection bag, an infusion bag, and a blood bag. Excavation and manual dialysis As a building material, wall materials, bed materials, etc. can be cited. In addition, industrial hoses, food hoses, vacuum cleaner hoses, wrap films, various covering materials other than electric wires, coated materials for handles, and soft dolls can be cited. The above-mentioned molded article may be suitably subjected to processing such as foaming, powdering, stretching, printing, painting, plating, and the like. The hydrogenated block copolymer composition of the present embodiment can be used extremely effectively as a hose or a tube because it exhibits the effects of softness 142282.doc -40 - 201020289, low rebound elasticity, transparency, and excellent kinkability. A hollow composition. [Examples] Hereinafter, the present invention will be more specifically illustrated by the examples and comparative examples, but the present invention is not limited to the following examples. » &lt;Specific method for polymer structure, method for measuring physical properties&gt; (1) Styrene content of hydrogenated block copolymers (I) and (III) Using a block copolymer before hydrogenation, using an ultraviolet spectrophotometer ( It is manufactured by Shimadzu Corporation, UV-2450). (2) The polystyrene block content of the hydrogenated block copolymers (1) and (III) is a block copolymer before hydrogenation, and is described in IM Kolthoff, et al., J. Polym. Sci. 1, 429 (1946). The tetrazoic acid method was used for the determination. In the decomposition of the block copolymer, a 0.1 g/125 mL tertiary butanol solution of hungry acid was used. The amount of the oxime bond of the φ (3) hydrogenated block copolymers (I) and (III) was measured using an infrared spectrophotometer (manufactured by JASCO Corporation, FT/IR-230) using a block copolymer before hydrogenation. . The vinyl bond amount of the copolymer was calculated by the Hampton method. (4) Molecular weight and molecular weight distribution of the hydrogenated block copolymers (1) and (III) were measured by GPC [device: LC-10 (manufactured by Shimadzu Corporation), column: TSKgelGMHXL (4.6 mm x 30 cm)]. The solvent used tetrahydrofuran. The measurement was carried out under the conditions of a temperature of 35 °C. The molecular weight is determined by using a commercially available standard polystyrene to obtain a calibration curve of the molecular weight of the peak of the layer 142282.doc -41 · 201020289 (using the peak molecular weight of standard polystyrene). Weight average molecular weight. Further, the molecular weight when a plurality of peaks are present in the chromatogram means the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak of the chromatogram). . Further, the molecular weight distribution is a ratio of a weight average molecular weight (Mw) obtained by a molecular weight distribution to a number average molecular weight (??). (5) The hydrogenation ratio of the double bond of the conjugated diene monomer unit of the hydrogenated block copolymers (1) and (III) was carried out using a hydrogenated modified copolymer using a nuclear magnetic resonance apparatus (manufactured by BRUKER, DPX-400). Determination. (6) Tan5 peak temperature First, the sample was cut into a size of 12.5 mm in width and 40 mm in length to prepare a sample for measurement. Then, the sample for measurement was set to a twisted geometry of the apparatus ARES (trade name, manufactured by TA Instruments Co., Ltd.), and the measured length was 25 mm, the strain was 0.5%, the frequency was 1 Hz, and the temperature rising rate was Determined at 3 ° C / min. The tanS peak temperature is a value obtained based on the peak value detected by the automatic measurement by RSI Orchestrator (trade name, manufactured by TA Instruments Co., Ltd.). (7) Hardness The value after 10 seconds was measured with a durometer type A in accordance with JIS K6253. Further, (-) of the hardness barriers in Tables 3 and 4 below indicates no unit. 142282.doc -42- 201020289 The value of hardness is preferably 96 or less. (8) Tensile strength (Tb) and elongation at break (Eb) According to JIS K6251, the measurement was carried out at No. 3 dullness and crosshead speed of 5 〇〇 mm/min. The tensile strength is preferably 9 〇 kg/cm 2 or more in practical use. The elongation at break is preferably 500% or more, which is practically desirable. (9) Tripso type rebound elasticity The measurement was carried out at 23 eC in accordance with JIS K6255'. The rebound resilience is ideally less than 3〇0/〇. (10) Kink resistance The tube-shaped formed body having an inner diameter of 4 mm and an outer diameter of 6 mm was used. The tensile compression tester was used to measure the stress when the tube was bent, and the stress curve was shown. v. Body and β A tube having a length of 30 cm was set to 1 〇 Cm ′ between the chucks and the bending was measured at a crosshead speed of 400 mm/min. The stress curve is shown in Figure 1. &lt;Twistedness relaxation determination&gt; Fig. 1 is the moment when the tube is kinked. The slower the part is, the better the kinks are. As a method of judging, first, a tangent line A, b is formed on a straight line portion before and after the kink moment 1 on the stress curve. The greater the difference between the positions where the cutting edge A B is not separated from the stress curve, the better the kink relaxation is. This is determined by the following equation as the distance between the A-B tangent lines. 142282.doc •43- 201020289 (the distance between the chucks when the tangent B leaves the stress curve)-(the distance between the chucks when the tangent line A leaves the stress curve)=the distance between the tangent lines AB is more than 7 mm between the tangent lines. · ◎

The distance between the tangents of the AB is less than 7 mm and is more than 5 mm: the distance between the tangential lines of 〇AB is less than 5 mm: X &lt;the determination of the kinking distance&gt; The second of the stresses of Fig. 1 is taken as the kinking position of the tube, and the movement between the chucks The longer the distance, the better the kink distance, and the judgment is made at the 3rd level of ◎, 〇, and X from the good. The kink position is 60 mm or more: ◎ The kink position is more than 50 mm: the kink position is less than 50 mm: X &lt; comprehensive kink resistance judgment> The kink easing judgment and the kink distance are both ◎: ◎ kinking One of the determination of the sex determination and the kink distance is 〇, and the other is ◎: ◎ The kinks of the kinks and the kinks are judged by 扭:〇

