HK1077310B

HK1077310B - Hydrogenated copolymer and composition thereof

Info

Publication number: HK1077310B
Application number: HK05109268.1A
Authority: HK
Inventors: Masahiro Sasagawa; Toshinori Shiraki; Shigeki Takayama; Shigeru Sasaki; Katsumi Suzuki; Takahiro Hisasue; Kazuo Moritou
Original assignee: 旭化成株式会社
Priority date: 2002-06-27
Filing date: 2003-06-26
Publication date: 2007-10-26

Description

Hydrogenated copolymer and composition containing the same

Background

Technical Field

The present invention relates to a hydrogenated copolymer. More specifically, the present invention relates to a hydrogenated copolymer obtained by hydrogenating an unhydrogenated copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units, the hydrogenated copolymer comprising:

at least one polymer block selected from the group consisting of a polymer block (A) of vinyl aromatic monomer units and a hydrogenated polymer block (C) obtained by hydrogenating an unhydrogenated polymer block of conjugated diene monomer units, wherein the unhydrogenated polymer block of conjugated diene monomer units has a specific vinyl bond content, and

at least one hydrogenated copolymer block (B) obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units,

wherein, when the hydrogenated copolymer does not contain the hydrogenated polymer block (C), the hydrogenated copolymer contains at least two polymer blocks (A),

wherein the hydrogenated copolymer has: a specific vinyl aromatic monomer unit content, a specific polymer block (A) content, a specific weight average molecular weight, a specific hydrogenation ratio measured for double bonds in conjugated diene monomer units, a characteristic that at least one peak of loss tangent (tan. delta.) is observed in a dynamic viscoelasticity spectrum obtained for the hydrogenated copolymer at-10 to 80 ℃, and a characteristic that, when the hydrogenated copolymer does not contain the hydrogenated polymer block (C), substantially no crystallization peak ascribed to at least one hydrogenated copolymer block (B) is observed in a Differential Scanning Calorimetry (DSC) chart obtained for the hydrogenated copolymer at-20 to 80 ℃.

The hydrogenated copolymer of the present invention has excellent properties with respect to flexibility, tensile strength, abrasion resistance, impact scratch resistance and crosslinkability.

The present invention also relates to a first-order modified, hydrogenated copolymer obtained by modifying the hydrogenated copolymer, and a second-order modified, hydrogenated copolymer obtained by modifying the first-order modified, hydrogenated copolymer. The first-order modified, hydrogenated copolymer and the second-order modified, hydrogenated copolymer have excellent properties in terms of flexibility, tensile strength, abrasion resistance, impact scratch resistance, adhesion properties and crosslinkability.

Further, the present invention relates to a hydrogenated copolymer composition comprising a hydrogenated copolymer and at least one polymer selected from a thermoplastic resin and a rubbery polymer (hereinafter, the at least one polymer is often referred to as "component (b)"); a first-order modified, hydrogenated copolymer composition comprising a first-order modified, hydrogenated copolymer and a component (b); and a second-order modified, hydrogenated copolymer composition comprising the second-order modified, hydrogenated copolymer and the component (b).

The hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention are advantageous not only in that they are suitable for use as foams, building materials, vibration damping, soundproofing materials, electric wire coatings, etc., but also in that when they are subjected to a crosslinking reaction in the presence of a crosslinking agent, a crosslinked product having excellent properties with respect to abrasion resistance, heat resistance, etc. can be obtained. Further, the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, and the second-order modified, hydrogenated copolymer of the present invention can be advantageously used for adhesive compositions, asphalt compositions, and the like.

Prior Art

With respect to a block copolymer comprising conjugated diene monomer units and vinyl aromatic hydrocarbon monomer units, when its vinyl aromatic hydrocarbon monomer unit content is low, the block copolymer exhibits not only excellent elasticity at room temperature (which is equivalent to the elasticity of a conventional, vulcanized natural or synthetic rubber) but also excellent processability at high temperature, which is equivalent to the processability of a conventional thermoplastic resin, even when it is unvulcanized. Therefore, such block copolymers having a relatively low content of vinyl aromatic hydrocarbon monomer units are widely used in various fields such as rubber shoes, modifiers for plastics, modifiers for asphalt and adhesives.

