CN102119190B - Hydrogenated block copolymer composition and molded article using same - Google Patents

Abstract

The present invention provides a hydrogenated block copolymer composition comprising: 5 to 95 mass% of a hydrogenated block copolymer which is a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene, the hydrogenated block copolymer having the following characteristics (1) to (4); and 5 to 95 mass% of (ii) at least 1 olefin resin. (1) Has at least 1 polymer block of the following (b) and (c). (b) A hydrogenated copolymer block comprising a vinyl aromatic compound and a conjugated diene. (c) Hydrogenated polymer blocks based on conjugated dienes. (2) The content of the vinyl aromatic compound in the (b) is 40-80% by mass. (3) The content of (c) in is 20 to 80 mass%. (4) The hydrogenated block copolymer has at least 1 peak of tan δ (loss tangent) in the viscoelasticity measurement chart at 0 ℃ or higher and 60 ℃ or lower, and at least 1 peak in the range of less than 0 ℃.

Description

Hydrogenated block copolymer composition and molded article using same

technical field

The present invention relates to a hydrogenated block copolymer composition and a molded article using the composition.

Background technique

Conventionally, hollow molded articles such as tubes and hoses have been required to have transparency and bending resistance, and soft vinyl chloride-based resins are mainly used as their materials.

However, since soft vinyl chloride resins contain a large amount of plasticizers, especially when used for medical purposes, there is a problem of leaching into liquid medicine or blood, and there are also environmental loads caused by the generation of chlorine gas during incineration. problem, and therefore an alternative material is needed.

In view of the above problems, various thermoplastic elastomer compositions have been proposed in recent years, especially styrene-based elastomer compositions excellent in flexibility (for example, see Patent Documents 1 to 6).

Patent Document 1 proposes a tube composed of two types of hydrogenated copolymers, an olefin-based resin, and a softener for rubber.

Patent Document 2 proposes a composition composed of a hydrogenated block copolymer, an olefin-based copolymer, and a plasticizer.

Patent Document 3 proposes a composition composed of a polyolefin resin, a hydrogenated diene copolymer, and a polymethylpentene resin.

Patent Document 4 proposes a composition composed of a hydrogenated diene-based copolymer and a polyolefin resin.

Patent Document 5 proposes a composition composed of a hydrogenated diene-based copolymer and a thermoplastic polymer.

Patent Document 6 proposes a pipe composed of two types of hydrogenated block copolymers and a polyolefin-based resin.

However, especially hollow molded articles such as pipes and hoses are required to have transparency and bending resistance in consideration of their practical use. Regarding transparency, the compatibility of the composition becomes an important factor, and regarding bending resistance, energy absorption and flexibility in a room temperature region become important factors.

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-287163

Patent Document 2: Japanese Patent Application Laid-Open No. 9-316287

Patent Document 3: Japanese Patent Application Laid-Open No. 11-189689

Patent Document 4: Japanese Patent Laid-Open No. 2005-247895

Patent Document 5: Japanese Patent Laid-Open No. 2005-255856

Patent Document 6: International Publication No. 2009/031625

Contents of the invention

However, for hollow molded articles such as pipes and hoses molded using the above-mentioned conventionally proposed styrene-based elastomer compositions, they do not yet have sufficient properties in terms of the balance between transparency and bending resistance. Issues for improvement.

Accordingly, an object of the present invention is to provide a composition having flexibility, low resilience, that is, excellent energy absorbability at room temperature, and an excellent balance between transparency and bending resistance, and to provide pipes, flexible A hollow molded body such as a tube.

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, found that resilience and flexibility are related to bending resistance.

In addition, the bending resistance refers to the performance that satisfies both the ease of the speed at the moment of bending and the performance of shortening the distance between the bent pipes when bending a hollow molded body such as a pipe or a hose. .

In addition, it was found that a hydrogenated block copolymer composition using a hydrogenated block copolymer having a specific The segment copolymer has a peak of tan δ (loss tangent) in a viscoelasticity measurement chart in a specific temperature range.

In addition, it was found that a hydrogenated block copolymer composition with high flexibility, specifically a hydrogenated block copolymer composition using a hydrogenated block copolymer having a remarkable effect of reducing the tensile elastic modulus, has the above-mentioned high shortening angle. The distance between the bent tubes is the effect of shortening the bending diameter, thus completing the present invention.

The present invention is as follows.

[1]

A hydrogenated block copolymer composition is provided, which contains:

5 to 95% by mass of (i) a hydrogenated block copolymer having the following characteristics (1) to (4), the hydrogenated block copolymer being a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene ;as well as

5 to 95% by mass of (ii) at least one type of olefin-based resin.

(1) having at least one polymer block of the following (b), (c);

(b) hydrogenated copolymer blocks composed of vinyl aromatic compounds and conjugated dienes;

(c) Hydrogenated polymer blocks based on conjugated dienes;

(2) The content of the vinyl aromatic compound in (b) is 40-80% by mass;

(3) The content of (c) in (i) is 20-80% by mass;

(4) In the viscoelasticity measurement chart of the hydrogenated block copolymer (i), there is at least one peak of tanδ (loss tangent) between 0°C and below 60°C, and at least one peak is present in the range of less than 0°C A peak of tanδ.

[2]

A hydrogenated block copolymer composition is provided, which contains:

2.5 to 92.5% by mass of (i) a hydrogenated block copolymer having the following characteristics (1) to (4), the hydrogenated block copolymer being a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene ;

5-95% by mass of (ii) at least one olefin-based resin: and

2.5 to 92.5% by mass of (iii) a hydrogenated block copolymer having the following characteristics (5) to (9), the hydrogenated block copolymer being a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene .

(1) having at least one polymer block of the following (b), (c);

(b) hydrogenated copolymer blocks composed of vinyl aromatic compounds and conjugated dienes;

(c) Hydrogenated polymer blocks based on conjugated dienes;

(2) The content of the vinyl aromatic compound in (b) is 40-80% by mass;

(3) The content of (c) in (i) is 20-80% by mass;

(4) In the viscoelasticity measurement chart of the hydrogenated block copolymer (i), there is at least one peak of tanδ (loss tangent) between 0°C and below 60°C, and at least one peak is present in the range of less than 0°C a peak of tanδ;

(5) having at least 2 polymer blocks (A) mainly composed of vinyl aromatic compounds, and at least 1 hydrogenated polymer block (B) mainly composed of conjugated diene;

(6) The content of all vinyl aromatic compounds in the hydrogenated block copolymer (iii) is more than 10% by mass and less than 25% by mass;

(7) The amount of vinyl bonds in the hydrogenated polymer block (B) mainly composed of conjugated diene is 62 mass% or more and less than 99 mass%;

(8) The weight-average molecular weight of the hydrogenated block copolymer is 30,000 to 300,000;

(9) 75% or more of the double bonds of the conjugated diene monomer units in the hydrogenated block copolymer are hydrogenated.

[3]

There is provided the hydrogenated block copolymer composition according to the above [2], wherein the hydrogenated block copolymer of (iii) contains 0.1 to 9.1% by mass of the conjugated diene-based The hydrogenated polymer block (B).

[4]

The hydrogenated block copolymer composition according to any one of the above-mentioned [1] to [3] is provided, wherein the hydrogenated block copolymer of (i) contains the (c) at least one terminal to co- Conjugated diene-based hydrogenated polymer block.

[5]

The hydrogenated block copolymer composition as described in any one of the above [1] to [4] is provided, wherein the content of all vinyl aromatic compounds in the hydrogenated block copolymer of (i) is 20 ~50% by mass.

[6]

The hydrogenated block copolymer composition according to any one of the above-mentioned [1] to [5] is provided, wherein the (c) vinyl bond in the hydrogenated polymer block mainly composed of conjugated diene is The amount is 50% by mass or more.

[7]

The hydrogenated block copolymer composition according to any one of the above-mentioned [1] to [6] is provided, wherein the (b) in the hydrogenated block copolymer of (i) is composed of vinyl aromatic The content of the hydrogenated copolymer block composed of the compound and the conjugated diene is 20 to 80% by mass.

[8]

The hydrogenated block copolymer composition as described in any one of the above [1] to [7] is provided, wherein the hydrogenated block copolymer of (i) has at least one (a) vinyl aromatic The compound is a polymer block of the host.

[9]

There is provided the hydrogenated block copolymer composition according to the above [8], wherein the (a) polymer block mainly composed of a vinyl aromatic compound in the hydrogenated block copolymer of (i) The content is 3 to 30% by mass.

[10]

The hydrogenated block copolymer composition as described in any one of the above [1] to [7] is provided, wherein the hydrogenated block copolymer of (i) has at least one (d) vinyl bond in 25% by mass or less of a polymer block mainly composed of a conjugated diene.

[11]

The hydrogenated block copolymer composition as described in the above-mentioned [10] is provided, wherein the (d) vinyl bond amount in the hydrogenated block copolymer of (i) is 25% by mass or less and the conjugated The content of the polymer block mainly composed of diene is 3 to 30% by mass.

[12]

The hydrogenated block copolymer composition according to any one of the above [1] to [11], wherein the hydrogenated block copolymer of (i) has a weight average molecular weight of 50,000 to 600,000.

[13]

The hydrogenated block copolymer composition as described in any one of the above [1] to [12] is provided, wherein the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer of (i) More than 75% of it is hydrogenated.

[14]

There is provided the hydrogenated block copolymer composition according to any one of [1] to [13] above, wherein the olefin-based resin of (ii) contains at least one type of polypropylene-based resin.

[15]

A molded article molded using the hydrogenated block copolymer composition according to any one of [1] to [14] above is provided.

[16]

A hollow molded article molded using the hydrogenated block copolymer composition according to any one of [1] to [14] above is provided.

According to the present invention, it is possible to obtain a hydrogenated block copolymer composition comprising a hydrogenated block copolymer and an olefin-based resin, which is excellent in flexibility, low resilience, transparency, and bending resistance, and a hydrogenated block copolymer composition using the Molded body of hydrogenated block copolymer composition.

Description of drawings

FIG. 1 shows a stress curve when a tube is bent in the measurement of bending resistance.

Detailed ways

Hereinafter, specific embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail. In addition, this invention is not limited to the following embodiment, Various deformation|transformation can be implemented within the range of the summary.

[Hydrogenated block copolymer composition]

As will be described later, the hydrogenated block copolymer composition of the present embodiment is roughly divided into the hydrogenated block copolymer composition of the first embodiment and the hydrogenated block copolymer composition of the second embodiment.

The hydrogenated block copolymer composition in the first embodiment contains:

5 to 95% by mass of (i) a hydrogenated block copolymer that is a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene, the hydrogenated block copolymer having the following characteristics (1) to (4) ;as well as

5 to 95% by mass of (ii) at least one type of olefin-based resin.

(1) having at least one polymer block of the following (b), (c);

(b) hydrogenated copolymer blocks composed of vinyl aromatic compounds and conjugated dienes;

(c) Hydrogenated polymer blocks based on conjugated dienes;

(2) The content of the vinyl aromatic compound in (b) is 40-80% by mass;

(3) The content of (c) in (i) is 20-80% by mass;

(4) At least one peak of tan δ (loss tangent) in the viscoelasticity measurement chart of the hydrogenated block copolymer (i) exists between 0°C and 60°C, and at least one peak exists in the range of less than 0°C .