Any one of the kinks of the kinks and the kink distance is X: X (11) haze value (haze), and the transparency is determined by using a haze meter (manufactured by Sakamoto Denshoku Co., Ltd., NDH-1001DP). The haze value (haze) of the sheet-like molded body having a thickness of 2 mm in the liquid paraffin was measured, and as a transparency index, it was evaluated in the order of ◎, 〇, and X from the start. Haze value is less than 30%: transparency ◎ haze value is 30 or more and less than 50%: transparency 〇 142282.doc • 44· 201020289

The haze value was 50% or more: transparency X &lt; Preparation of hydrogenation catalyst&gt; The hydrogenation catalyst used in the production of the vaporized block copolymer was prepared by the following method in the following examples and comparative examples. The reaction vessel equipped with the stirring device was purged with nitrogen, and 1 liter of cyclohexane which was dried and purified was placed therein. Then, bis(η5-cyclopentadienyl)titanium carbide was added as 1 〇〇 millimolar.添加 While fully stirring it, add a positively pulverized solution containing trimethyl sulfonium 2 〇〇 millimolar and allow to react at room temperature for about 3 days. Thereby, a chlorine catalyst is obtained. &lt;Hydrogenated block copolymer&gt; The hydrogenated block copolymers (1)-1 to (1)_7 and (Ill)-1 to (πΐ)_3 constituting the hydrogenated block copolymer composition were prepared in the following manner. (The hydrogenated block copolymer was subjected to batch polymerization using a tank type reactor equipped with a stirring device and a jacket (the inner volume was φ L). First, a cyclohexane solution containing 9 parts by mass of styrene was introduced (concentration was 2〇). (% by mass). Then, n-butyllithium is added in an amount of 84 parts by mass relative to 100 parts by mass of all monomers, and N, N, N, N, _ tetramethylethylene is added with respect to n-butyl chain 1 molar. Amine (hereinafter referred to as "TMEDA")!.8 moles, and then added sodium terpolate sodium 〇.08 mol with respect to n-butyl lithium 1 mol, and polymerized at 7 (rc for 2 〇 minutes. Then, A cyclohexane solution containing 25 parts by mass of styrene and a cyclohexane solution (concentration: 2% by mass) containing 142282.doc -45·201020289 butadiene 21 parts by mass were added, and polymerization was carried out for 45 minutes. Then, a cyclohexane solution containing 45 parts by mass of butadiene was introduced, and polymerization was carried out for 1 hour at 6 Torr&gt;c. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained in the above manner, benzene thereof The ethylene content was 34% by mass, the polystyrene block content was 9% by mass, and the vinyl bond amount was 66% by mass ( The conjugated diene polymer block has a vinyl bond amount of 77 mass, a weight average molecular weight of 148,000, and a molecular weight distribution of 1〇2. Further, in the obtained block copolymer, each of the block copolymer is used. ❹ 1〇〇 mass damage, adding a hydrogenation catalyst prepared in the above manner on a Ti basis, and performing an argonization reaction under a hydrogen pressure of .7 MPa at a temperature of 65 r. Then, with respect to the copolymer 100 The hydrogenated block copolymer (I)-1 was obtained as a stabilizer by adding 3 parts by mass of 3_(3,5-di-t-butyl-4-phenylphenyl)propionic acid octadecylacetate as a stabilizer. The hydrogenated block copolymer obtained had a hydrogenation rate of 98%. (Hydrogenated block copolymer (Ι)_2) © Batching using a tank type reactor equipped with a stirring device and a jacket (the inner volume is ι〇L) First, a cyclohexane solution containing 7 parts by mass of styrene (concentration of other mass °/〇) was charged. Then, n-butyl group was added with respect to all monomers 1 and 二Lithium 0.089 quality injury 'relative to Zheng Ding _ ] each; ΈΓ τ- .j- . Adding 1.8 Mole of TMEDA, into the ear Adding a third sodium pentaerythritol 0.08 mol, 142282.doc -46- 201020289, at a temperature of 70 ° C for 20 minutes, compared to the positive Ding 丨 丨 工 工 工 工 工 工 工 工 工 工 工 工 142 142 57 parts by mass of a cyclohexane solution (20% by mass) was polymerized at 60 ° C for 1 hour. Then, a cyclohexane solution containing 18 parts by mass of stupid ethylene and a cyclohexane solution containing 14 parts by mass of butadiene were added ( The concentration was 2% by mass), and polymerization was carried out for 7 minutes at 7 Torr.

Then, a cyclohexane solution containing 4 parts by mass of styrene was placed in Kagawa. Polymerize for 20 minutes under C. Thereafter, methanol was added to stop the polymerization. In the drum segment obtained in the above manner, the amount of phenethyl is ruthenium. /〇, the content of the polystyrene baking block is u mass%, the amount of the vinyl bond is the amount % (the amount of the vinyl bond of the conjugated diene polymer block is 77% by mass), and the weight average molecular weight is 137,000. The molecular weight distribution is 1〇3. Further, the obtained block copolymer is subjected to a hydrogenation reaction in the same manner as the above (hydrogenated segment copolymer (1)-1), and a stabilizer is added in the same manner as the above (nitride block copolymer (1)_1). A chlorinated block copolymer (1)-2 was obtained. The hydrogenated block copolymer obtained had a hydrogenation rate of 98%. (The bismuth block copolymer is batch-polymerized using a tank reactor equipped with a stirring device and a jacket (the inner volume is ι〇L). One hundred thousand, the donor contains 35 parts by mass of cyclohexane solution (The concentration is 20 mass. Following =, adding n-butyl linoleum 71 mass loss relative to 100 parts by mass of all monomers. Adding 1.8 mol of TMEDA to n-butyl lithium 1 mol, 142282.doc -47 201020289 Furthermore, sodium tert-amylate 〇〇8 mol was added to 4 ears of n-butyl clock, and polymerization was carried out at 6 (TC for 1 hour). Then, a cyclohexane solution containing benzoic acid was added (concentration was 20% by mass, at 7 〇. (: Polymerization for 2 〇 minutes. Then, adding 24 parts by mass of styrene ring solution and 21 parts by mass of butadiene in cyclohexane solution (concentration is mass) %), it was polymerized for 45 minutes under 7 Torr. Then, 9 parts by mass of a cyclohexane solution containing styrene was charged, and polymerization was carried out at 7 (n: 20 minutes). Thereafter, methanol was added to stop the polymerization reaction. The obtained block copolymer has a styrene content of the mass % 'polystyrene block content 2% by mass, the amount of the ethylenic bond was 6% by mass (the amount of the vinyl bond of the conjugated diene polymer block was 75% by mass), and the weight average molecular weight was 184,000', and the molecular weight distribution was 1.05. Further, The obtained block copolymer was subjected to a hydrogenation reaction in the same manner as the above (hydrogenated block copolymer (Ι)·1), and was added in the same manner as in the above (hydrogenated block copolymer (1)-1). Stabilizer, hydrogenated block copolymer (1)-3. The hydrogenated block copolymer obtained has a hydrogenation rate of 99 〇/〇. (Hydrogenated block copolymer (1)-4) using a stirring device and a clamp A tank type reactor (internal volume of 1 〇L) was used for batch polymerization. First, 9 parts by mass of a cyclohexane solution containing styrene (concentration: 2 〇 mass%) was charged. Then, relative to all monomers 1 〇 0 parts by mass and n-butyl lithium hydride 78 142282.doc • 48- 201020289 parts by mass, 丨8 moles of tmeda is added relative to n-butyl lithium oxime, and then relative to n-butyl lithium 1 Moore was added to the third acetonitrile sodium (10) molar and polymerized at 70 ° C for 20 minutes. 