On the other hand, when the block copolymer comprising conjugated diene monomer units and vinyl aromatic hydrocarbon monomer units has a relatively high content of vinyl aromatic hydrocarbon monomer units, the block copolymer is a thermoplastic resin having excellent properties in terms of transparency and impact resistance. Therefore, such block copolymers having a relatively high content of vinyl aromatic hydrocarbon monomer units can be advantageously used in various fields such as packaging containers for foods, packaging materials for daily commodities, packaging materials for household electric appliances, packaging materials for industrial parts and the field of toys.

Further, the hydrogenated product of the above block copolymer has excellent weather resistance and excellent heat resistance, and therefore the hydrogenated product is favorably used not only in the above various fields but also in the fields of automobile parts, medical equipment and the like.

However, the above-mentioned block copolymer is disadvantageous in the following points. When the block copolymer has a low vinyl aromatic hydrocarbon monomer unit content, although the block copolymer has excellent flexibility, the block copolymer has poor abrasion resistance, thus making it difficult to widen the range of use of such block copolymers. On the other hand, when the block copolymer has a higher content of vinyl aromatic hydrocarbon monomer units, the block copolymer is poor in flexibility and thus is not suitable for use as a flexible material.

For a random copolymer comprising conjugated diene monomer units and vinyl aromatic hydrocarbon monomer units, attempts have been made to allow the random copolymer to exhibit excellent flexibility. For example, unexamined japanese patent application laid-open specification No. hei 2-158643 (corresponding to U.S. patent No.5,109,069) discloses a composition containing a hydrogenated diene copolymer and a polypropylene resin, wherein the hydrogenated diene copolymer is obtained by hydrogenating a random copolymer comprising conjugated diene monomer units and vinyl aromatic hydrocarbon monomer units and having a vinyl aromatic hydrocarbon monomer unit content of 3 to 50% by weight, a molecular weight distribution of 10 or less (wherein the molecular weight distribution refers to the ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)), and a vinyl bond content of 10 to 90% as measured for the conjugated diene monomer units in the random copolymer. Further, unexamined Japanese patent application laid-open Specification No. Hei 6-287365 discloses a composition containing a hydrogenated diene copolymer and a polypropylene resin, wherein the hydrogenated diene copolymer is obtained by hydrogenating a random copolymer comprising conjugated diene monomer units and vinyl aromatic hydrocarbon monomer units and having a vinyl aromatic hydrocarbon monomer unit content of 5 to 60% by weight and a vinyl bond content of 60% or more as measured for the conjugated diene monomer units in the random copolymer.

Meanwhile, with respect to the hydrogenated diene copolymer contained in the composition disclosed in the above-mentioned patent document, it has been attempted to use the hydrogenated diene copolymer as a substitute for the soft polyvinyl chloride resin. The soft polyvinyl chloride resin causes various environmental problems such as the generation of halogen gas upon incineration of the resin, and the generation of environmental hormones due to a plasticizer used in the resin. Therefore, the development of an alternative material for the soft polyvinyl chloride resin is urgently required. However, the above-mentioned hydrogenated diene copolymer has unsatisfactory properties with respect to abrasion resistance, impact scratch resistance and the like, which are important for a material used as a substitute for a soft polyvinyl chloride resin.

In recent years, it has been attempted to cause the above-mentioned block copolymer comprising conjugated diene monomer units and vinyl aromatic hydrocarbon monomer units and having a higher content of vinyl aromatic hydrocarbon monomer units to exhibit excellent flexibility.

For example, Japanese patent application unexamined publication (Tokuhyo) No. Hei 10-501833 (corresponding to U.S. Pat. No.6,031,053) discloses a block copolymer comprising a conjugated diene polymer block and a conjugated diene/vinyl aromatic hydrocarbon copolymer block. However, this block copolymer has unsatisfactory abrasion resistance.