The hydrogenated block copolymer composition in the second embodiment contains:

2.5 to 92.5% by mass of (i) a hydrogenated block copolymer that is a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene, the hydrogenated block copolymer having the following characteristics (1) to (4) ;

5-95% by mass of (ii) at least one olefin-based resin: and

2.5 to 92.5% by mass of (iii) a hydrogenated block copolymer that is a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene, the hydrogenated block copolymer having the following characteristics (5) to (9) .

(1) having at least one polymer block of the following (b), (c);

(b) hydrogenated copolymer blocks composed of vinyl aromatic compounds and conjugated dienes;

(c) Hydrogenated polymer blocks based on conjugated dienes;

(2) The content of the vinyl aromatic compound in (b) is 40-80% by mass;

(3) The content of (c) in (i) is 20-80% by mass;

(4) At least one peak of tan δ (loss tangent) in the viscoelasticity measurement chart of the hydrogenated block copolymer (i) exists between 0°C and 60°C, and at least one peak exists in the range of less than 0°C ;

(5) having at least 2 polymer blocks (A) mainly composed of vinyl aromatic compounds, and at least 1 hydrogenated polymer block (B) mainly composed of conjugated diene;

(6) The content of all vinyl aromatic compounds in the hydrogenated block copolymer (iii) is more than 10% by mass and less than 25% by mass;

(7) The amount of vinyl bonds in the hydrogenated polymer block (B) mainly composed of conjugated diene is 62 mass% or more and less than 99 mass%;

(8) The weight-average molecular weight of the hydrogenated block copolymer is 30,000 to 300,000;

(9) 75% or more of the double bonds of the conjugated diene monomer units 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.

<(i) a hydrogenated block copolymer as a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene and (iii) a hydrogenated block copolymer which is a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene Copolymer>

Hereinafter, the hydrogenated block copolymer of (i) and the hydrogenated block copolymer of (iii) may be simply referred to as hydrogenated block copolymer (i) and hydrogenated block copolymer (iii).

(vinyl aromatic compounds)

Examples of vinyl aromatic compounds constituting the hydrogenated block copolymer (i) and hydrogenated block copolymer (iii) include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene , 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc.

In particular, styrene is preferable from the viewpoint of the balance between price and mechanical strength.

These substances may be used alone or in combination of two or more.

The content of all vinyl aromatic compounds in the hydrogenated block copolymer (i) is preferably 20% by mass to 50% by mass, more preferably 23% by mass to 48% by mass, even more preferably 25% by mass to 46% by mass.

If the content of the vinyl aromatic compound in the hydrogenated block copolymer (i) exceeds 50% by mass, the transparency of the final target hydrogenated block copolymer composition tends to be impaired, and if it is less than 20% by mass, If so, there exists a tendency for a low resilience and poor bending resistance.

The total vinyl aromatic compound content in the hydrogenated block copolymer (iii) exceeds 10% by mass and less than 25% by mass, preferably 11% by mass to 24% by mass, more preferably 12% by mass to 23% by mass.

When the content of the vinyl aromatic compound in the hydrogenated block copolymer (iii) is 25% by mass or more, the transparency and flexibility of the final target hydrogenated block copolymer composition tend to be impaired. If it is 10% by mass or less, the strength tends to decrease and the adhesiveness tends to deteriorate.

The content of all vinyl aromatic compounds in the hydrogenated block copolymers (i) and (iii) can be measured with an ultraviolet spectrophotometer using the copolymer before hydrogenation or the copolymer after hydrogenation as a sample. .

(conjugated diene)

The conjugated diene constituting the hydrogenated block copolymer (i) and the hydrogenated block copolymer (iii) means a diene having one pair of conjugated double bonds.

Examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3 -pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and the like. In particular, 1,3-butadiene and isoprene are preferred from the viewpoint of a good balance between moldability and mechanical strength.

These substances may be used alone or in combination of two or more.

In addition, in the constitution of the hydrogenated block copolymer composition in this embodiment, "mainly" means that the proportion in a predetermined copolymer or in a copolymer block is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more.

(hydrogenated copolymer block (b))

The hydrogenated copolymer block (b) is composed of a vinyl aromatic compound and a conjugated diene.

The content of the vinyl aromatic compound in the hydrogenated copolymer block (b) is 40% by mass to 80% by mass, preferably 45% by mass to 75% by mass, more preferably 50% by mass to 70% by mass.

When the content of the vinyl aromatic compound in the hydrogenated copolymer block (b) exceeds 80% by mass, the flexibility and transparency of the finally obtained hydrogenated block copolymer composition tend to be impaired. On the other hand, if it is less than 40% by mass, the resilience tends to be low and the bending resistance tends to be poor.

The hydrogenated copolymer block in the hydrogenated block copolymer (i) ( The content of b) is preferably 20% by mass to 80% by mass, more preferably 25% by mass to 70% by mass, even more preferably 30% by mass to 60% by mass.

In addition, the content of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (i) can be measured by a nuclear magnetic resonance apparatus (NMR) or the like.

The amount of vinyl bonds in the conjugated diene moiety in the copolymer block before hydrogenation of the hydrogenated copolymer block (b) can be controlled by using a regulator such as a tertiary amine compound or an ether compound described later.

In the case of using 1,3-butadiene as the conjugated diene, from the viewpoint of obtaining a good balance of transparency, low resilience, and bending resistance in the final target hydrogenated block copolymer composition In the hydrogenated copolymer block (b), the 1,2-vinyl bond content of the conjugated diene moiety in the copolymer block before hydrogenation is preferably 5 to 60%, more preferably 10 to 50%.

In the case of using isoprene as the conjugated diene, or in the case of using 1,3-butadiene in combination with isoprene, the 1,2-vinyl bond and the 3,4-vinyl bond The total amount is preferably 3 to 75%, more preferably 5 to 60%.

In addition, in the present embodiment, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (here, when 1,3-butadiene is used as the conjugated diene, is 1, 2-vinyl bond amount) is called vinyl bond amount.

The amount of vinyl bonds can be measured by using the copolymer before hydrogenation as a sample and measuring with an infrared spectrophotometer (for example, the Hampton method).

(Hydrogenated polymer block (c) mainly composed of conjugated diene)

The hydrogenated polymer block (c) is mainly composed of a conjugated diene.

From the viewpoint of transparency and flexibility of the finally obtained hydrogenated block copolymer composition, the content of the hydrogenated polymer block (c) in the hydrogenated block copolymer (i) is 20% by mass to 80% by mass %, preferably 25% by mass to 70% by mass, more preferably 30% by mass to 60% by mass.

The vinyl bond amount of the conjugated diene before hydrogenation in the hydrogenated polymer block (c) affects the compatibility with the olefin-based resin (ii) described later. In order to improve the compatibility and improve the finally obtained The transparency and fluidity of the hydrogenated block copolymer composition are preferably at least 50% by mass, more preferably at least 55% by mass, and still more preferably at least 60% by mass.

(Polymer block (a) mainly composed of vinyl aromatic compound)

The hydrogenated block copolymer (i) preferably has at least one polymer block (a) mainly composed of a vinyl aromatic compound.

The content of the polymer block (a) mainly composed of a vinyl aromatic compound in the hydrogenated block copolymer (i) is preferably 3 to 30% by mass, more preferably 5 to 28% by mass, and even more preferably 7 to 28% by mass. 25% by mass.

When the content of the vinyl aromatic compound-based polymer block (a) in the hydrogenated block copolymer (i) is less than 3% by mass, in the final target hydrogenated block copolymer composition, there is Strength tends to decrease and heat resistance deteriorates, and when it exceeds 30% by mass, flexibility and transparency tend to be impaired.

The content of the polymer block (a) mainly composed of vinyl aromatic compounds can be determined by using osmium tetroxide as a catalyst to oxidatively decompose the copolymer before hydrogenation by using tert-butyl hydroperoxide (I.M.KOLTHOFF , et al., J.Polym.Sci.1, the method recorded in 429 (1946), hereinafter referred to as " osmium tetroxide method ".),

In addition, regarding the content of the polymer block (a) mainly composed of a vinyl aromatic compound, the copolymer before hydrogenation and the copolymer after hydrogenation can also be used as samples, and nuclear magnetic resonance (NMR) ( The method described in Y.Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). Hereinafter referred to as "NMR method".) is measured.

In addition, in this case, the content of the polymer block (a) mainly composed of a vinyl aromatic compound (as Os) measured by the osmium tetroxide method using the copolymer before hydrogenation, and the NMR method The content of the vinyl aromatic compound-based polymer block (a) (referred to as Ns) measured from the hydrogenated copolymer has a correlation represented by the following formula.

(Os)＝-0.012(Ns) ² +1.8(Ns)-13.0...(F)

Therefore, in the present embodiment, when the content of the polymer block (a) mainly composed of a vinyl aromatic compound in the hydrogenated copolymer is determined by the NMR method, the content obtained by the above formula (F) is The value of (Os) is defined as the content of the polymer block (a) mainly composed of a vinyl aromatic compound specified in this embodiment.

(Conjugated diene-based polymer block (d) having a vinyl bond content of 25% by mass or less)

The hydrogenated block copolymer (i) preferably has at least one polymer block (d) mainly composed of a conjugated diene having a vinyl bond content of 25% by mass or less.

The amount of vinyl bonds in the polymer block (d) mainly composed of conjugated diene is preferably 25% by mass or less, more preferably 23% by mass or less, further preferably 20% by mass or less.

If the amount of vinyl bonds in the polymer block (d) mainly composed of conjugated diene exceeds 25% by mass, the final target hydrogenated block copolymer composition may suffer from decreased strength and poor heat resistance. tendency.

The content of the polymer block (d) mainly composed of a conjugated diene having a vinyl bond content of 25% by mass or less in the hydrogenated block copolymer (i) is preferably 3 to 30% by mass, more preferably 5% by mass. ~28% by mass, more preferably 7 to 25% by mass.

If the content of the polymer block (d) mainly composed of conjugated diene in the hydrogenated block copolymer (i) is less than 3% by mass and the amount of vinyl bonds is 25% by mass or less, the final target hydrogenation In the block copolymer composition, the strength tends to decrease and the heat resistance tends to deteriorate, and if it exceeds 30% by mass, the flexibility tends to be impaired.

(Polymer block (A) mainly composed of vinyl aromatic compound)

The hydrogenated block copolymer (iii) has at least two polymer blocks (A) mainly composed of a vinyl aromatic compound.

The ratio of the polymer block (A) to all the vinyl aromatic compounds in the hydrogenated block copolymer (iii) is preferably 80% by weight or more, more preferably 85% by weight or more, more preferably 90% by weight or more.

When the ratio of the polymer block (A) is less than 80%, the strength tends to decrease and the heat resistance tends to deteriorate in the final target hydrogenated block copolymer composition.

(Hydrogenated polymer block (B) mainly composed of conjugated diene)

The hydrogenated block copolymer (iii) has at least one hydrogenated polymer block (B) mainly composed of a conjugated diene.

From the viewpoint of the transparency and flexibility of the finally obtained hydrogenated block copolymer composition, the content of the hydrogenated copolymer block (B) mainly composed of conjugated diene in the hydrogenated block copolymer (iii) is preferably It is more than 75 mass % and less than 90 mass %, More preferably, it is 76 mass % - 89 mass %, More preferably, it is 77 mass % - 88 mass %.