27 parts by mass of a cyclohexane solution containing styrene and a cyclohexane solution containing 19 parts by mass of butadiene (concentration: 2% by mass) were polymerized at 7 Torr for 45 minutes. Then, the input contained butadiene 45. A mass portion of the cyclohexane solution was polymerized at 6 (rc) for 1 hour. Then, ethyl benzoate oxime 1 mol was added to n-butyl lithium oxime, and the mixture was reacted at 7 (TC for 10 minutes). Thereafter, methanol was added to terminate the polymerization reaction. The block copolymer obtained in the above manner had a styrene content of about 9% by mass, a polystyrene block content of 9% by mass, and a vinyl bond amount of 63% by mass. The decadiene polymer block had a vinyl bond amount of 73% by mass, a weight average molecular weight of 163,000, and a molecular weight distribution of 12 Å. Further, the coupling ratio obtained from the peak area ratio of the Gpc curve was 25 〇/〇. Further, the obtained block copolymer is subjected to a hydrogenation reaction in the same manner as the above (hydrogenated block copolymer (1)-1), and a stabilizer is added in the same manner as the above (hydrogenated block copolymer). Hydrogenated block copolymer (1)-4. The hydrogenated block copolymer obtained has a hydrogenation rate of 98 Å/〇. (Hydrogenated block copolymer (1)-5) Using a groove type with a stirring device and a jacket The reactor (internal volume is 1 〇L), and batch polymerization is carried out. 142282.doc -49· 201020289 First, the investment includes a cyclohexane solution of 9 parts by mass of dibutyl sulphate (managed 20% by mass). All „(5 monomers 1 〇〇 part by mass plus n-butyl lithium 〇〇79 mass damage added to 正5 mol top EDA relative to n-butyl oxime i-mole, polymerized at 70 ° C for 20 minutes Then, 175 mol of TMEDA was added with respect to n-butyllithium molars, and then a third sterol sodium quinone 8 mol was added with respect to n-butyllithium molars, and 27 parts by mass of styrene was added. a cyclohexane solution and a cyclohexane solution containing 19 masses of butadiene (concentration: 2〇% by mass), in Chuan Chong Polymerization was carried out for 45 minutes. Then, a cyclohexane solution containing 45 parts by mass of butyl was added to the mixture at 6 Torr for 1 hour. Thereafter, methanol was added to stop the polymerization. The block copolymer obtained in the above manner was obtained. The styrene content is 27% by mass, and the vinyl bond amount is 61% by mass (the amount of the vinyl bond of the conjugated diene polymer block is 76% by mass, and the conjugated diene polymer block (d) The amount of the vinyl bond was 18% by mass, the weight average molecular weight was 2,300,000, and the molecular weight distribution was 1.05. Further, with respect to the obtained block copolymer, the above (hydrogenated block copolymer (1)-1) was utilized. The hydrogenation reaction is carried out in the same manner, and a stabilizer is added in the same manner as the above (hydrogenated block copolymer (1)-1) to obtain a hydrogenated block copolymer (1)-5. The hydrogenation rate of the obtained hydrogenated block copolymer 98% (Hydrogenated block copolymer (1)-6) Batch polymerization was carried out using a tank type reactor equipped with a stirring device and a jacket (the inner volume was 1〇142282.doc. &lt;〇201020289 L). First, 'the investment includes 9 parts by mass of benzophenone, and the mass % of cyclohexane is dissolved. On the other hand, n-butyl lithium hydrazine 79 '# parts by weight was added with respect to 100 parts by mass of all the monomers, and TMEDA of 〇·3 mole was added with respect to 1 mM of the monomer, and polymerization was carried out at 7 ° C. Then, a cyclohexane solution containing 38 parts by mass of styrene and a cyclohexane solution (concentration: 20% by mass) containing 49 parts by mass of styrene were added, and polymerization was carried out for 1 hour at 70 ° C. Next, 4 parts by mass of a cyclohexane solution containing styrene was charged and polymerized at 7 Torr for 20 minutes. Then, methanol was added to stop the polymerization reaction. The block copolymer obtained in the above manner had a styrene content of 51% by mass. The polystyrene block content was 13% by mass, the vinyl bond amount was 21% by mass, the weight average molecular weight was 1,500,000, and the molecular weight distribution was 丨〇9. Further, the obtained block copolymer was subjected to a hydrogenation reaction in the same manner as in the above (hydrogenated intercalated copolymer (1)-1), and was the same as the above (hydrogenated block copolymer (1)-1). A method of adding a stabilizer to obtain a hydrogenated block copolymer. The hydrogenated block copolymer obtained had a hydrogenation rate of 98%. (Hydrogenated block copolymer (1)-7) Batch polymerization was carried out using a tank type reactor equipped with a stirring device and a jacket (the internal volume was 1 〇 L). First, 22 parts by mass of a cyclohexane solution containing styrene (concentration: 20% by mass) was charged. 142282.doc •51 201020289 Then, adding 24 parts by mass of n-butyl chain oxime to 100 parts by mass of all monomers, adding 18 moles of the top leg relative to the n-butyl group, and then relative to n-butyllithium 1 mole was added with 0.08 mol of sodium lapentoxide, and polymerization was carried out at 70 ° C for 30 minutes. Then, a cyclohexane calcination solution (concentration: 20% by mass) containing 57 parts by mass of butadiene was added and polymerized at 60 ° C for 1 hour. Then, a cyclohexane solution containing 21 parts by mass of styrene was injected and polymerized for 30 minutes under grasping. Then, the sub alcohol was added to stop the polymerization. The block copolymer obtained in a broad manner has a styrene content of 杓% by mass. The butadiene portion has a vinyl bond content of 76% by mass, a weight average molecular weight of 91,000, and a molecular weight distribution of 1.07. Further, the obtained block copolymer is subjected to a hydrogenation reaction in the same manner as in the above (ammonia ring copolymer (1)·〇, and is stabilized by the same method as the above (gasified block copolymer (1)·1}). A hydrogenated block copolymer (1)-7 is obtained. The hydrogenation rate is 990/. The trough type reactor (the internal volume is 10 obtained hydrogenated block copolymer) (the hydrogenated block copolymer is used with a stirring device and a clamp) In the case of L), batch polymerization is carried out. First, a cyclohexane solution containing 5 parts by mass of styrene (concentration: 汕% by mass) is charged. Then, n-butyl fluorene is added with respect to 100 parts by mass of all monomers. 