On the other hand, unexamined japanese patent application laid-open specification No. hei 2-300250 discloses a block copolymer comprising a conjugated diene polymer block and a vinyl aromatic hydrocarbon polymer block, wherein the conjugated diene polymer block comprises only isoprene monomer units or a mixture of isoprene monomer units and butadiene monomer units and has a total content of 3, 4-vinyl bonds and 1, 2-vinyl bonds of 40% or more, and wherein at least one peak of loss tangent (tan δ) is observed at 0 ℃ in a dynamic viscoelasticity spectrum obtained for the block copolymer. However, this block copolymer has unsatisfactory abrasion resistance.

WO 98/12240 (corresponding to GB 0927210) discloses a molding material composed mainly of a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising a polymer block composed mainly of styrene monomer units and a copolymer block composed mainly of butadiene monomer units and styrene monomer units. Further, unexamined Japanese patent application laid-open Specification No. Hei 3-185058 discloses a resin composition comprising a polyphenylene ether resin, a polyolefin resin and a hydrogenated product of a vinyl aromatic hydrocarbon/conjugated diene random copolymer, wherein the hydrogenated product of the vinyl aromatic hydrocarbon/conjugated diene random copolymer is substantially the same as the hydrogenated block copolymer used in the above-mentioned WO 98/12240. However, any of the hydrogenated copolymers described in the above-mentioned patent documents has poor flexibility and is therefore unsuitable as a substitute for a soft polyvinyl chloride resin.

Therefore, although there is an urgent need to develop alternative materials for the soft polyvinyl chloride resin having various environmental problems, materials having desired properties (such as excellent flexibility and excellent abrasion resistance) comparable to those of the soft polyvinyl chloride resin have not yet been obtained.

Summary of the invention

In this situation, the present inventors have conducted extensive and intensive studies in order to solve the above-mentioned problems of the prior art. As a result, it has unexpectedly been found that these problems can be solved by a hydrogenated copolymer obtained by hydrogenating an unhydrogenated copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units, the hydrogenated copolymer comprising:

Based on this finding, the present invention has been completed.

Accordingly, it is an object of the present invention to provide a hydrogenated copolymer having excellent properties in terms of flexibility, tensile strength, abrasion resistance, impact scratch resistance and crosslinkability.

It is another object of the present invention to provide a first-order modified, hydrogenated copolymer obtained by modifying a hydrogenated copolymer, and a second-order modified, hydrogenated copolymer obtained by modifying a first-order modified, hydrogenated copolymer. The first-order modified, hydrogenated copolymer and the second-order modified, hydrogenated copolymer have excellent properties in terms of flexibility, tensile strength, abrasion resistance, impact scratch resistance, adhesion properties and crosslinkability.

It is still another object of the present invention to provide a composition comprising any one of a hydrogenated copolymer, a first-order modified, hydrogenated copolymer and a second-order modified, hydrogenated copolymer, and at least one polymer selected from a thermoplastic resin and a rubbery polymer (the at least one polymer is often referred to as "component (b)").

The above and other objects, features and advantages of the present invention will become apparent from the following detailed description and appended claims.

Detailed description of the invention

In one aspect of the present invention, there is provided a hydrogenated copolymer obtained by hydrogenating an unhydrogenated copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units, the hydrogenated copolymer comprising:

at least one polymer block selected from the group consisting of a polymer block (A) of vinyl aromatic monomer units and a hydrogenated polymer block (C) obtained by hydrogenating an unhydrogenated polymer block of conjugated diene monomer units, wherein the unhydrogenated polymer block of conjugated diene monomer units has a vinyl bond content of less than 30%, and

at least one hydrogenated copolymer block (B) obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units, the unhydrogenated random copolymer block having a weight ratio of conjugated diene monomer units/vinyl aromatic monomer units of 45/55 to 10/90,

the hydrogenated copolymer has the following characteristics (1) to (6):

(1) the hydrogenated copolymer has a content of vinyl aromatic monomer units of more than 40 to less than 95% by weight, based on the weight of the hydrogenated copolymer,