The amount of vinyl bonds in the hydrogenated polymer block (B) mainly composed of conjugated diene affects the compatibility with the olefin resin (ii) described later. In order to improve the compatibility, the final hydrogenated polymer block The transparency, flexibility and fluidity of the segment copolymer composition are such that the amount is not less than 62% by mass and less than 99% by mass, preferably 65% by mass to 95% by mass, more preferably 68% by mass to 90% by mass.

<tanδ (loss tangent) in the viscoelasticity measurement chart of the hydrogenated block copolymer (i)>

The hydrogenated block copolymer (i) has at least one tanδ (loss tangent) peak at 0 to 60°C, preferably 2 to 50°C, more preferably 4 to 40°C in the viscoelasticity measurement chart.

This peak of tan δ is a peak generated by the hydrogenated copolymer block (b) in the hydrogenated block copolymer (i). Regarding the existence of the peak, at least one peak exists in the range of 0 to 60° C., which is necessary for obtaining low resilience and bending resistance of the hydrogenated block copolymer composition which is finally aimed at.

In addition, in the viscoelasticity measurement chart, in addition to the above-mentioned 0-60°C, the hydrogenated block copolymer (i) exists at less than 0°C, preferably -60--5°C, more preferably -50--10°C At least 1 peak of tan δ (loss tangent).

This peak of tan δ is a peak generated by the hydrogenated copolymer block (c) in the hydrogenated block copolymer (i). Regarding the existence of the peak, at least one peak exists in the range of less than 0°C, which is necessary for the final target hydrogenated block copolymer composition to obtain sufficient flexibility and transparency for practical use at low temperatures .

In addition, tan δ can be measured using a viscoelasticity measuring device (manufactured by TA Instruments Co., Ltd., ARES) under the conditions of a strain of 0.5%, a frequency of 1 Hz, and a heating rate of 3°C/min.

<Weight Average Molecular Weight of Hydrogenated Block Copolymer (i)>

From the viewpoint of achieving a good balance of heat resistance, mechanical strength, and fluidity (moldability) in the final target hydrogenated block copolymer composition, the weight average molecular weight of the hydrogenated block copolymer (i) Preferably it is 50,000 to 600,000, more preferably 70,000 to 500,000, still more preferably 100,000 to 400,000.

<Weight Average Molecular Weight of Hydrogenated Block Copolymer (iii)>

From the viewpoint of achieving a good balance of heat resistance, mechanical strength, and fluidity (molding processability) in the final target hydrogenated block copolymer composition, the weight average molecular weight of the hydrogenated block copolymer (iii) It is 30,000 to 300,000, preferably 40,000 to 250,000, more preferably 50,000 to 200,000.

Here, the weight-average molecular weights of the hydrogenated block copolymers (i) and (iii) are measured by gel permeation chromatography (GPC), and a calibration curve obtained by measuring commercially available standard polystyrene is used. (Created using the peak molecular weight of standard polystyrene).

<Molecular Weight Distribution of Hydrogenated Block Copolymers (i), (iii)>

The molecular weight distributions of the hydrogenated block copolymers (i) and (iii) are determined by measurement by GPC, and can be calculated from the ratio of the weight average molecular weight to the number average molecular weight.

The molecular weight distribution of the hydrogenated block copolymers (i) and (iii) is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less.

<Hydrogenation rate of double bond of conjugated diene monomer unit in hydrogenated block copolymer (i)>

From the viewpoint of obtaining good heat resistance and weather resistance in the final target hydrogenated block copolymer composition, the hydrogenation of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (i) The ratio is preferably 75% or more, more preferably 80% or more, and still more preferably 85% or more.

<Hydrogenation rate of double bond of conjugated diene monomer unit in hydrogenated block copolymer (iii)>

Hydrogenation of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (iii) from the viewpoint of obtaining good heat resistance and weather resistance in the final target hydrogenated block copolymer composition The ratio is preferably 75% or more, more preferably 80% or more, and still more preferably 85% or more.

<Hydrogenation Rate of Aromatic Double Bonds of Vinyl Aromatic Compound Units in Hydrogenated Block Copolymers (i) and (iii)>

The hydrogenation rate of the aromatic double bonds of the vinyl aromatic compound units of the hydrogenated block copolymers (i) and (iii) is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and still more preferably 20%. %the following.

Here, the hydrogenation rate of the hydrogenated block copolymers (i) and (iii) can be measured using a nuclear magnetic resonance apparatus (NMR) or the like.

<Crystalline Peak of Hydrogenated Block Copolymer (i)>

The hydrogenated block copolymer (i) is preferably a hydrogenated product in which, in the differential scanning calorimetry (DSC) chart, the above-mentioned vinyl aromatic and Crystallization peaks generated by hydrogenated copolymer block (b) composed of conjugated diene.

Here, "the crystallization peak due to the hydrogenated copolymer block (b) composed of vinyl aromatic and conjugated diene does not substantially exist in the range of -20 to 80°C" means that in this temperature range In , the peak due to crystallization of the hydrogenated copolymer block (b) composed of vinyl aromatic and conjugated diene does not appear, or means that even when the peak due to crystallization is confirmed , the crystallization peak heat generated by the crystallization is also less than 3J/g, preferably less than 2J/g, more preferably less than 1J/g, more preferably no crystallization peak heat.

As described above, if there is substantially no crystallization peak generated by the hydrogenated copolymer block (b) composed of vinyl aromatic and conjugated diene in the range of -20 to 80°C, the hydrogenated block Favorable flexibility can be obtained in the block copolymer (i), and it is suitable for softening the final target hydrogenated block copolymer composition.

In order to obtain a hydrogenated block copolymer (i) that does not substantially have crystallization peaks generated by the hydrogenated copolymer block (b) composed of vinyl aromatic and conjugated diene in the range of -20 to 80°C, It is sufficient to carry out the polymerization reaction under the conditions described below using a prescribed regulator for adjusting the amount of vinyl bonds and the copolymerization of the vinyl aromatic compound and the conjugated diene, and hydrogenate the copolymer thus obtained. .

<Structures of Hydrogenated Block Copolymers (i), (iii)>

The structure of the hydrogenated block copolymer (i) is not particularly limited, and examples thereof include those having a structure represented by the following general formula.

(bc) _n , c-(bc) _n , b-(cb) _n , (bc) _m -X, (cb) _m -X, c-(ba) _n , c-(ab) _n , c-( aba) _n , c-(bab) _n , c-(bca) _n , a-(cbca) _n , ac-(ba) _n , ac-(ab) _n , ac-(ba) _n -b, [( abc) _n ] _m -X, [a-(bc) _n ] _m -X, [(ab) _n -c] _m -X, [(aba) _n -c] _m -X, [(bab) _n - c] _m -X, [(cba) _n ] _m -X, [c-(ba) _n ] _m -X, [c-(aba) _n ] _m -X, [c-(bab) _n ] _m - X, c-(bd) _n , c-(db) _n , c-(dbd) n , c-(bdb) _n , c-(bcd) _n , d-(cbcd) _{n ,} dc-(bd) _n , dc-(db) _n , dc-(bd) _n -b, [(dbc) _n ] _m -X, [d-(bc) _n ] _m -X, [(db) _n -c] _m -X , [(dbd) _n -c] _m -X, [(bdb) _n -c] _m -X, [(cbd) _n ] _m -X, [c-(bd) _n ] _m -X, [c- (dbd) _n ] _m -X, [c-(bdb) _n ] _m -X

In addition, in each of the above general formulas, a represents a polymer block (a) mainly composed of a vinyl aromatic compound, and b represents a hydrogenated copolymer block (b) composed of a vinyl aromatic compound and a conjugated diene. , c represents a hydrogenated copolymer block (c) mainly composed of a conjugated diene, and d represents a polymer block (d) mainly composed of a conjugated diene having a vinyl bond content of 25% by mass or less.

n is an integer of 1 or more, preferably an integer of 1-5.

m is an integer of 2 or more, preferably an integer of 2-11.

X represents the residue of a coupling agent or the residue of a polyfunctional initiator.

The structure of the hydrogenated block copolymer (iii) is not particularly limited, and examples thereof include those having a structure represented by the following general formula.

A-(BA) _n , B-(AB) _m , (AB) _n , (AB) _m -X, (BA) _m -X

In addition, in each of the above general formulas, A is a polymer block (A) mainly composed of a vinyl aromatic compound, and B is a hydrogenated polymer block (B) mainly composed of a conjugated diene compound.

n is an integer of 1 or more, preferably an integer of 1-5.

m is an integer of 2 or more, preferably an integer of 2-8.

X represents the residue of a coupling agent or the residue of a polyfunctional initiator.

When multiple blocks (a), block (b), block (c) and block (d) exist in the hydrogenated block copolymer (i), their molecular weight, composition and other structures can be the same , can also be different.

In addition, the boundary of each block does not necessarily need to be clearly distinguished.

The distribution of the vinyl aromatic compound in the hydrogenated block copolymers (i) and (iii) is not particularly limited as long as it satisfies the range of the vinyl aromatic compound content in the present embodiment, and may be uniformly distributed or may be distributed so that Tapered, stepped, convex, concave.

In addition, a plurality of distribution forms of the vinyl aromatic compound may respectively coexist.

In addition, in the hydrogenated block copolymers (i) and (iii), a plurality of segments having different vinyl aromatic compound contents may coexist.

In addition, the distribution of the vinyl bond units in each of the blocks (a) to (d) and (A) and (B) in the hydrogenated block copolymers (i) and (iii) is not particularly limited, and may have distributed. The distribution of vinyl bonds can be controlled by adding a regulator described later during polymerization, or by changing the temperature during polymerization.

In addition, the hydrogenation rate of the conjugated diene monomer units in the hydrogenated block copolymers (i) and (iii) may also have a distribution. The distribution of the hydrogenation rate can be controlled by changing the distribution of vinyl bond units, or after copolymerizing isoprene and butadiene, hydrogenation is carried out using a hydrogenation catalyst described later. The difference between the hydrogenation rate of the hydrogenation unit and the butadiene unit is controlled.

The hydrogenated block copolymer (i) preferably has a polymer block (a) at at least one terminal from the viewpoint of obtaining good heat resistance and mechanical strength in the final target hydrogenated block copolymer composition Structure.

In addition, from the viewpoint of improving the compatibility with the olefin-based resin (ii) described later, and obtaining good transparency and flexibility in the final target hydrogenated block copolymer composition, the hydrogenated block copolymer (i) It is preferably a structure having (c) a hydrogenated polymer block mainly composed of a conjugated diene at at least one terminal.

Specifically, in the above general formula representing the structure of the hydrogenated block copolymer (i), c-(ba) _n , c-(aba) _n , ac-(ba) _n are preferred, and c-(ba) n is more preferred. (ba) _n , c-(aba) _n .

The hydrogenated block copolymer (i) may be any mixture of copolymers having the structure represented by the above general formula.

The hydrogenated block copolymer (iii) preferably has at least two or more polymer blocks (A) from the viewpoint of obtaining good heat resistance and mechanical strength in the final target hydrogenated block copolymer composition One or more structures exist at the terminal.

Specifically, among the above structures, A-(BA) _n and (AB) _n are preferable.

The hydrogenated block copolymer (iii) may be any mixture of copolymers having the structure represented by the above general formula.