67 parts by mass relative to the n-butyl group! Add 1 8 moles of τΜΕ〇Α to Moer, and then add the third pentanol to the molars of n-butyl groups. 142282.doc -52- 201020289 Polymerization was carried out at 70 ° C for 20 minutes. Then, a cyclohexane solution containing 20 parts by mass of styrene and a cyclohexane solution containing 65 parts by mass of butadiene (concentration of 2% by mass) were added at 7 〇. Polymerization was carried out for 1 hour under c&gt;c. Then, the input contained 5 parts by mass of styrene. The cyclohexane solution was polymerized at 7 (rc) for 20 minutes. Then, 5 parts by mass of a cyclohexane solution containing butadiene was added, and polymerization was carried out at 7 (rc for 20 minutes. Then, methanol was added to stop the polymerization. The block copolymer obtained in the above manner had a styrene content of 3% by mass, a vinyl bond amount of the butadiene portion of 65% by mass, a weight average molecular weight of 2,100, and a molecular weight distribution of 1.06. With respect to the obtained block copolymer, a hydrogenation reaction is carried out by the same method as the above (hydrogenated block copolymer (1)-1), and hydrogenation is carried out by adding a stabilizer in the same manner as the above (hydrogenated copolymer) (1). Block copolymer (1)-8. The hydrogenation ratio of the hydrogenated block copolymer obtained was 98%. (Hydrogenated block copolymer j) A tank type reactor equipped with a stirring device and a jacket (the inner volume is ι 〇L) 'Batch polymerization. First, '7 parts by mass of a cyclohexane solution containing styrene (concentration: 20% by mass) was added. Then, 0.082 parts by mass of n-butyl group was added to 100 parts by mass of all monomers. Add 1 to the n-butyl clock 1 mole .8 Moher's TMEDA, with respect to n-butyl clock! Add the third pentanol sodium oxime (10) Moer, 142282.doc • 53· 201020289 Polymerize at 70 ° C for 20 minutes. 87 parts by mass of a diene solution (concentration: 20% by mass) of a diene, and polymerized at 6 (TC for 1.5 hours). Then, a cyclohexane solution containing 6 parts by mass of styrene was introduced, and polymerization was carried out for 20 minutes at 7:7. Then, the sterol was added to stop the polymerization. The block copolymer obtained in the above manner had a styrene content of .% by mass, the vinyl bond amount of the butadiene portion was 78% by mass, and the weight average molecular weight was It is 151,000 and has a molecular weight distribution of 1.〇6. Further, with respect to the obtained copolymer, (iv) hydrogenation reaction is carried out in the same manner as the above (nitride block copolymer (1)-1), and the same method as above (gasification block copolymer (D-υ) is added. Stabilizer, hydrogenated block copolymer (III)-1 was obtained. The hydrogenated block copolymer obtained had a hydrogenation rate of 990/0. (Hydrogenated block copolymer (111)-2) using a mixing device and a clamp A trough reactor (with an internal volume of 10 L) was subjected to batch polymerization. First, 9 parts by mass of a styrene solution containing cyclohexane (concentration of 2% by weight) was charged. Then, relative to all monomers 0.078 parts by mass of n-butyllithium was added in an amount of 1 part by mass, and 〇5 mol of TMEDA was added to n-butyllithium molars, and polymerization was carried out at 70 ° C for 20 minutes. Then, the addition of butyl bromide 82 was added. A part by weight of a cyclohexane solution (concentration: 2% by weight) was polymerized at 70 ° C for 1 hour. Then, 9 parts by weight of a cyclohexane solution (concentration of 2% by weight) containing styrene was charged at 70 Polymerization at ° C for 20 minutes. 142282.doc •54- 201020289 The block copolymer obtained in the above manner, The stupid ethylene content is 18% by weight, the butadiene portion has a vinyl bond content of 51% by weight, the weight average molecular weight is 106,000, and the molecular weight distribution is 1 〇 4. Further, for the obtained block copolymer, the use and the above (Hydrogenation block copolymer (1)_1) The hydrogenation reaction is carried out in the same manner as in the above (hydrogenated block copolymer (1)-1) by adding a stabilizer to obtain a hydrogenated block copolymer (111)- 2. The hydrogenation rate of the obtained hydrogenated block copolymer is 99%. (Hydrogenated block copolymer (111)-3) A tank type reactor equipped with a stirring device and a jacket (the internal volume is (7) L)' The batch polymerization was carried out. First, 16 parts by mass of a cyclohexane solution (concentration: 20% by weight) containing styrene was charged. Then, 0.095 parts by mass of n-butyllithium was added to 1 part by mass of all the monomers, relative to Polymerization was carried out at 70 ° C for 30 minutes with the addition of 〇 3 Mole TMEDA. • Then, a solution of butadiene oxime in a cyclohexane solution (concentration of 20% by weight) was added. ), polymerize at 7 (TC for 5 minutes. The final input contains styrene) /6 Cyclohexane solution (concentration: 2% by weight) at 7 Torr. Polymerization at the submerged minute. 13 Block copolymer obtained in the above manner, the styrene content is "% by weight, Ding Er The vinyl group has an ethylenic bond amount of 37% by weight, a weight average molecular weight of 83,000, and a molecular weight distribution of 〇5. Further, the obtained block copolymer 'is carried out in the same manner as the above (hydrogenated block copolymer). In the hydrogenation reaction, a stabilizer was added in the same manner as described above (gas 142282.doc • 55·201020289-blocked copolymer (i)-i) to obtain a hydrogenated block copolymer (111)-3. The hydrogenated block copolymer obtained had a hydrogenation rate of 99%. &lt;Olefin-based resin (11)&gt; As the olefin-based resin (II), PC630A (manufactured by PP/Sun Allomer; random copolymer, MFR = 7.5) was used. [Production Examples 1 to 5] For the hydrogenated block copolymer produced in the above manner, (1)_2, (1)-3, (I)-4, (1)_5, a 4 inch roll was used alone for 2 inches. 〇〇c来辗® Flat' then use a hydraulic press to 2 〇〇. 〇, 1 〇〇 kg/cm2 was extruded to form a 2 mm thick formed sheet. [Production Examples 6 to 8] The hydrogenated block copolymers (1)_6, (1)_7, and (1)-8' produced in the above manner were each independently used in a 4 inch roll at 2 inches &lt;) (: After that, it was extruded by a hydraulic presser at 20 (TC, 1 〇〇 kg/cm 2 to prepare a molded sheet having a thickness of 2 mm.