(2) the hydrogenated copolymer has a content of the polymer block (A) of 0 to 60% by weight, based on the weight of the hydrogenated copolymer,

(3) the hydrogenated copolymer had a weight average molecular weight of 30,000-1,000,000,

(4) the hydrogenated copolymer has a hydrogenation ratio of 75% or more as measured with respect to the double bonds in the conjugated diene monomer units,

(5) at least one peak of loss tangent (tan. delta.) is observed in a dynamic viscoelasticity spectrum obtained for the hydrogenated copolymer at-10 to 80 ℃, and

(6) when the hydrogenated copolymer does not contain the hydrogenated polymer block (C), substantially no crystallization peak ascribed to the at least one hydrogenated copolymer block (B) is observed in a Differential Scanning Calorimetry (DSC) chart obtained for the hydrogenated copolymer at-20 to 80 ℃.

In order that the present invention may be more readily understood, the following description illustrates the principal features and various preferred embodiments of the invention.

1. A hydrogenated copolymer obtained by hydrogenating an unhydrogenated copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units, the hydrogenated copolymer comprising:

the hydrogenated copolymer has the following characteristics (1) to (6):

2. A hydrogenated copolymer according to item 1 above, which comprises at least one hydrogenated polymer block (C), at least one hydrogenated copolymer block (B) and optionally at least one polymer block (A),

wherein the hydrogenated copolymer further has the following characteristics (7) and (8):

(7) the hydrogenated copolymer has a content of at least one hydrogenated polymer block (C) of 10 to 50% by weight, a content of at least one hydrogenated copolymer block (B) of 30 to 90% by weight, and a content of polymer block (A) of 0 to 40% by weight, each based on the weight of the hydrogenated copolymer, and

(8) the hydrogenated copolymer has a content of vinyl aromatic monomer units of more than 40% by weight to less than 90% by weight, based on the weight of the hydrogenated copolymer.

3. The hydrogenated copolymer according to item 2 above, wherein substantially no crystallization peak ascribed to the at least one hydrogenated copolymer block (B) is observed in a Differential Scanning Calorimetry (DSC) chart obtained for the hydrogenated copolymer at-20 to 80 ℃.

4. A hydrogenated copolymer according to item 1 above, which comprises at least two polymer blocks (A) and at least one hydrogenated copolymer block (B),

wherein the hydrogenated copolymer further has the following characteristics (9) and (10):

(9) the hydrogenated copolymer has a content of vinyl aromatic monomer units of more than 50 to less than 95% by weight, based on the weight of the hydrogenated copolymer, and

(10) the hydrogenated copolymer has a content of at least two polymer blocks (A) of 5 to 60% by weight, based on the weight of the hydrogenated copolymer.

5. The hydrogenated copolymer according to item 1 above, which is a foam.

6. The hydrogenated copolymer according to item 1 above, which is a building material, vibration damping, sound insulating material or electric wire coating material.

7. A crosslinked hydrogenated copolymer obtained by subjecting the hydrogenated copolymer of item 1 above to a crosslinking reaction in the presence of a crosslinking agent.

8. A hydrogenated copolymer composition comprising:

1 to 99 parts by weight of the above (a-0) hydrogenated copolymer of item 1, relative to 100 parts by weight of the total amount of the components (a-0) and (b), and

99 to 1 part by weight of (b) at least one polymer selected from a thermoplastic resin other than the hydrogenated copolymer (a-0) and a rubbery polymer other than the hydrogenated copolymer (a-0), relative to 100 parts by weight of the total amount of the components (a-0) and (b).

9. The hydrogenated copolymer composition according to item 8 above, which is a foam.

10. The hydrogenated copolymer composition according to item 8 above, which is a building material, a vibration damping, a sound insulating material or an electric wire coating material.

11. A crosslinked hydrogenated copolymer composition obtained by subjecting the hydrogenated copolymer composition of item 8 above to a crosslinking reaction in the presence of a crosslinking agent.