In addition, it is preferable that the hydrogenated block copolymer (iii) contains 0.1 to 9.1% by mass of the above-mentioned (B ) a hydrogenated polymer block based on a conjugated diene.

<Other examples of structures of hydrogenated block copolymers (i), (iii)>

The above-mentioned hydrogenated block copolymers (i) and (iii) may be modified block copolymers in which atomic groups having predetermined functional groups are bonded.

In addition, the modified block copolymer may be a secondary modified block copolymer.

<Methods for producing hydrogenated block copolymers (i) and (iii)>

Hydrogenated block copolymers (i) and (iii) are obtained in the state before hydrogenation by, for example, using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent to make vinyl aromatic It can be obtained by living anionic polymerization of group compounds and conjugated diene compounds.

(solvent)

Examples of hydrocarbon solvents include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane, cycloheptane, methylcycloheptane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

(polymerization initiator)

As a polymerization initiator, organic alkali metal compounds such as aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amino alkali metal compounds known to have anionic polymerization activity for vinyl aromatic compounds and conjugated dienes can generally be used.

As the organoalkali metal compound, aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms are preferable, and compounds containing one lithium in one molecule and dilithium containing two or more lithiums in one molecule can be used. compound, trilithium compound, tetralithium compound.

Specifically, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diiso The reaction product of propenylbenzene and sec-butyllithium, the reaction product of divinylbenzene and sec-butyllithium and a small amount of 1,3-butadiene, etc.

In addition, organic alkali metal compounds disclosed in US Patent No. 5,708,092 specification, UK Patent No. 2,241,239 specification, and US Patent No. 5,527,753 specification can also be used.

(regulator)

When a vinyl aromatic compound is copolymerized with a conjugated diene using an organoalkali metal compound as a polymerization initiator, the vinyl bond (1 , 2 or 3,4 bonds) content, or the random copolymerization of vinyl aromatic compounds and conjugated dienes to adjust.

As such a regulator, for example, a tertiary amine compound, an ether compound, or a metal alcoholate compound may be added.

The modifiers may be used alone or in combination of two or more.

As the tertiary amine compound, a compound represented by the general formula R ¹ R ² R ³ N (where R ¹ , R ² , and R ³ represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group) can be used.

Examples include trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethyl ethylenediamine, N, N, N', N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylaminoethylpiperazine, N, N, N', N ", N"-pentamethylethylenetriamine, N, N'-dioctyl-p-phenylenediamine, etc.

As the ether compound, linear ether compounds, cyclic ether compounds, and the like can be utilized.

Examples of linear ether compounds include dialkyl ethers of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Compounds; dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

Examples of cyclic ether compounds include tetrahydrofuran, dioxane, 2,5-dimethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2-bis(2-tetrahydrofuryl)propane , alkyl ethers of furfuryl alcohol, etc.

Examples of the metal alcoholate compound include sodium tert-amylate, sodium tert-butoxide, potassium tert-amyloxide, potassium tert-butoxide, and the like.

(aggregation method)

As a method for polymerizing a vinyl aromatic compound and a conjugated diene polymer using an organic alkali metal compound as a polymerization initiator, conventionally known methods can be utilized.

For example, batch polymerization, continuous polymerization, or any combination thereof may be used. In particular, batch polymerization is preferred because a copolymer excellent in heat resistance can be obtained.

The polymerization temperature is preferably 0°C to 180°C, more preferably 30°C to 150°C. The polymerization time varies depending on conditions, but is usually within 48 hours, preferably 0.1 to 10 hours.

In addition, the atmosphere of the polymerization system is preferably an inert gas atmosphere such as nitrogen.

The polymerization pressure is not particularly limited as long as it is set within the pressure range capable of maintaining the monomer and the solvent in the liquid phase in the above temperature range.

In addition, care must be taken not to mix impurities such as water, oxygen, and carbon dioxide into the polymerization system that would deactivate the catalyst and the active polymer.

In addition, at the end of the above-mentioned polymerization step, a required amount of a bifunctional or higher-functional coupling agent may be added to perform a coupling reaction.

Conventionally known coupling agents can be used as the bifunctional coupling agent, and are not particularly limited.

Examples include trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxy Alkoxysilane compounds such as dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyl dihalogenated compounds such as dibromosilane; acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

In addition, conventionally known coupling agents can be used as the trifunctional or higher multifunctional coupling agent, and are not particularly limited. Examples include polyhydric alcohols of three or more valences; polyhydric alcohols such as epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane, etc. Epoxy compounds; such as methyltrichlorosilane, tert-butyltrichlorosilane, silicon tetrachloride and their bromides, etc., are represented by the general formula R _4-n SiX _n (wherein, R represents carbon atoms with 1 to 20 Hydrocarbyl, X represents a halogen atom, and n represents an integer of 3 to 4) represents a silicon halide compound; polyvalent halides such as methyl tin trichloride, tert-butyl tin trichloride, tin tetrachloride, etc. are represented by the general formula A tin halide compound represented by R _4-n S _n X _n (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents an integer of 3 to 4).

In addition, dimethyl carbonate, diethyl carbonate, or the like can also be used.

(modification process)

As described above, the hydrogenated block copolymers (i) and (iii) may be modified block copolymers incorporating atomic groups having functional groups. The atomic group having a functional group is preferably bonded as a pre-step of the hydrogenation step described later.

The "atomic group having a functional group" includes an atomic group containing at least one functional group selected from the following functional groups: for example, a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a sulfur group, Carboxylic acid group, aldehyde group, thioaldehyde group, carboxylate group, amide group, sulfonic acid group, sulfonate group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group , epoxy group, epithio group, thioether group, isocyanate group, isothiocyanate group, silicon halide group, silanol group, alkoxy silicon group, tin halide group, boric acid group, boron-containing group, boric acid Salt base, alkoxy tin base, phenyl tin base, etc.

In particular, it is preferably an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilyl group.

The "atomic group having a functional group" is bonded via a modifier.

Examples of modifiers include tetraglycidyl m-xylylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4- Methoxybenzophenone, γ-Glycidoxyethyltrimethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-Glycidoxypropyldimethylphenoxy base silane, bis(γ-glycidoxypropyl) methylpropoxysilane, 1,3-dimethyl-2-imidazolinone, 1,3-diethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, N-methylpyrrolidone, etc.

Modified block copolymers are obtained, for example, by anionic living polymerization using a functional group-containing polymerization initiator or a functional group-containing unsaturated monomer; or by addition reaction of a modifier forming or containing a functional group to the living terminal, whereby a modified block copolymer can be obtained.

As another method, by reacting an organoalkali metal compound such as an organolithium compound with a block copolymer (metallation reaction), and adding a functional group-containing modifier to the block polymer to which an organoalkali metal is added , thus obtaining a modified block copolymer.

However, in the case of the latter method, a modified hydrogenated block copolymer can also be produced by performing a metallation reaction after obtaining the hydrogenated block copolymers (i) and (iii), and then reacting a modifier.

The temperature for performing the modification reaction is preferably 0 to 150°C, more preferably 20 to 120°C. The time required for the modification reaction varies depending on other conditions, but is preferably within 24 hours, more preferably 0.1 to 10 hours.

Depending on the type of modifying agent used, when the modifying agent is reacted, the amino group or the like may usually become an organometallic salt, but in this case, it is treated with a compound containing active hydrogen such as water or alcohol , can be transformed into amino groups, etc. In addition, in such a modified copolymer, a part of unmodified copolymer may be mixed in the modified copolymer.

In addition, the above-mentioned modified block copolymer may be a secondary modified block copolymer.

The secondary modified block copolymer is obtained by reacting a secondary modifier reactive to the functional groups of the modified block copolymer with the modified block copolymer.

As the secondary modifying agent, a modifying agent containing a functional group selected from, for example, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilyl group can be enumerated. A secondary modifier of functional groups among these functional groups.

However, when the functional group is an acid anhydride group, it may be a secondary modifier having one acid anhydride group.

As described above, when the secondary modifier is reacted with the modified block copolymer, the amount of the secondary modifier is preferably 0.3 to 10 per equivalent of functional groups bonded to the modified block copolymer. mol, more preferably 0.4 to 5 mol, still more preferably 0.5 to 4 mol.

A known method can be used for the method of reacting the modified block copolymer with the secondary modifier, and it is not particularly limited. Examples thereof include a melt-kneading method described later, a method of dissolving or dispersing and mixing each component in a solvent or the like, and reacting them. In addition, these secondary modifications are preferably performed after the hydrogenation step.

As the secondary modifier, specifically, maleic anhydride, pyromellitic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluene diisocyanate, tetraglycidyl-1, 3-bisaminomethylcyclohexane, bis-(3-triethoxysilylpropyl)-tetrasulfide, and the like.

In addition, the hydrogenated block copolymers (i) and (iii) can be modified by grafting α, β-unsaturated carboxylic acid or its derivatives such as its anhydride, esterified product, amidated product, imidated product to form a modified permanent block copolymers.

As α, the specific example of β-unsaturated carboxylic acid or derivative thereof, can enumerate maleic anhydride, maleic anhydride imide, acrylic acid or its ester, methacrylic acid or its ester, bridge-cis-bicyclo[ 2.2.1] -5-heptene-2,3-dicarboxylic acid or its anhydride, etc.

The added amount of the α,β-unsaturated carboxylic acid or its derivative is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the hydrogenated block copolymers (i) and (iii).

The reaction temperature in the case of performing graft modification is preferably 100 to 300°C, more preferably 120 to 280°C.

As a specific method of graft modification, for example, the method described in JP-A-62-79211 can be utilized.

(Hydrogenation reaction process)

The hydrogenated block copolymers (i) and (iii) are obtained by subjecting the above-mentioned non-hydrogenated non-modified or modified block copolymers to a hydrogenation reaction using a predetermined hydrogenation catalyst.

The hydrogenation catalyst is not particularly limited, and known catalysts can be used, that is, (1) Supported heterogeneous hydrogenation in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc. Catalysts; (2) So-called Ziegler-type hydrogenation catalysts using organic acid salts of Ni, Co, Fe, Cr, etc., transition metal salts such as acetylacetonate, and reducing agents such as organoaluminum; (3) Ti, Ru, Rh Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as , Zr, etc.

Specifically, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, and Japanese Patent Publication No. 1-53851 can be used. . The hydrogenation catalyst described in Japanese Patent Application Publication No. 2-9041.

As a preferable hydrogenation catalyst, a titanocene compound, a reducing organometallic compound, or a mixture thereof is mentioned.

As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specifically, dicyclopentadiene titanium dichloride, monopentamethylcyclopentadiene titanium trichloride, etc. have at least one (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fluorene Compounds with ligands based on the skeleton.

Examples of the reducing organometallic compound include organoalkali metal compounds such as organolithium compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The hydrogenation reaction will be described.

The reaction temperature is usually in the range of 0 to 200°C, preferably in the range of 30 to 150°C.

The pressure of hydrogen used in the hydrogenation reaction is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, more preferably 0.3 to 5 MPa.

The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours.

The hydrogenation reaction can use any one of a batch process, a continuous process or a combination thereof.

The catalyst residue is removed from the solution of the hydrogenated block copolymer obtained through the hydrogenation reaction as necessary, and the hydrogenated block copolymer is separated from the solution.