In the table, the hydrogenated block copolymers (I)-()_ of the above [Production Examples 1 to 5] and the structure of each of (1)^ of the hydrogenated block copolymers (1) of [Examples 6 to 8] showed the following items. The value. The content of the vinyl group fragrant compound of the royal group (% by mass) (a) the polymer of the vinyl aromatic * (f * 〇 / 〇) sputum as the main part of the &lt; group compound and conjugated diene The hydrogenated copolymer (b) contains the content of the vinyl aromatic moiety (mass. / 〇). 142282.doc -56- 201020289 (C) content of the hydrogenated polymer block mainly composed of a conjugated diene (% by mass) The content (% by mass) of the vinyl aromatic compound in the hydrogenated copolymer block of the above (b). The amount of the vinyl bond (% by mass) in the hydrogenated copolymer block of the above (c). 10,000) Hydrogenation rate (%) of double bonds of a total of diene monomer units. Further, in Table 1, hydrogenated block copolymers (1)-1 to (1)-5, (1)-6 to (1)- The peak temperature of tanS (loss tangent) in the viscoelasticity measurement chart of φ 8 in the temperature range of less than 0 ° C and 0 to 60 ° C. 142282.doc -57- 201020289 [I 朗 回 回 to toUB ;铼难龙W(I)荽龄沭鸹qq/f .1--^ 1 Manufacturing Example 8 1 | Composition (1)-8 | Ο ΓΠ 〇ΙΓ) 00 &lt;n 1 ITi \〇20.1 00 〇 \ -15.2 1 Manufacturing Example 7 | Composition (1)-7 rn ΓΟ 1 1 1 v〇〇&lt; ON ON -26.0 1 Production Example 6 |Component (1)-6 m VH 1 1 1 15.9 00 Os ^ -13.9J 1 Production Example 5 Component (1) -5 1 JT1 OS [20.3 | oo ON -36.2 18.9 Manufacturing Example 4 Composition (1)-4 ν〇inch JO 1 OS yn ΓΛ 16.3 00 On -30.2 18.8 Manufacturing Example 3 |Component (1)-3 1 JQ 18.4 1 ON -32.2 〇〇Manufacturing Example 2 Ingredient (1)-2 〇\ ΚΤΛ &lt;N m 卜iTi 1 13.7 00 ON -31.2 17.8 Manufacturing Example 1 Composition (1)-1 % Os 1 14.8 OO -30.2 25.8 All vinyl Aromatic compound content (% by mass) Content of polymer plate segment (a) (mass ° / 〇) Content of polymer block (b) (% by mass) Content of polymer block (c) (% by mass) Polymerization Content of the block (d) (% by mass) 5 !〇e茗^ ΦΊ Gong®w φ ·4〇 The amount of vinyl bond in the polymer block (c) (% by mass) Weight average molecular weight (million) The hydrogenation rate (%) of the double bond of the conjugated diene monomer unit is less than 0 °C 0~60 °C ΐαηδ peak temperature (°C) .. f 3t^ .. S5f ^ 142282.doc -58- 201020289 Table 2 In the [Production Example 9 to 丨u, the structure of the hydrogenated block copolymer (III)-1~(ΙΠ)_3 is shown. This is the value of the following items. The content of all ethylene-based aromatic compounds (mass ° / 〇). (C) A vinyl bond amount (% by mass) in the hydrogenated polymer block mainly composed of a conjugated diene. Weight average molecular weight (million) Hydrogenation rate (%) of double bond of conjugated diene monomer unit [Table 2] Disk preparation example 9 _ Manufacturing Example 10 Production Example 11 Component (ra)-1 Component (m)-2 Component (111)-3 All. p ethyl field and scented compound content (quality 13 13 32 polymer block (B) vinyl bond one ~ 78 51 37 weight average molecular weight (million) - 15.1 10.6 8.3 a total of one thin monomer unit Hydrogenation rate of double bond (%, 99 99 99 [Examples 1 and 2]

The powdered hydrogenated block copolymer (1) was "mixed with an olefin-based resin (Π) in a ratio shown in the following Table 3" to be flattened with a 4 inch roll at 17 inches, and then oil was used. The pressurizing machine was extruded at 2 〇〇, 1 〇〇 kg/cm 2 to prepare a molded sheet having a thickness of 2 mm. Further, the hydrogenated block copolymer (1) 丨 and the olefin resin (π) were prepared. The mixture was blended at a ratio shown in the following Table 3, and extruded at 23 ° C using a 2 〇 twin-screw extruder to prepare a tubular molded body having an inner diameter of 4 mm and an outer diameter of 6 melons. And 4] the powdered hydrogenated block copolymer (1)_2 and the olefin resin 142282.doc •59· 201020289 (II) are formulated in the ratio shown in the following Table 3, using a 4 inch roll It was extruded at 17 (TC), and then extruded at 200 ° C and 100 kg/cm 2 by a hydraulic press to prepare a 2 mm thick formed sheet. Further, the above hydrogenated block copolymer ( 1)-2 and olefin-based resin (11) were blended in the ratio shown in Table 3 below, and extruded at 230 ° C using a 20 ηηιηφ twin-screw extruder to prepare an inner diameter of 4 mm and an outer diameter of 6 mm. Tube [Examples 5 and 6] The hydrogenated block copolymer (1)-3 obtained in the form of a powder and the olefin resin (II) were blended at a ratio shown in the following Table 3, using 4 inches. The roll was made up of 170. (: 辗 flat, and then extruded by 200 ° C, 100 kg/cm 2 using a hydraulic press machine to make a 2 mm thick formed sheet. The copolymer (1)-3 and the olefin resin (π) were blended at a ratio shown in the following Table 3, and extruded at 230 ° C using a 20 ηπηφ twin-screw extruder to prepare an inner diameter of 4 mm and an outer diameter. The tube-shaped molded body of 6 mm. [Examples 7 and 8] The hydrogenated block copolymer (1)-4 prepared in the form of a powder and the olefin resin (Π) were subjected to a ratio shown in Table 3 below. The mixture was prepared by flattening at 70 ° C with