12. An adhesive composition comprising:

100 parts by weight of the hydrogenated copolymer (a-0) of item 1 above, and 20 to 400 parts by weight of a tackifier (n).

13. An asphalt composition comprising:

0.5 to 50 parts by weight of the hydrogenated copolymer (a-0) of item 1 above, and 100 parts by weight of the asphalt (o).

14. A first-order modified, hydrogenated copolymer comprising the hydrogenated copolymer of item 1 above and a functional group-containing first-order modifier group bonded to the hydrogenated copolymer.

15. The first-order modified, hydrogenated copolymer according to item 14 above, wherein the first-order modifier group has at least one functional group selected from the following: a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxyl group, a thiocarboxyl group, an aldehyde group, a thioaldehyde group, a carboxylate group, an amide group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphoester group, an amino group, an imino group, a cyano group, a pyridyl group, a quinolyl group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilane group, a tin halide group, an alkoxy tin group and a phenyl tin group.

16. The first-order modified, hydrogenated copolymer according to item 15 above, wherein the first-order modifier group has at least one functional group selected from the group consisting of functional groups represented by the following formulae (1) to (14):

(1)-NR¹-R⁵-OH ，

(2)-N[R⁵-OH]₂ ，

(3)-NR¹-R⁵-Si(OR⁶)₃ ，

(4)-N[R⁵-Si(OR⁶)₃]₂ ，

(10)-O-R⁵-Si(OR⁶)₃ ，

and

wherein, in structural formulae (1) to (14):

n represents a nitrogen atom, Si represents a silicon atom, O represents an oxygen atom, C represents a carbon atom, and H represents a hydrogen atom,

R¹to R⁴Each independently represents a hydrogen atom or C₁-C₂₄A hydrocarbon group optionally having a substituent selected from the group consisting of hydroxyl, epoxy, amino, silanol and C₁-C₂₄At least one functional group in the alkoxysilyl group,

each R⁵Independently represent C₁-C₄₈A hydrocarbon group optionally having a substituent selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group and C₁-C₂₄At least one functional group in the alkoxysilyl group, and

each R⁶Independently represent a hydrogen atom or C₁-C₈An alkyl group.

17. The first-order modified, hydrogenated copolymer according to item 14 above, which is a foam.

18. A crosslinked, first-order modified, hydrogenated copolymer obtained by subjecting the first-order modified, hydrogenated copolymer of item 14 above to a crosslinking reaction in the presence of a crosslinking agent.

19. A first-order modified, hydrogenated copolymer composition comprising:

1 to 99 parts by weight of (a-1) the above first-order modified, hydrogenated copolymer of item 14, relative to 100 parts by weight of the total amount of components (a-1) and (b), and

99 to 1 part by weight of (b) at least one polymer selected from a thermoplastic resin different from the first-order modified, hydrogenated copolymer (a-1) and a rubbery polymer different from the first-order modified, hydrogenated copolymer (a-1), relative to 100 parts by weight of the total amount of the components (a-1) and (b).

20. The first-order modified, hydrogenated copolymer composition according to item 19 above, which is a foam.

21. A crosslinked, first-order modified, hydrogenated copolymer composition obtained by subjecting the first-order modified, hydrogenated copolymer composition of item 19 above to a crosslinking reaction in the presence of a crosslinking agent.

22. An adhesive composition comprising:

100 parts by weight of the above first-order modified, hydrogenated copolymer (a-1) of item 14, and

20 to 400 parts by weight of a tackifier (n).

23. A bitumen composition comprising:

0.5 to 50 parts by weight of the above first-order modified, hydrogenated copolymer (a-1) of item 14, and 100 parts by weight of the asphalt (o).

24. A second-order modified, hydrogenated copolymer obtained by reacting the first-order modified, hydrogenated copolymer of item 14 above with a second-order modifier, wherein the second-order modifier has a functional group reactive with the functional group of the first-order modifier group of the first-order modified, hydrogenated copolymer.

25. The second-order modified, hydrogenated copolymer according to item 24 above, wherein the functional group of the second-order modifier comprises at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group.