As the separation method, for example, the method of adding a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated modified copolymer, to the reaction liquid after hydrogenation to precipitate and recover the polymer; A method in which the reaction liquid is put into the reaction solution, and the solvent is removed by stripping to recover; a method in which the polymer solution is directly heated and the solvent is distilled off, etc.

In addition, stabilizers such as various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers may be added to the hydrogenated block copolymers (i) and (iii).

<(ii) Olefin-based resin>

The olefin-based resin (ii) constituting the hydrogenated block copolymer composition in this embodiment will be described.

Examples of the olefin-based resin (ii) include polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4 - Homopolymers of α-olefins such as methyl-1-pentene and 1-octene.

In addition, a random copolymer or a block copolymer composed of a combination of olefins selected from ethylene, propylene, butene, pentene, hexene, octene and the like can be mentioned.

Examples include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1 -hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer , propylene-4-methyl-1-pentene copolymer, ethylene-propylene-1-butene copolymer, propylene-1-hexene-ethylene copolymer, propylene-1-octene-ethylene copolymer and other ethylene and /or propylene-α-olefin copolymers.

In addition, copolymers of ethylene and/or propylene include copolymers with other unsaturated monomers shown below.

Examples include ethylene and/or propylene with acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic anhydride, aryl maleimide, alkyl maleic acid, Copolymers of unsaturated organic acids such as imide or derivatives thereof; copolymers of ethylene and/or propylene with vinyl esters such as vinyl acetate; and copolymers of ethylene and/or propylene with dicyclopentadiene, Copolymers of non-conjugated dienes such as 4-ethylidene-2-norbornene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene.

(ii) The olefin-based resin preferably contains at least one kind of polypropylene-based resin.

In addition, the olefin-based resin (ii) may be modified with a predetermined functional group.

As a functional group, an epoxy group, a carboxyl group, an acid anhydride, a hydroxyl group etc. are mentioned, for example.

Examples of the compound or modifier having a functional group for modifying the olefin resin (ii) include the following compounds.

Examples include unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether; maleic acid, fumaric acid, itaconic acid, and citraconic acid , Allyl succinic acid, maleic anhydride, fumaric anhydride, itaconic anhydride and other unsaturated organic acids.

In addition, ionomers, chlorinated polyolefins, etc. are mentioned.

The olefin-based resin (ii) is preferably a polypropylene homopolymer, an ethylene polymer, or an - Polypropylene-based resins such as propylene random or block copolymers.

In particular, an ethylene-propylene random copolymer is more preferable from the viewpoint of transparency and flexibility.

The olefin-based resin (ii) may be composed of a single material, or two or more materials may be used in combination.

[Hydrogenated block copolymer composition]

As described above, the hydrogenated block copolymer composition in the present embodiment includes a hydrogenated block copolymer composition containing the hydrogenated block copolymer (i) and at least one type of olefin as the first embodiment The resin (ii) contains, as a second embodiment, the hydrogenated block copolymer (i), at least one olefin-based resin (ii), and the hydrogenated block copolymer (iii).

In the hydrogenated block copolymer composition of the first embodiment, the content of the hydrogenated block copolymer (i) is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, still more preferably 15% by mass to 85% 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 deteriorate. On the other hand, if it exceeds 95% by mass, the strength and heat resistance of the hydrogenated block copolymer composition tend to deteriorate.

In the hydrogenated block copolymer composition of the second embodiment, the contents of the hydrogenated block copolymers (i) and (iii) are preferably 2.5% by mass to 92.5% by mass, more preferably 5% by mass to 85% by mass %, more preferably 7.5% by mass to 77.5% by mass.

When the contents of the hydrogenated block copolymers (i) and (iii) are each less than 2.5% by mass, the flexibility of the hydrogenated block copolymer composition tends to deteriorate.

On the other hand, if it exceeds 92.5% by 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 resin (ii) described above, the hydrogenated block copolymer composition in this embodiment may be mixed with, for example, any rubber softener, modified agents, additives, etc.

The softener for rubber can soften the target hydrogenated block copolymer composition and impart fluidity (moldability). As the softening agent for rubber, for example, mineral oil, liquid or low molecular weight synthetic softening agent can be utilized, especially, preferably naphthene-based and/or paraffin-based process oil or extender oil .

Mineral oil-based rubber softeners are mixtures of aromatic rings, naphthenic rings, and paraffin chains. Those whose carbon atoms in the paraffin chain account for more than 50% of the total carbon atoms are called paraffin systems. A substance having 30 to 45% of ring carbon atoms is called a naphthene system, and a substance having an aromatic carbon number of more than 30% is called an aromatic system.

As the synthetic softener, polybutene, low-molecular-weight polybutadiene, liquid paraffin, etc. can be used, and the above-mentioned softener for mineral oil-based rubber is more preferable.

When high heat resistance and mechanical properties are required for the target hydrogenated block copolymer composition, the kinematic viscosity at 40° C. of the mineral oil-based rubber softener to be used is preferably 60 cst or more, preferably 120 cst or more. The rubber softeners may be used alone or in combination of two or more.

The modifier has a function of improving the scratch resistance of the surface of the target hydrogenated block copolymer composition or improving the adhesion. As the modifying agent, organopolysiloxane can be utilized. The organopolysiloxane exhibits the surface modification effect of the hydrogenated block copolymer composition and also functions as a wear resistance improving auxiliary agent.

The form of the modifier may be any of a low-viscosity liquid to a high-viscosity liquid or a solid, but from the viewpoint of ensuring good dispersibility in the hydrogenated block copolymer composition, suitable It is a liquid, that is, silicone oil. In addition, the kinematic viscosity is preferably 90 cst or more, more preferably 1000 cst or more, from the viewpoint of suppressing exudation of polysiloxane itself. Specific examples of polysiloxane include general-purpose silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane, or alkyl-modified, polyether-modified, fluorine-modified, and alcohol-modified silicone oils. , Amino modified, epoxy modified and other modified silicone oils. Although not particularly limited, dimethyl polysiloxane is suitable because it has a high effect as a wear resistance improving auxiliary agent. These organopolysiloxanes may be used alone or in combination of two or more.

As additives, as long as they are fillers, lubricants, mold release agents, plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, reinforcing agents, colorants, thermoplastic resins , or additives generally used for mixing rubbery polymers are not particularly limited.

Examples of fillers include silica, talc, mica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate and other inorganic fillers; carbon black and other organic fillers.

Examples of lubricants include stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide and the like.

As a plasticizer, organopolysiloxane, mineral oil, etc. are mentioned.

As an antioxidant, hindered phenolic antioxidant is mentioned.

Examples of the thermal stabilizer include phosphorus-based, sulfur-based, and amine-based thermal stabilizers.

As a light stabilizer, a hindered amine light stabilizer is mentioned.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.

Examples of the reinforcing agent include organic fibers, glass fibers, carbon fibers, metal whiskers, and the like.

Titanium oxide, iron oxide, carbon black, etc. are mentioned as a coloring agent.

Other examples include additives described in "Gom Plastic Compounded Drugs (Rubber-Plastic Compounded Drugs)" (edited by Laber Digiest Co., Ltd. (Rubber Digest)).

The hydrogenated block copolymer composition in the present embodiment can be produced by a conventionally known method.

For example, the following method can be used: each component ( A method of melt-kneading the above-mentioned hydrogenated block copolymers (i) and (iii), polyolefin resin (ii) and other additives); a method of removing the solvent by heating after dissolving or dispersing mixing each component; and the like. In particular, a melt-kneading method using an extruder is suitable from the viewpoint of productivity and good kneading properties.

The shape of the hydrogenated block copolymer composition is not particularly limited, and it can be in any shape such as a granular shape, a sheet shape, a linear shape, or a chip shape. In addition, molded articles may be produced directly after melt-kneading.

[Molded article using hydrogenated block copolymer composition]

The above-mentioned hydrogenated block copolymer composition can be processed by, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding (sand ittsu molding), hollow molding, extrusion molding, vacuum molding, rotational molding, powder slush molding (powder molding) (Sratsush molding), foam molding, lamination molding, calender molding, blow molding, etc. can be processed into molded articles useful for practical use.

For example, it can be made into thin plates, films, injection molded products of various shapes, hollow molded products, pressure molded products, vacuum molded products, extrusion molded products, foam molded products, nonwoven fabrics or fibrous molded products, Various molded products such as synthetic leather.

These molded products can be used, for example, in automotive parts, food packaging materials, medical devices, home appliance components, electronic device components, building materials, industrial parts, household goods, toy materials, shoe materials, fiber materials, and the like.

Specific examples of automotive parts include side moldings, grommets, knobs, weather strips, window frames and their sealing materials, armrests, assistant handles, door handles, handles, operation boxes, head Pillows, dashboards, bumpers, spoilers, storage covers for airbag devices, etc.

Examples of medical equipment include medical tubes, medical hoses, catheters, blood bags, transfusion bags, platelet storage bags, artificial dialysis bags, and the like.

As a building material, a wall material, a floor material, etc. are mentioned.

Other examples include industrial hoses, food hoses, vacuum cleaner hoses, electric cooling seals, electric wires, various other covering materials, covering materials for handles, soft dolls, and the like.

Processes such as foaming, powdering, stretching, bonding, printing, coating, and plating may also be appropriately performed on the above-mentioned molded article.

The hydrogenated block copolymer composition in this embodiment exhibits excellent effects in terms of flexibility, low resilience, transparency, and bending resistance, and therefore is extremely useful as a hollow composition such as a hose or a tube.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to a following example.

<Identification method of polymer structure and measurement method of physical properties>

(1) Styrene content of hydrogenated block copolymers (i) and (iii)

Using the block copolymer before hydrogenation, it measured with the ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450).

(2) Polystyrene block content of hydrogenated block copolymers (i) and (iii)

Using the block copolymer before hydrogenation, it was measured according to the osmium tetroxide method described in I.M.Kolthoff, et al., J.Polym.Sci.1, 429 (1946).

A 0.1 g/125 ml tert-butanol solution of osmic acid was used for the decomposition of the block copolymer.

(3) Vinyl bond amount of hydrogenated block copolymers (i) and (iii)

Using the block copolymer before hydrogenation, it measured with the infrared spectrophotometer (manufactured by JASCO Corporation, FT/IR-230). The amount of vinyl bonds in the copolymer was calculated by the Hampton method.

(4) Molecular weight and molecular weight distribution of hydrogenated block copolymers (i) and (iii)

Measurement was performed by GPC [device: LC-10 (manufactured by Shimadzu Corporation), column: TSKgel GMHXL (4.6 mm×30 cm)].

As a solvent, tetrahydrofuran was used. It carried out under the measurement conditions of temperature 35 degreeC.

The molecular weight is the weight average molecular weight obtained by measuring a commercially available standard polystyrene to obtain a calibration curve (prepared using the peak molecular weight of standard polystyrene), and using this calibration curve to obtain the molecular weight at the peak of the chromatogram.

In addition, the molecular weight when there are a plurality of peaks in the chromatogram is the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in the chromatogram).

In addition, the molecular weight distribution is the ratio (Mw/Mn) of the obtained weight average molecular weight (Mw) and the number average molecular weight (Mn).

(5) Hydrogenation rate of double bonds of conjugated diene monomer units of hydrogenated block copolymers (i) and (iii)

Using the hydrogenated modified copolymer, the measurement was performed with a nuclear magnetic resonance apparatus (manufactured by BRUKER, DPX-400).