a 4 inch roll, and then extrusion molding at 200 ° C and 100 kg/cm 2 using a hydraulic press to make a 2 mm thick formed sheet. The hydrogenated block copolymer (1)_4 and the olefin resin (π) were blended at a ratio shown in the following Table 3, and extruded at 23 ° C using a 20 ηπηφ twin-screw extruder to prepare an inner diameter of 4 mm. With an outer diameter of 6 mm The shape is 142282.doc -60- 201020289. [Examples 9 and 10] The hydrogenated block copolymer (1)-5 and the diluted hydrocarbon resin (II) which are formed into a powder form are shown in Table 3 below. The ratio shown is adjusted, and the mixture is flattened at a temperature of 17 ° C using a 4 inch pair of rolls, and then extruded at 200 ° C and 1 〇〇 kg / cm 2 by a hydraulic press to prepare a 2 mm thick layer. Formed sheet. Further, 'the above-mentioned hydrogenated segment copolymer (1)-5 and the dilute-smoke resin (II) were blended at a ratio shown in the following Table 3, and extruded at 230 ° C using a 20 ηηιηφ twin-screw extruder. A tube-shaped formed body having an inner diameter of 4 mm and an outer diameter of 6 mm. [Comparative Example 1] The hydrogenated block copolymer (1)_6 thus obtained in the form of a powder and the olefin-based resin (II) were blended at a ratio shown in the following Table 3, and were passed at a pressure of 17 Torr with a 4 inch roll. (: 辗 辗 ' ' Afterwards, using a hydraulic presser to perform dust forming at 200 ° C, l oo kg / cm 2 to produce a 2 mm thick formed sheet. φ Also, the above hydrogenated block copolymer ( 1)-6 and olefin-based resin (11) were blended at a ratio shown in the following Table 3, and extruded at 230 C using a 2 mm &lt;j) twin-screw extruder to prepare an inner diameter of 4 mm and an outer diameter. It is a tube-shaped formed body of 6 claws. [Comparative Example 2] The powdered hydrogenated block copolymer (1)_7 and the olefin resin (Π) were blended at a ratio shown in the following Table 3, and were flattened with a 4-inch roll, and then oil was used. A press press was used to extrude it by 2 〇〇, 1 〇 () kg/cm 2 to form a 2 mm thick formed sheet. 142282.doc •61 - 201020289 Further, the above hydrogenated block copolymer (1)-7 and a rare hydrocarbon resin (π) or less

The ratios shown in Table 3 were adjusted, and extruded at 230 ° C using a 20 ηηπιφ twin-screw extruder to prepare a tube-shaped formed body having an inner diameter of 4 mm and an outer diameter of 6 mm. [Comparative Example 3] The powdered hydrogenated block copolymer (1)_8 and the olefin resin (II) were blended in the ratio shown in Table 3 below. Then use a hydraulic press to 200. (:, 100 kg/cm2 was extrusion-molded) A 2 mm thick formed sheet was produced.

Further, 'the hydrogenated block copolymer (1)_8 and the olefin resin (π) were blended at a ratio shown in the following Table 3, and extruded at 230 ° C in a 2 〇 mm &lt;|) twin-screw extruder. A tube-shaped formed body having a diameter of 4 mm and an outer diameter of 6 mm. [Examples 11 to 14] The hydrogenated block copolymer (1)_1, (丨(1)-oxime, and olefin-based resin (II)) which were prepared into a powder form were blended at a ratio shown in the following Table 4, and used 4 The British roll was flattened at 17 ° C, and then extruded by a hydraulic press at 200 ° C and 1 〇〇 kg / cm 2 to produce a 2 mm thick formed sheet. The hydrogenated block copolymer (1)_丨, (ΠΙ)_丨 and the olefin-based resin (II) were blended in the ratio shown in Table 4 below, and extruded at 230 ° C using a 2 〇 mnu)) twin-screw extruder. A tube-shaped formed body having an inner diameter of 4 mm and an outer diameter of 6 mm was produced. [Comparative Examples 4 and 5] The hydrogenated block copolymer (Ι)_6, (πΐ)-1 and olefin 142282.doc • 62· 201020289 resin (II) which were prepared into a powder form are shown in Table 4 below. The ratio was adjusted, and it was flattened at 170 ° C with a 4 inch blade, and then extruded by a hydraulic press at 200 Å and 1 〇〇 kg/cm 2 to form a 2 mm thick formed sheet. . Further, the hydrogenated block copolymers (1)-6, (III)·1 and the olefin-based resin (II) were blended at a ratio shown in the following Table 4, and used a 20 ηιηιφ twin-screw extruder at 230°. Extrusion under C, a tube-shaped formed body having an inner diameter of 4 mm and an outer diameter of 6 mm was produced. [Comparative Example 6] The powdered hydrogenated block copolymers (1)-7, (III)-1 and the olefin resin (II) were blended at a ratio shown in the following Table 4, using 4 inches. The roll was flattened at 170 C, and then extruded by a hydraulic press at 2 ° C and 100 kg/cm 2 to form a 2 mm thick formed sheet. Further, 'the hydrogenated block copolymer (Ι)-7, (ΙΠ)-1 and the olefin-based resin (II) were blended at a ratio shown in the following Table 4, and a 20 mm &lt;|) twin-screw extruder was used. Extrusion at 230 ° C to produce a tube-shaped formed body having an inner diameter of 4 mm and an outer diameter of 6 mm. [Comparative Example 7] The powdered hydrogenated block copolymer (Ι)-1, (ΠΙ)-2 and the olefin-based resin (II) were blended at a ratio shown in the following Table 4, using 4 inches. The roll was flattened at 17 ° C, and then extruded by a hydraulic press at 200 ° C and 1 〇〇 kg / cm 2 to form a 2 mm thick formed sheet. Further, the hydrogenated block copolymer (1)-1, (ΙΠ) 2 and the olefin resin (II) were blended at a ratio shown in the following Table 4, and extruded at 23 °C using a 20 ηηηιφ twin-screw extruder. Prepare a tube shape with an inner diameter of 4 mm and an outer diameter of 6 mm 142282.doc • 63- 201020289 Shaped body. [Comparative Example 8] The powdered hydrogenated block copolymer (Ι)-1 '(ΠΙ)_3 and the olefin-based resin (II) were blended at a ratio shown in the following Table 4, and used in 4 inches. The roller was flattened at 170 C. Thereafter, the hydraulic press was used to 2 Torr. 