26. The second-order modified, hydrogenated copolymer according to item 24 above, which is a foam.

27. A crosslinked, second-order modified, hydrogenated copolymer obtained by subjecting the second-order modified, hydrogenated copolymer of item 24 above to a crosslinking reaction in the presence of a crosslinking agent.

28. A second-order modified, hydrogenated copolymer composition comprising:

1 to 99 parts by weight of (a-2) the above second-order modified, hydrogenated copolymer of item 24, relative to 100 parts by weight of the total amount of components (a-2) and (b), and

99 to 1 part by weight of (b) at least one polymer selected from a thermoplastic resin different from the second-order modified, hydrogenated copolymer (a-2) and a rubbery polymer different from the second-order modified, hydrogenated copolymer (a-2), relative to 100 parts by weight of the total amount of the components (a-2) and (b).

29. The second-order modified, hydrogenated copolymer composition according to item 28 above, which is a foam.

30. A crosslinked, second-order modified, hydrogenated copolymer composition obtained by subjecting the second-order modified, hydrogenated copolymer composition of item 28 above to a crosslinking reaction in the presence of a crosslinking agent.

31. An adhesive composition comprising:

100 parts by weight of the above second-order modified, hydrogenated copolymer (a-2) of item 24, and 20 to 400 parts by weight of a tackifier (n).

32. An asphalt composition comprising:

0.5 to 50 parts by weight of the above second-order modified, hydrogenated copolymer (a-2) of item 24, and 100 parts by weight of the asphalt (o).

Hereinafter, the present invention is described in detail.

In the present invention, the monomer units of a polymer are named according to a nomenclature where the name of the initial monomer from which the monomer unit is derived is used together with the term "monomer unit" attached thereto. For example, the term "vinyl aromatic monomer unit" refers to a monomer unit formed in a polymer obtained by polymerization of a vinyl aromatic monomer. The vinyl aromatic monomer units have a molecular structure in which two carbon atoms of a substituted ethylene group derived from a substituted vinyl group form a linking group with adjacent vinyl aromatic monomer units, respectively. Similarly, the term "conjugated diene monomer unit" refers to a monomer unit formed in a polymer obtained by polymerization of a conjugated diene monomer. The conjugated diene monomer unit has a molecular structure in which two carbon atoms of the olefin corresponding to the conjugated diene monomer constitute a linking group with the adjacent conjugated diene monomer unit, respectively.

The hydrogenated copolymer of the present invention is obtained by hydrogenating an unhydrogenated copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units (hereinafter, this unhydrogenated copolymer is often referred to as "base unhydrogenated copolymer"). The hydrogenated copolymer of the present invention comprises:

at least one hydrogenated copolymer block (B) obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units.

Each of the polymer block (a) and the hydrogenated polymer block (C) exerts a function similar to that of a physical crosslinking point, and is referred to as a "hard segment". On the other hand, the hydrogenated copolymer block (B) is referred to as a "soft segment".

It is preferred that the hydrogenated copolymer of the present invention contains at least two polymer blocks belonging to the hard segment. When the hydrogenated copolymer of the present invention does not contain the hydrogenated polymer block (C), it is required that the hydrogenated copolymer contains at least two polymer blocks (A). When the hydrogenated copolymer of the present invention contains at least two polymer blocks belonging to the hard segment, the hydrogenated copolymer exhibits excellent tensile elongation at break. Specifically, in this case, for example, the tensile elongation at break of the hydrogenated copolymer is generally 100% or more, preferably 200% or more, more preferably 300% or more, as measured at a pulling rate of 200 mm/min.

When the hydrogenated copolymer of the present invention contains the hydrogenated polymer block (C), the hydrogenated copolymer has excellent crosslinkability.