(6) tanδ peak temperature

First, a sample is cut into a size of 12.5 mm in width and 40 mm in length, and this is used as a sample for measurement.

Next, this measurement sample was set in the twisted layout (Geometri-1) of the device ARES (manufactured by TA Instruments. Co., Ltd., trade name), and the effective measurement length was 25 mm, the strain was 0.5%, the frequency was 1 Hz, and the heating rate was 3 ° C / Find out under the condition of minutes.

The tan δ peak temperature is a value obtained from the peak detected by the automatic measurement of RSI Orchestrator (manufactured by TA Instruments Co., Ltd., trade name).

(7) Hardness

According to JIS K6253, the value after 10 seconds is measured with a type A hardness tester.

In addition, (-) in the column of the hardness in following Table 5 and Table 6 means no unit.

The hardness value is preferably 96 or less.

(8) Tensile strength (Tb), elongation at break (Eb)

According to JIS K6251, it is measured under the conditions of a No. 3 dumbbell shape and a crosshead speed of 500mm/min.

The tensile strength is expected to be 90 kg/cm ² or more in practical applications.

The elongation at break is expected to be 500% or more in practical use.

(9) Pendulum (Tripso) type resilience

Measured at 23°C according to JIS K6255.

Resilience is expected to be less than 30%.

(10) Bending resistance

Using a tubular molded body with an inner diameter of 4 mm and an outer diameter of 6 mm, the stress at the time of pipe bending was measured with a tensile compression tester, and the stress curve is shown in the figure.

Specifically, a tube with a length of 30 cm was set between chucks (chayers) for 10 cm, and the bending measurement was performed at a crosshead speed of 400 mm/min.

The stress curves are shown in Fig. 1.

<Judgement of bending ease>

1 in Fig. 1 is the moment when the pipe is bent. The slower the portion of 1, the better the bending relaxation property.

As a judging method, first, tangent lines A and B are drawn on the straight line portions before and after the moment 1 of bending on the stress curve.

The greater the difference between the positions of the tangents A and B away from the stress curve, the better the bending relaxation, which is recorded as the distance between the tangents A-B, and calculated and judged by the following formula.

(The moving distance between the chucks when the tangent B leaves the stress curve)-(The moving distance between the chucks when the tangent A leaves the stress curve)=A-B Distance between the tangents

The distance between A-B tangents is more than 7mm:◎

The distance between A-B tangents is less than 7mm and more than 5mm: ○

The distance between A-B tangents is less than 5mm: ×

<Bending distance judgment>

2 in Fig. 1 at which the stress reaches the maximum is taken as the distance between the chucks at the moment of bending the pipe. The longer the moving distance between the chucks is, the better the bending distance is. There are 3 stages of ◎, ○, and × from good to bad. judge.

The bending position is above 60mm:◎

The bending position is above 50mm: ○

The bending position is less than 50mm: ×

<Comprehensive judgment of bending resistance>

Both the judgment of bending ease and the judgment of bending distance are ◎:◎

In the judgment of bending ease and the judgment of bending distance, either ○ or ◎:◎

Both the judgment of bending relaxation and the judgment of bending distance are ○:○

Any one of the judgment of bending ease and the judgment of bending distance is ×: ×

(11) Haze value (turbidity), transparency judgment

Using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., NDH-1001DP), the haze value (turbidity) of a thin plate-shaped molded article with a thickness of 2 mm in liquid paraffin was measured. ◎, ○, and × are judged in three stages.

Haze value less than 30%: transparency◎

Haze value of 30% or more and less than 50%: Transparency ○

Haze value above 50%: Transparency ×

<Preparation of hydrogenation catalyst>

In Examples and Comparative Examples to be described later, hydrogenation catalysts used for production of hydrogenated block copolymers were prepared by the following method.

The reaction vessel equipped with a stirring device was replaced with nitrogen in advance, and 1 liter of dried and purified cyclohexane was charged thereinto.

Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added.

While fully stirring this, a n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was reacted at room temperature for about 3 days. A hydrogenation catalyst is thus obtained.

<Hydrogenated block copolymer>

The hydrogenated block copolymers (i)-1 to (i)-7 and (iii)-1 to (iii)-3 constituting the hydrogenated block copolymer composition were prepared as follows.

(Hydrogenated block copolymer (i)-1)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 9 parts by mass of styrene was charged.

Next, 0.084 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, and 1.8 moles of N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as is "TMEDA."), and 0.08 mol of sodium tert-amylate was further added to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes.

Next, a cyclohexane solution containing 25 parts by mass of styrene and a cyclohexane solution containing 21 parts by mass of butadiene (concentration: 20% by mass) were added, and polymerized at 70° C. for 45 minutes.

Next, a cyclohexane solution containing 45 parts by mass of butadiene was charged, and polymerized at 60° C. for 1 hour. Then, methanol was added to stop the polymerization reaction.

In the block copolymer obtained as described above, the styrene content was 34% by mass, the polystyrene block content was 9% by mass, and the vinyl bond amount was 66% by mass (the vinyl group of the conjugated diene polymer block The bond amount is 77% by mass), the weight average molecular weight is 148,000, and the molecular weight distribution is 1.02.

In addition, the hydrogenation catalyst prepared above was added to the obtained block copolymer at 100 ppm based on Ti with respect to 100 parts by mass of the block copolymer, and hydrogenation was carried out under the conditions of a hydrogen pressure of 0.7 MPa and a temperature of 65°C. reaction.

Next, as a stabilizer, 0.3 parts by mass of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added to 100 parts by mass of the copolymer to obtain a hydrogenated block Copolymer (i)-1.

The hydrogenation rate of the obtained hydrogenated block copolymer was 98%.

(Hydrogenated block copolymer (i)-2)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 7 parts by mass of styrene was charged.

Next, 0.089 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, 1.8 moles of TMEDA was added to 1 mole of n-butyllithium, and 0.08 moles of sodium tert-amyloxide was added to 1 mole of n-butyllithium, Polymerization was carried out at 70°C for 20 minutes.

Next, a cyclohexane solution (concentration: 20% by mass) containing 57 parts by mass of butadiene was added and polymerized at 60°C for 1 hour.

Next, a cyclohexane solution containing 18 parts by mass of styrene and a cyclohexane solution containing 14 parts by mass of butadiene (concentration: 20% by mass) were added, and polymerized at 70° C. for 45 minutes.

Next, a cyclohexane solution containing 4 parts by mass of styrene was charged and polymerized at 70° C. for 20 minutes. Methanol was then added to stop the polymerization.

In the block copolymer obtained as described above, the styrene content was 29% by mass, the polystyrene block content was 11% by mass, and the vinyl bond content was 70% by mass (the vinyl group of the conjugated diene polymer block The bond amount was 77% by mass), the weight average molecular weight was 137,000, and the molecular weight distribution was 1.03.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (i)-2.

The hydrogenation rate of the obtained hydrogenated block copolymer was 98%.

(Hydrogenated block copolymer (i)-3)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 35 parts by mass of butadiene was charged.

Next, 0.071 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, 1.8 moles of TMEDA was added to 1 mole of n-butyllithium, and 0.08 moles of sodium tert-amyloxide was added to 1 mole of n-butyllithium, Polymerization was carried out at 60°C for 1 hour.

Next, a cyclohexane solution (concentration: 20% by mass) containing 11 parts by mass of styrene was added and polymerized at 70°C for 20 minutes.

Next, a cyclohexane solution containing 24 parts by mass of styrene and a cyclohexane solution containing 21 parts by mass of butadiene (concentration: 20% by mass) were added, and polymerized at 70° C. for 45 minutes.

Next, a cyclohexane solution containing 9 parts by mass of styrene was charged and polymerized at 70° C. for 20 minutes. Methanol was then added to stop the polymerization.

In the block copolymer obtained as described above, the styrene content was 44% by mass, the polystyrene block content was 20% by mass, and the vinyl bond content was 60% by mass (the vinyl group in the conjugated diene polymer block The bond amount is 75% by mass), the weight average molecular weight is 184,000, and the molecular weight distribution is 1.05.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (i)-3.

The hydrogenation rate of the obtained hydrogenated block copolymer was 99%.

(Hydrogenated block copolymer (i)-4)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 9 parts by mass of styrene was charged.

Next, 0.078 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, 1.8 moles of TMEDA was added to 1 mole of n-butyllithium, and 0.08 moles of sodium tert-amyloxide was added to 1 mole of n-butyllithium, Polymerization was carried out at 70°C for 20 minutes.

Next, a cyclohexane solution containing 27 parts by mass of styrene and a cyclohexane solution containing 19 parts by mass of butadiene (concentration: 20% by mass) were added, and polymerized at 70° C. for 45 minutes.

Next, a cyclohexane solution containing 45 parts by mass of butadiene was charged, and polymerized at 60° C. for 1 hour.

Next, 0.1 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Methanol was then added to stop the polymerization.

In the block copolymer obtained as described above, the styrene content was 36% by mass, the polystyrene block content was 9% by mass, and the vinyl bond amount was 63% by mass (the vinyl group of the conjugated diene polymer block The bond amount was 73% by mass), the weight average molecular weight was 163,000, and the molecular weight distribution was 1.20. In addition, the coupling ratio obtained from the peak area ratio of the GPC curve was 25%.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (i)-4.

The hydrogenation rate of the obtained hydrogenated block copolymer was 98%.

(Hydrogenated block copolymer (i)-5)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 9 parts by mass of butadiene was charged.

Next, 0.079 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, and 0.05 mol of TMEDA was added to 1 mol of n-butyllithium, followed by polymerization at 70° C. for 20 minutes.

Next, 1.75 moles of TMEDA was added to 1 mole of n-butyllithium, and 0.08 moles of sodium tert-amyloxide was added to 1 mole of n-butyllithium, and a cyclohexane solution containing 27 parts by mass of styrene and 19 parts by mass of butane were added. A cyclohexane solution of diene (concentration: 20% by mass) was polymerized at 70° C. for 45 minutes.

Next, a cyclohexane solution containing 45 parts by mass of butadiene was charged, and polymerized at 60° C. for 1 hour. Then, methanol was added to stop the polymerization reaction.

In the block copolymer obtained as described above, the styrene content was 27% by mass, and the amount of vinyl bonds was 61% by mass (the amount of vinyl bonds in the conjugated diene polymer block (c) was 76% by mass, total The conjugated diene polymer block (d) had a vinyl bond content of 18% by mass), a weight average molecular weight of 203,000, and a molecular weight distribution of 1.05.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (i)-5.

The hydrogenation rate of the obtained hydrogenated block copolymer was 98%.

(Hydrogenated block copolymer (i)-6)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 9 parts by mass of styrene was charged.

Next, 0.079 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, and 0.3 mol of TMEDA was added to 1 mol of n-butyllithium, followed by polymerization at 70° C. for 20 minutes.

Next, a cyclohexane solution containing 38 parts by mass of styrene and a cyclohexane solution containing 49 parts by mass of butadiene (concentration: 20% by mass) were added, and polymerized at 70° C. for 1 hour.

Next, a cyclohexane solution containing 4 parts by mass of styrene was charged and polymerized at 70° C. for 20 minutes. Next, methanol was added to stop the polymerization reaction.

In the block copolymer obtained as described above, the styrene content was 51% by mass, the polystyrene block content was 13% by mass, the amount of vinyl bonds was 21% by mass, the weight average molecular weight was 159,000, and the molecular weight distribution was 1.09 .