〇, 1〇〇 kg/cm was extruded to produce a formed sheet of 2 melons. Further, the hydrogenated block copolymers (1)-丨, (111)_3 and the olefin-based resin (II) were blended at a ratio shown in the following Table 4, and were passed through a 2 mm (|) twin-screw extruder at 23 Torr. Extrusion under C, a tube-shaped formed body having an inner diameter of 4 mm and an outer diameter of 6 mm was produced. The hydrogenated block copolymer composition of [Examples 1 to 10] and [Comparative Examples 1 to 3] '(7) hardness, (8) tensile strength (Tb), elongation at break (Eb), (9) The respective measured values and evaluation results of tripso-type rebound elasticity, (1〇) kink resistance, (n) haze value (haze), and transparency determination are shown in Table 3 below. 142282.doc -64· 201020289 [Γηΐ

142282.doc Comparative Example 3 1 1 1 1 1 1 1 〇〇〇00 o H &lt;N m 5 χ 卜 ^ XXX oo Comparative Example 2 1 1 1 1 1 1 S 1 〇σΝ 〇00 S χ Ό ο XX as Od X Comparative Example 1 1 1 1 1 1 § 1 1 〇〇\ mom yr) CN cK m η x 00 "X inch X &lt;NX 0's bird 2 1 1 1 meaning 1 1 1 〇〇\ 〇〇〇VO ΓΟ ΓΟ 〇 ITi ◎ S ◎ CN Example 9 1 1 1 1 〇 1 1 1 cn 00 oo o T—H VO (N 00 〇^Τί ◎ 'O © Example 8 1 1 1 % 1 1 1 1 〇00 00 omo 00 CN CN m (Ν Ο ◎ vn 〇 O inch embodiment 7 1 1 1 〇 1 1 1 1 § ON cn o 卜 CN OO Ο Ο in ◎ (N ^ (N @ &lt; N Example 6 1 1 1 1 1 1 1 〇 o o oo &lt; N 5 o V 〇 〇 〇 〇 〇 〇 〇 〇 〇 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O m Example 4 1 1 1 1 1 1 1 〇00 CN m H o 1—H (N ^ 〇ο 〇〇·〇〇Os Celluloid Example 3 1 〇1 1 1 1 1 1 i—H o 卜 inch S 〇卜卜:〇in 〇K〇Example 2 % i 1 1 1 1 1 1 〇 inch ON iH o Os CN 卜&lt;Ν Ο ◎ \D uS O m Example 1 〇1 1 1 1 1 1 soo VO oo m ◎ Os ^ (N © &lt;N component (1)-1 component (1)-2 component (1)-3 component (1)-4 component (1)-5 component (1)- 6 Ingredients (1)-7 Ingredients (1)-8 Ingredients (II) Hardness (X- after l〇s) rO I e rebound elastic (%) ? w 5» ^ 鲮垅1 游S7 ηβ*1 锩s« U 耐 kneading resistance comprehensive judgment haze (%) transparency determination formula basic physical property • 65- 201020289 For the hydrogenated block copolymer compositions of [Examples 11 to 14] and [Comparative Examples 4 to 8], (7) hardness, (8) tensile strength (Tb), elongation at break (Eb), (9) tripso-type rebound elastic, (10) kink resistance, (11) haze value (haze), The respective measured values and evaluation results of the transparency determination are shown in Table 4 below. [Table 4] Table-4. Physical properties of hydrogenated copolymer composition

Example 11 Example 12 Example 13 Example 14 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Formulation ingredients (1)-1 52.5 45 30 15 _ • - 30 30 Composition (1)-6 • • _ 30 15 • - Composition (1)-7 _ One • • 15 _ Composition (111)-1 7.5 15 30 45 30 45 45 - Composition (ΠΙ)-2 • _ - - - - 30 - Composition (111)-3 30 Composition (II) 40 40 40 40 40 40 40 40 40 Basic hardness (X- after 10 s) 90 91 88 87 92 89 87 91 93 Physical properties Tb (kg/cm2) 110 128 140 164 219 204 149 176 194 Eb ( 〇 〇 〇 980 980 980 980 980 980 980 980 〇〇XXXXX Movement distance between chucks (mm) 55.1 58.3 62.1 67.4 44.3 46.4 48.4 45.8 44.2 Kink distance determination 〇〇◎ ◎ XXXXX Kink resistance comprehensive judgment ◎ ◎ ◎ ◎ XXXXX Haze (%) 48.6 49.7 49.2 45.6 93.6 71.0 38.7 54.9 59.6 Transparency determination 〇〇〇〇 XX 〇 XX Example 1 In the case of 14th, the hydrogenated block copolymers (1)-1 to (1)-5, and (III)-1 which satisfy the constituent elements of the present invention are used as constituent components, thereby obtaining practically good flexibility and rebounding. A hydrogenated block copolymer composition which is low in elasticity and excellent in kink resistance and transparency. In Comparative Examples 1 to 8, the hydrogenated block copolymers (1)-6 to (1)-8, (111)-2, and (111)-3 which do not satisfy the constitutional requirements of the present invention are used as constituent components, and thus For the high rebound resilience, the kink resistance can not be obtained in a practically good evaluation. -66-142282.doc 201020289 Price', transparency also deteriorated. The present application is based on a patent application filed on Jan. 12, 2008, the entire disclosure of which is incorporated herein by reference. [Industrial availability]

The hydrogenated block copolymer composition of the present invention is excellent in balance of flexibility, low rebound elasticity, kink resistance, and transparency, and is industrially useful as a hollow molded body such as a pipe or a hose, or an automobile interior or exterior decoration. Materials, toys, home appliance parts, medical appliances, etc. I industry parts, other groceries [Simple description of the diagram] Figure 1 is a kink resistance measurement chart.