When the hydrogenated copolymer of the present invention does not contain the hydrogenated polymer block (C), it is required that substantially no crystallization peak ascribed to the at least one hydrogenated copolymer block (B) is observed in a Differential Scanning Calorimetry (DSC) chart obtained for the hydrogenated copolymer at-20 to 80 ℃. In the present invention, "substantially no crystallization peak is observed at-20 to 80 ℃ means that no peak indicating the presence of crystallization (i.e., crystallization peak) is observed in the above-mentioned temperature range, or no crystallization peak is observed in the above-mentioned temperature range, but the quantity of heat at the crystallization peak is less than 3J/g, preferably less than 2J/g, more preferably less than 1J/g, still more preferably zero.

When the hydrogenated copolymer of the present invention contains the hydrogenated polymer block (C), the hydrogenated copolymer does not necessarily satisfy the above requirement that substantially no crystallization peak ascribed to the at least one hydrogenated copolymer block (B) is observed in a Differential Scanning Calorimetry (DSC) chart obtained for the hydrogenated copolymer at-20 to 80 ℃. However, even when the hydrogenated copolymer contains the hydrogenated polymer block (C), it is preferred that substantially no crystallization peak ascribed to the at least one hydrogenated copolymer block (B) is observed in a Differential Scanning Calorimetry (DSC) chart obtained for the hydrogenated copolymer at-20 to 80 ℃.

When substantially no crystallization peak ascribed to the at least one hydrogenated copolymer block (B) is observed in a DSC chart obtained for the hydrogenated copolymer at-20 to 80 ℃, the hydrogenated copolymer has excellent flexibility and, therefore, is suitable for use as a substitute for a soft polyvinyl chloride resin. The above-mentioned hydrogenated copolymer, characterized in that substantially no crystallization peak ascribed to at least one hydrogenated copolymer block (B) is observed in a DSC chart obtained with respect to the hydrogenated copolymer at-20 to 80 ℃, can be obtained by hydrogenating an unhydrogenated copolymer obtained by polymerization under the following conditions in the presence of the following vinyl bond formation-controlling agent and/or an agent for controlling random copolymerization of a conjugated diene and a vinyl aromatic compound.

When the hydrogenated copolymer of the present invention contains the hydrogenated polymer block (C), it is preferable that a crystallization peak ascribed to the hydrogenated polymer block (C) is observed at a temperature of 30 ℃ or more, more desirably 45 to 100 ℃, still more desirably 50 to 90 ℃ in a DSC chart obtained for the hydrogenated copolymer. Preferably, the amount of heat at the crystallization peak is 3J/g or more, more advantageously 6J/g or more, still more advantageously 10J/g or more.

The crystallization peak temperature and the amount of heat at the crystallization peak temperature can be measured using a Differential Scanning Calorimetry (DSC) apparatus.

The hydrogenated copolymer of the present invention has a content of the vinyl aromatic monomer units of more than 40% by weight to less than 95% by weight, based on the weight of the hydrogenated copolymer of the present invention. Due to this characteristic, the hydrogenated copolymer of the present invention has excellent properties in terms of flexibility, abrasion resistance and impact scratch resistance. The content of the vinyl aromatic monomer units in the hydrogenated copolymer is preferably from 44% by weight to less than 90% by weight, more preferably from 48 to 88% by weight, based on the weight of the hydrogenated copolymer, from the viewpoint of flexibility, abrasion resistance and impact scratch resistance of the hydrogenated copolymer. When the hydrogenated copolymer does not contain the hydrogenated polymer block (C), the content of the vinyl aromatic monomer units in the hydrogenated copolymer is preferably from more than 50% by weight to less than 95% by weight, more preferably from more than 55% by weight to less than 92% by weight, still more preferably from more than 60% by weight to less than 88% by weight, still more preferably from 62 to 85% by weight, based on the weight of the hydrogenated copolymer. On the other hand, when the hydrogenated copolymer contains the hydrogenated polymer block (C), the content of the vinyl aromatic monomer units in the hydrogenated copolymer is preferably from more than 40% by weight to less than 90% by weight, more preferably from 44 to 85% by weight, still more preferably from 48 to 80% by weight, still more preferably from 50 to 70% by weight, based on the weight of the hydrogenated copolymer.