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (i)-6.

The hydrogenation rate of the obtained hydrogenated block copolymer was 98%.

(Hydrogenated block copolymer (i)-7)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 22 parts by mass of styrene was charged.

Next, 0.124 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, 1.8 moles of TMEDA was added to 1 mole of n-butyllithium, and 0.08 moles of sodium tert-amyloxide was added to 1 mole of n-butyllithium, Polymerization was carried out at 70°C for 30 minutes.

Next, a cyclohexane solution (concentration: 20% by mass) containing 57 parts by mass of butadiene was added and polymerized at 60°C for 1 hour.

Next, a cyclohexane solution containing 21 parts by mass of styrene was charged and polymerized at 70° C. for 30 minutes. Next, methanol was added to stop the polymerization reaction.

In the block copolymer obtained as described above, the styrene content was 43% by mass, the amount of vinyl bonds in the butadiene portion was 76% by mass, the weight average molecular weight was 91,000, and the molecular weight distribution was 1.07.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (i)-7.

The hydrogenation rate of the obtained hydrogenated block copolymer was 99%.

(Hydrogenated block copolymer (i)-8)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 5 parts by mass of styrene was charged.

Next, 0.067 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, 1.8 moles of TMEDA was added to 1 mole of n-butyllithium, and 0.08 moles of sodium tert-amyloxide was added to 1 mole of n-butyllithium, Polymerization was carried out at 70°C for 20 minutes.

Next, a cyclohexane solution containing 20 parts by mass of styrene and a cyclohexane solution containing 65 parts by mass of butadiene (concentration: 20% by mass) were added, and polymerized at 70° C. for 1 hour.

Next, a cyclohexane solution containing 5 parts by mass of styrene was charged and polymerized at 70° C. for 20 minutes.

Next, a cyclohexane solution containing 5 parts by mass of butadiene was added and polymerized at 70° C. for 20 minutes. Next, methanol was added to stop the polymerization reaction.

In the block copolymer obtained as described above, the styrene content was 30% by mass, the amount of vinyl bonds in the butadiene portion was 65% by mass, the weight average molecular weight was 201,000, and the molecular weight distribution was 1.06.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (i)-8.

The hydrogenation rate of the obtained hydrogenated block copolymer was 98%.

(hydrogenated block copolymer (iii)-1)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by mass) containing 7 parts by mass of styrene was charged.

Next, 0.082 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, 1.8 moles of TMEDA was added to 1 mole of n-butyllithium, and 0.08 moles of sodium tert-amyloxide was added to 1 mole of n-butyllithium, Polymerization was carried out at 70°C for 20 minutes.

Next, a cyclohexane solution (concentration: 20% by mass) containing 87 parts by mass of butadiene was added and polymerized at 60°C for 1.5 hours.

Next, a cyclohexane solution containing 6 parts by mass of styrene was charged and polymerized at 70° C. for 20 minutes. Next, methanol was added to stop the polymerization reaction.

In the block copolymer obtained as described above, the styrene content was 13% by mass, the amount of vinyl bonds in the butadiene portion was 78% by mass, the weight average molecular weight was 151,000, and the molecular weight distribution was 1.06.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Method A stabilizer was added to obtain a hydrogenated block copolymer (iii)-1.

The hydrogenation rate of the obtained hydrogenated block copolymer was 99%.

(hydrogenated block copolymer (iii)-2)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by weight) containing 9 parts by mass of styrene was charged. Next, 0.078 parts by mass of n-butyllithium was added to 100 parts by mass of all the monomers, and 0.5 mol of TMEDA was added to 1 mol of n-butyllithium, followed by polymerization at 70° C. for 20 minutes.

Next, a cyclohexane solution (concentration: 20% by weight) containing 82 parts by weight of butadiene was added and polymerized at 70°C for 1 hour.

Next, a cyclohexane solution (concentration: 20% by weight) containing 9 parts by weight of styrene was charged, and polymerized at 70° C. for 20 minutes.

In the block copolymer obtained as described above, the styrene content was 18% by weight, the amount of vinyl bonds in the butadiene portion was 51% by weight, the weight average molecular weight was 106,000, and the molecular weight distribution was 1.04.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (iii)-2.

The hydrogenation rate of the obtained hydrogenated block copolymer was 99%.

(hydrogenated block copolymer (iii)-3)

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration: 20% by weight) containing 16 parts by mass of styrene was charged. Next, 0.095 parts by mass of n-butyllithium was added to 100 parts by mass of all monomers, and 0.3 mol of TMEDA was added to 1 mol of n-butyllithium, followed by polymerization at 70° C. for 30 minutes.

Next, a cyclohexane solution (concentration: 20% by weight) containing 68 parts by weight of butadiene was added and polymerized at 70°C for 50 minutes. Finally, a cyclohexane solution (concentration: 20% by weight) containing 16 parts by weight of styrene was charged, and polymerized at 70° C. for 30 minutes.

In the block copolymer obtained as described above, the styrene content was 32% by weight, the amount of vinyl bonds in the butadiene portion was 37% by weight, the weight average molecular weight was 83,000, and the molecular weight distribution was 1.05.

Furthermore, the obtained block copolymer was hydrogenated by the same method as the above (hydrogenated block copolymer (i)-1), and the same method as the above (hydrogenated block copolymer (i)-1) was used. Methods A stabilizer was added to obtain a hydrogenated block copolymer (iii)-3.

The hydrogenation rate of the obtained hydrogenated block copolymer was 99%.

<Olefin resin (ii)>

As the olefin-based resin (ii), PC630A (manufactured by PP/SunAllomer Ltd.; random copolymer, MFR=7.5) was used.

[Manufacturing examples 1 to 5]

For hydrogenated block copolymers (i)-1, (i)-2, (i)-3, (i)-4, (i)-5 made as described above, use 4 inch rolls separately at 200 Roll pressing at 200° C., followed by press molding with a press at 200° C. and 100 kg/cm ² , to produce molded sheets with a thickness of 2 mm.

[Manufacturing Examples 6-8]

For the hydrogenated block copolymers (i)-6, (i)-7, and (i)-8 produced as described above, they were rolled separately using 4-inch rolls at 200° C., and then pressed at 200° C. ℃, 100kg/cm ² conditions for press molding, to produce 2mm thick molded sheet.

Hydrogenated block copolymers (i)-1 to (i)-5 of the above-mentioned [Production Examples 1 to 5] and hydrogenated block copolymers (i)-6 to (i) of [Production Examples 6 to 8] )-8, the numerical values of the following items are shown in the following Tables 1 to 3.

・Content of all vinyl aromatic compounds (mass%)

・(a) Content (mass %) of polymer block mainly composed of vinyl aromatic compound

・(b) Content (mass%) of hydrogenated copolymer block composed of vinyl aromatic compound and conjugated diene

・(c) Content (mass%) of hydrogenated polymer block mainly composed of conjugated diene

・The content (mass %) of the vinyl aromatic compound in the (b) hydrogenated copolymer block

・The amount of vinyl bonds in the (c) hydrogenated copolymer block (mass %)

· Weight average molecular weight (10,000)

・Hydrogenation rate (%) of the double bond of the conjugated diene monomer unit

In addition, in the following Tables 1 to 3, tan δ ( Loss tangent) peak temperature in the temperature range of less than 0°C and 0-60°C.

In addition, in the following Tables 1 to 3, the polymer blocks (a) to (c) represent the following polymer blocks, respectively.

Polymer block (a): polymer block mainly composed of vinyl aromatic compound

Polymer block (b): Hydrogenated copolymer block composed of vinyl aromatic compound and conjugated diene

Polymer block (c): Hydrogenated polymer block mainly composed of conjugated diene

[Table 1]

[Table 2]

[table 3]

In the following Table 4, numerical values of the following items which are the structures of the hydrogenated block copolymers (iii)-1 to (iii)-3 of [Manufacture Examples 9 to 11] are shown.

・Content of all vinyl aromatic compounds (mass%)

・The amount of vinyl bonds in the hydrogenated polymer block (B) mainly composed of conjugated diene (mass %)

· Weight average molecular weight (10,000)

・Hydrogenation rate (%) of the double bond of the conjugated diene monomer unit

In addition, in Table 4 below, the polymer block (B) represents a hydrogenated polymer block (B) mainly composed of a conjugated diene.

[Table 4]

[Examples 1 and 2]

Mix the powdered hydrogenated block copolymer (i)-1 and olefin-based resin (ii) at the ratio shown in Table 5 below, roll-press with a 4-inch roll at 170°C, and then use a press to Press molding was carried out under the conditions of 200°C and 100kg/cm ² to produce a molded sheet with a thickness of 2mm.

In addition, the hydrogenated block copolymer (i)-1 and olefin-based resin (ii) were mixed at the ratio shown in the following Table 5, and extruded at 230° C. using a 20 mmφ twin-screw extruder to produce A tubular molded body with a diameter of 6mm.

[Example 3 and 4]

Mix the powdered hydrogenated block copolymer (i)-2 and olefin-based resin (ii) at the ratio shown in Table 5 below, roll-press with a 4-inch roll at 170°C, and then use a press to Press molding was carried out under the conditions of 200°C and 100kg/cm ² to produce a molded sheet with a thickness of 2mm.

In addition, the hydrogenated block copolymer (i)-2 and the olefin-based resin (ii) were mixed at the ratio shown in the following Table 5, and extruded at 230° C. using a 20 mmφ twin-screw extruder to produce an inner diameter of 4 mm. A tubular molded body with a diameter of 6mm.

[Examples 5 and 6]

Mix the powdered hydrogenated block copolymer (i)-3 and olefin-based resin (ii) at the ratio shown in Table 5 below, roll-press with a 4-inch roll at 170°C, and then use a press to Press molding was carried out under the conditions of 200°C and 100kg/cm ² to produce a molded sheet with a thickness of 2mm.

In addition, the hydrogenated block copolymer (i)-3 and olefin-based resin (ii) were mixed at the ratio shown in the following Table 5, and extruded at 230° C. using a 20 mmφ twin-screw extruder to produce A tubular molded body with a diameter of 6 mm.

[Examples 7 and 8]

Mix the powdered hydrogenated block copolymer (i)-4 and olefin-based resin (ii) at the ratio shown in Table 5 below, roll-press at 170°C with a 4-inch roll, and then use a press to Press molding was carried out under the conditions of 200°C and 100kg/cm ² to produce a molded sheet with a thickness of 2mm.

In addition, the hydrogenated block copolymer (i)-4 and olefin-based resin (ii) were mixed in the ratio shown in the following Table 5, and extruded at 230° C. using a 20 mmφ twin-screw extruder to produce A tubular molded body with a diameter of 6 mm.

[Examples 9 and 10]

The powdered hydrogenated block copolymer (i)-5 and olefin resin (ii) were mixed in the ratio shown in Table 5 below, rolled with a 4-inch roll at 170°C, and then pressed with a press to Press molding was carried out under the conditions of 200°C and 100kg/cm ² to produce a molded sheet with a thickness of 2mm.

In addition, the hydrogenated block copolymer (i)-5 and the olefin-based resin (ii) were mixed at the ratio shown in the following Table 5, and extruded at 230° C. using a 20 mmφ twin-screw extruder to produce A tubular molded body with a diameter of 6mm.