142282.doc -67·

Claims (1)

201020289 VII. Patent application scope: ι_ A hydrogenated block copolymer composition containing (I) a hydride of a copolymer of a vinyl aromatic compound and a conjugated diene and having the following characteristics a hydrogenated block copolymer; 5 to 95% by mass; and (Π) at least one olefin-based resin: 5 to 95 mass% per oxime; (1) a polymer having at least one of the following (b), (c) a segment, (b) a hydrogenated copolymer block comprising a vinyl aromatic compound and a conjugated diene, (c) a hydrogenated polymer block mainly composed of a conjugated diene, (2) ethylene in the above (b) The content of the aromatic compound is 4 〇 to 8 〇 mass%, (3) The content of the above (()) in the above (I) is 2 〇 8 〇 mass (4) Determination of viscoelasticity of the chlorinated block copolymer (1) In the graph, the wave is in the 〇. (: above and at least one below 6 〇 t, and at least one is present at less than 〇 ° c. 2. a hydrogenated block copolymer composition, (1) a nitride containing a copolymer of an ethylene-based aromatic compound and a co-diuret and having the following (1)~ (4) Characterized hydrogenated I-segment copolymer: 2.5 to 92.5 mass%; (η) at least a dilute hydrocarbon resin: 5 to 95% by mass; and (m) a vinyl aromatic compound and a conjugated diene a hydrogenated block copolymer having a hydride of a copolymer and having the following characteristics (5) to (9) (): 2.5 to 92.5 mass%; 142282.doc 201020289 (1) a polymer having at least one of the following (b), (4) a block, (b) a hydrogenated copolymer block comprising an ethylene-based aromatic compound and a conjugated diene, (c) a hydrogenated polymer block mainly composed of a conjugated diene, (2) in the above (b) The content of the vinyl aromatic compound is 4 〇 to 8 〇 mass%, (3) the above (I) content ((;) is 2 〇 to 8 〇 mass 〇乂, (4) hydrogenated block copolymer (1) The peak of the viscoelasticity measurement map (Q, loss tangent) is at 〇. (: above and 6 (at least one below rc, at least one when not 〇c, (5) has at least two with vinyl aromatic a polymer block (A) having a compound as a host, and at least one hydrogenated polymer block having a conjugated diene as a main component B), (6) The content of all the vinyl aromatic compounds in the hydrogenated block copolymer (ΠΙ) exceeds 10% by mass and does not exceed 25% by mass, (7) the above-mentioned hydrogenated polymer mainly composed of a common diene The amount of the vinyl bond in the block (B) is 62 mass % / 〇 or more and less than 99 mass 〇 / 〇, (8) the weight average molecular weight of the hydrogenated block copolymer is 30,000 to 3 million, (9) More than 75 % of the double bonds of the conjugated diene monomer units in the hydrogenated copolymer are hydrogenated. 3. The hydrogenated block copolymer composition according to claim 2, wherein the nitrided block copolymer of the above (ΠΙ) contains 0.1 to 9% by mass of the above-mentioned hydrogenated main body of the diene diene at least at one single end. Polymer block. 4. The hydrogenated block copolymer paper composition according to claim 1, wherein the nitrogen (142) 142282.doc -2- 201020289 block copolymer of the above (1) contains at least one terminal end of the above (4) hydrogenation polymerization mainly composed of a common dilute Block. 5. The hydrogenated block copolymer composition according to claim 2, wherein the hydrogenated block* polymer of the above (1) contains a hydrogenated polymer block having at least a single terminal and having a co-consumption of two as a main component. The hydrogenated block copolymer composition according to claim 3, wherein the hydrogenated block copolymer of the above (1) contains the above (c) hydrogenated polymer block having a conjugated diene as a main body at at least a single terminal. The hydrogenated block copolymer composition according to any one of claims 1 to 6, wherein the content of all the vinyl aromatic compounds in the hydrogenated block copolymer of the above (1) is from 20 to 50% by mass. 8. The hydrogenated block copolymer composition according to any one of claims 1 to 6, wherein the amount of the vinyl bond in the hydrogenated polymer block in which the above (c) is a conjugated diene is 50% by mass or more . 9. The hydrogenated block copolymer composition according to any one of claims 1 to 6, wherein the above (b) of the argonized block copolymer of (1) above comprises a vinyl aromatic sigma and a total of one The content of the dilute hydrogenated copolymer block is 20 to 8 % by mass. The hydrogenated block copolymer composition according to any one of claims 1 to 6, wherein the hydrogenated block copolymer of the above (1) has at least one (a) a polymer block mainly composed of a vinyl aromatic compound. 11. The hydrogenated segment copolymer composition according to the above item 1, wherein the content of the polymer block (a) having a vinyl aromatic compound as a main component in the hydrogenated block copolymer of the above (1) is 3~ 30 quality. /〇. The hydrogenated block copolymer composition according to any one of items 1 to 6, wherein the hydrogenated block copolymer of the above (1) has at least - (4) A polymer block having a vinyl bond amount of 25 里/〇 or less and a conjugated diene as a main component. The hydrogenated block copolymer composition of the above-mentioned item (1), wherein the (4) of the hydrogenated block copolymer of the above (1) is a polymer block having a conjugated diene as a main component of 25 mass% or less. The content is 3 to 30% by mass. The hydrogenated block copolymer composition according to any one of items 1 to 6, wherein the hydrogenated block copolymer of the above (1) has a weight average molecular weight of 50,000 to 60,000. The hydrogenated block copolymer composition according to any one of claims 1 to 6, wherein 75% or more of the double bonds of the conjugated diene monomer unit in the hydrogenated block copolymer of the above (1) are hydrogenated. The hydrogenated block copolymer composition according to any one of claims 1 to 6, wherein the olefin-based resin comprises at least one polypropylene-based resin. A shaped body formed by using the gasified block copolymer composition according to any one of claims 1 to 16. A hollow shaped body formed by using the hydrogenated block copolymer composition according to any one of claims 1 to 16. 142282.doc