[Comparative example 1]

Mix the powdered hydrogenated block copolymer (i)-6 and olefin-based resin (ii) at the ratio shown in Table 5 below, roll-press at 170° C. with a 4-inch roll, and then use a press to Press molding was carried out under the conditions of 200°C and 100kg/cm ² to produce a molded sheet with a thickness of 2mm.

In addition, the hydrogenated block copolymer (i)-6 and olefin-based resin (ii) were mixed at the ratio shown in Table 5 below, and extruded at 230° C. using a 20 mmφ twin-screw extruder to produce A tubular molded body with a diameter of 6mm.

[Comparative example 2]

Mix the powdered hydrogenated block copolymer (i)-7 and olefin-based resin (ii) at the ratio shown in Table 5 below, roll-press at 170° C. with a 4-inch roll, and then use a press to Press molding was carried out under the conditions of 200°C and 100kg/cm ² to produce a molded sheet with a thickness of 2mm.

In addition, the hydrogenated block copolymer (i)-7 and olefin-based resin (ii) were mixed at the ratio shown in the following Table 5, and extruded at 230° C. using a 20 mmφ twin-screw extruder to produce A tubular molded body with a diameter of 6mm.

[Comparative example 3]

Mix the powdered hydrogenated block copolymer (i)-8 and olefin-based resin (ii) at the ratio shown in Table 5 below, roll-press with a 4-inch roll at 170°C, and then use a press to Press molding was carried out under the conditions of 200°C and 100kg/cm ² to produce a molded sheet with a thickness of 2mm.

In addition, the hydrogenated block copolymer (i)-8 and olefin-based resin (ii) were mixed in the ratio shown in the following Table 5, and extruded at 230° C. with a 20 mmφ twin-screw extruder to produce 6mm tubular molded body.

[Embodiments 11-14]

The powdered hydrogenated block copolymers (i)-1 and (iii)-1 and the olefin resin (ii) were mixed in the ratio shown in Table 6 below, and rolled at 170° C. with a 4-inch roll, Then, press molding was performed under the conditions of 200° C. and 100 kg/cm ² using a press to produce a molded sheet with a thickness of 2 mm.

In addition, the hydrogenated block copolymers (i)-1, (iii)-1 and olefin-based resin (ii) were mixed in the ratio shown in the following Table 6, and extruded at 230° C. using a 20 mmφ twin-screw extruder, A tubular molded body having an inner diameter of 4 mm and an outer diameter of 6 mm was produced.

[Comparative Examples 4 and 5]

The powdered hydrogenated block copolymers (i)-6, (iii)-1 and olefin-based resin (ii) were mixed in the ratio shown in Table 6 below, and rolled at 170° C. with a 4-inch roll, Then, press molding was performed under the conditions of 200° C. and 100 kg/cm ² using a press to produce a molded sheet with a thickness of 2 mm.

In addition, the hydrogenated block copolymers (i)-6, (iii)-1 and olefin-based resin (ii) were mixed in the ratio shown in the following Table 6, and extruded at 230° C. using a 20 mmφ twin-screw extruder, A tubular molded 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 (i)-7, (iii)-1 and olefin resin (ii) were mixed in the ratio shown in Table 6 below, and rolled at 170° C. with a 4-inch roll. Then, press molding was performed under the conditions of 200° C. and 100 kg/cm ² using a press to produce a molded sheet with a thickness of 2 mm.

In addition, the hydrogenated block copolymers (i)-7, (iii)-1 and olefin-based resin (ii) were mixed in the ratio shown in Table 6 below, and extruded at 230° C. using a 20 mmφ twin-screw extruder, A tubular molded body having an inner diameter of 4 mm and an outer diameter of 6 mm was produced.

[Comparative Example 7]

The powdered hydrogenated block copolymers (i)-1, (iii)-2 and olefin-based resin (ii) were mixed in the ratio shown in Table 6 below, and rolled at 170° C. with a 4-inch roll, Then, press molding was performed under the conditions of 200° C. and 100 kg/cm ² using a press to produce a molded sheet with a thickness of 2 mm.

In addition, the hydrogenated block copolymers (i)-1, (iii)-2 and olefin resin (ii) were mixed in the ratio shown in the following Table 6, and extruded at 230° C. using a 20 mmφ twin-screw extruder, A tubular molded body having an inner diameter of 4 mm and an outer diameter of 6 mm was produced.

[Comparative Example 8]

The powdered hydrogenated block copolymers (i)-1, (iii)-3 and olefin-based resin (ii) were mixed in the ratio shown in Table 6 below, and rolled at 170° C. with a 4-inch roll, Then, press molding was performed under the conditions of 200° C. and 100 kg/cm ² using a press to produce a molded sheet with a thickness of 2 mm.

In addition, the hydrogenated block copolymers (i)-1, (iii)-3 and olefin-based resin (ii) were mixed in the ratio shown in the following Table 6, and extruded at 230° C. using a 20 mmφ twin-screw extruder, A tubular molded body having an inner diameter of 4 mm and an outer diameter of 6 mm was produced.

For the hydrogenated block copolymer compositions of [Examples 1 to 10] and [Comparative Examples 1 to 3], the above (7) hardness, (8) tensile strength (Tb), elongation at break (Eb), (9) Pendulum resilience, (10) Bending resistance (distance between tangents, moving distance between chucks, judgment), (11) Haze value (turbidity, transparency judgment) and evaluation The results are shown in Table 5 below.

[table 5]

Regarding the hydrogenated block copolymer compositions of [Examples 11 to 14] and [Comparative Examples 4 to 8], the above (7) hardness, (8) tensile strength (Tb), elongation at break (Eb), (9) Pendulum resilience, (10) Bending resistance (distance between tangents, moving distance between chucks, judgment), (11) Haze value (turbidity, transparency judgment) and evaluation The results are shown in Table 6 below.

[Table 6]

In Examples 1 to 14, since the hydrogenated block copolymers (i)-1 to (i)-5 and (iii)-1 satisfying the constitutional requirements of the present invention are used as constituents, the practical A hydrogenated block copolymer composition having good flexibility, low resilience, and an excellent balance between bending resistance and transparency.

In Comparative Examples 1 to 8, since hydrogenated block copolymers (i)-6 to (i)-8, (iii)-2, and (iii)-3 that do not satisfy the constituent requirements of the present invention were used as constituents, Resilience was high in both cases, and good practical evaluation was not obtained in judging the bending resistance, and the transparency also deteriorated.

This application is based on the Japanese Patent Application (Japanese Patent Application No. 2008-207857 ) filed with the Japan Patent Office on August 12, 2008, the content of which is incorporated herein by reference.

Industrial Applicability

The hydrogenated block copolymer composition of the present invention is excellent in balance of flexibility, low resilience, bending resistance, and transparency, and can be used as hollow molded articles such as pipes and hoses, automotive interior and exterior materials, building materials, toys, It has industrial applicability for home appliance parts, medical equipment, industrial parts, and other daily sundries.

Explanation of reference signs

1 represents the position in the stress curve at the moment of pipe bending.

2 represents the distance between the chucks at the moment when the tube is bent.

Claims (15)

1. A hydrogenated block copolymer composition comprising: 2.5% by mass to 92.5% by mass of (i) a hydrogenated block copolymer having the following characteristics (1) to (4), the hydrogenated block copolymer being a copolymer of a vinyl aromatic compound and a conjugated diene Hydride; 5% to 95% by mass of (ii) at least one olefin-based resin; and 2.5% to 92.5% by mass of (iii) a hydrogenated block copolymer having the following characteristics (5) to (9), the hydrogenated block copolymer being a copolymer of a vinyl aromatic compound and a conjugated diene Hydride; (1) having at least one polymer block of the following (b), (c), (b) hydrogenated copolymer blocks composed of vinyl aromatic compounds and conjugated dienes, (c) Hydrogenated polymer blocks based on conjugated dienes; (2) The content of the vinyl aromatic compound in (b) is 40% by mass to 80% by mass; (3) The content of (c) in (i) is 20% by mass to 80% by mass; (4) In the viscoelasticity measurement chart of the hydrogenated block copolymer (i), there is at least one peak of tanδ between 0°C and below 60°C, and at least one peak of tanδ exists in the range of less than 0°C, where tanδ represents the loss tangent; (5) having at least 2 polymer blocks (A) mainly composed of vinyl aromatic compounds, and at least 1 hydrogenated polymer block (B) mainly composed of conjugated diene; (6) The content of all vinyl aromatic compounds in the hydrogenated block copolymer (iii) is more than 10% by mass and less than 25% by mass; (7) The amount of vinyl bonds in the hydrogenated polymer block (B) mainly composed of conjugated diene is 62 mass% or more and less than 99 mass%; (8) The weight-average molecular weight of the hydrogenated block copolymer is 30,000 to 300,000; (9) 75% or more of the double bonds of the conjugated diene monomer units in the hydrogenated block copolymer are hydrogenated. 2. The hydrogenated block copolymer composition according to claim 1, wherein the (iii) hydrogenated block copolymer contains 0.1 mass % to 9.1 mass % of the conjugated diene-based Hydrogenated polymer block (B) of the host. 3. The hydrogenated block copolymer composition according to claim 1 or 2, wherein said (i) hydrogenated block copolymer contains said (c) hydrogenated polymer block. 4. The hydrogenated block copolymer composition according to claim 3, wherein the content of all vinyl aromatic compounds in the (i) hydrogenated block copolymer is 20% by mass to 50% by mass. 5. The hydrogenated block copolymer composition according to claim 3, wherein the amount of vinyl bonds in the (c) hydrogenated polymer block mainly composed of conjugated diene is 50% by mass or more. 6. The hydrogenated block copolymer composition according to claim 3, wherein said (b) hydrogenated block copolymer composed of vinyl aromatic compound and conjugated diene in said (i) hydrogenated block copolymer The content of the copolymer block is 20% by mass to 80% by mass. 7. The hydrogenated block copolymer composition according to claim 3, wherein the (i) hydrogenated block copolymer has at least one (a) polymer block mainly composed of a vinyl aromatic compound. 8. The hydrogenated block copolymer composition according to claim 7, wherein the (a) polymer block mainly composed of a vinyl aromatic compound in the (i) hydrogenated block copolymer The content is 3% by mass to 30% by mass. 9. The hydrogenated block copolymer composition as claimed in claim 3, wherein the (i) hydrogenated block copolymer has at least one (d) conjugated dioxane with a vinyl bond content of 25% by mass or less. Alkene-based polymer blocks. 10. The hydrogenated block copolymer composition as claimed in claim 9, wherein the (d) vinyl bond amount in the (i) hydrogenated block copolymer is 25 mass % or less in the form of conjugated di The content of the polymer block mainly composed of olefin is 3% by mass to 30% by mass. 11. The hydrogenated block copolymer composition according to claim 3, wherein the (i) hydrogenated block copolymer has a weight average molecular weight of 50,000 to 600,000. 12. The hydrogenated block copolymer composition according to claim 3, wherein 75% or more of double bonds of the conjugated diene monomer units in the (i) hydrogenated block copolymer are hydrogenated. 13. The hydrogenated block copolymer composition according to claim 3, wherein the (ii) olefin-based resin contains at least one type of polypropylene-based resin. A molded article molded using the hydrogenated block copolymer composition according to any one of claims 1 to 13. 15. A hollow molded article molded using the hydrogenated block copolymer composition according to any one of claims 1 to 13.

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