The content of the vinyl aromatic monomer units in the hydrogenated copolymer is approximately equal to the content of the vinyl aromatic monomer units in the base unhydrogenated copolymer. Therefore, the content of the vinyl aromatic monomer unit in the base unhydrogenated copolymer is used as the content of the vinyl aromatic monomer unit in the hydrogenated copolymer. The content of the vinyl aromatic monomer units in the base unhydrogenated copolymer was measured using an ultraviolet spectrophotometer.

The hydrogenated copolymer of the present invention has a content of the polymer block (A) of 0 to 60% by weight, based on the weight of the hydrogenated copolymer. Due to this characteristic, the hydrogenated copolymer of the present invention has excellent flexibility. From the viewpoint of the heat resistance of the hydrogenated copolymer, the content of the polymer block (A) in the hydrogenated copolymer is preferably from 5 to 60% by weight, more preferably from 8 to 50% by weight, still more preferably from 10 to 40% by weight, still more preferably from 12 to 35% by weight, based on the weight of the hydrogenated copolymer. On the other hand, from the viewpoint of flexibility and handling properties (anti-blocking property) of the hydrogenated copolymer, the content of the polymer block (A) in the hydrogenated copolymer is preferably from 0 to 40% by weight, more preferably from 1 to 40% by weight, still more preferably from 5 to 35% by weight, still more preferably from 10 to 30% by weight, based on the weight of the hydrogenated copolymer. Herein, the "anti-blocking property" refers to a property against an adhesion phenomenon (generally referred to as "blocking") in which, when, for example, a stacked resin molded article or a rolled resin film (which has resin surfaces in contact with each other) is stored for a long time, strong adhesion disadvantageously occurs between the resin surfaces, making it difficult to separate the resin surfaces from each other. Further, from the viewpoint of the crosslinkability of the hydrogenated copolymer, it is preferred that the content of the polymer block (A) in the hydrogenated copolymer is less than 5% by weight, more advantageously less than 2% by weight, based on the weight of the hydrogenated copolymer.

The content of the polymer block (A) (vinyl aromatic polymer block) in the hydrogenated copolymer is approximately equal to the content of the polymer block (A) in the base unhydrogenated copolymer. Therefore, the content of the polymer block (A) in the base unhydrogenated copolymer is used as the content of the polymer block (A) in the hydrogenated copolymer. The content of the polymer block (A) in the base unhydrogenated copolymer can be measured by the following method. The weight of the polymer block (a) is obtained by a method in which the base unhydrogenated copolymer is subjected to oxidative degradation using tert-butyl hydroperoxide in the presence of osmium tetroxide as a catalyst (i.e., a method described in i.m. kolthoff et al, j.polymer.sci., volume 1, p429 (1946)) (hereinafter often referred to as "osmium tetroxide degradation method"). By using the weight of the obtained polymer block (a), the content of the polymer block (a) in the base unhydrogenated copolymer is calculated from the following formula, provided that, among the polymer chains (formed by oxidative degradation) corresponding to the vinyl aromatic polymer block, the polymer chain having a degree of polymerization of about 30 or less is not considered in the measurement of the content of the polymer block (a).

Content of vinyl aromatic Polymer Block (A) (% by weight)

{ (weight of the vinyl aromatic polymer block (a) in the base unhydrogenated copolymer)/(total weight of the vinyl aromatic monomer units in the base unhydrogenated copolymer) } × 100.

Also, the content of the polymer block (A) in the hydrogenated copolymer can be obtained by a method in which the hydrogenated copolymer is directly analyzed by a Nuclear Magnetic Resonance (NMR) apparatus (see Y. tanaka et al, "RUBBER CHEMISTRY and TECHNOLOGY", Vol.54, p.685 (1981)) (hereinafter, this method is often referred to as "NMR method").

There is a correlation between a value of the content of the polymer block (A) obtained by the osmium tetroxide degradation method (hereinafter, this value is referred to as "Os value") and a value of the content of the polymer block (A) obtained by the NMR method (hereinafter, this value is often referred to as "Ns value"). More specifically, as a result of studies conducted by the present inventors on various copolymers having different contents of the vinyl aromatic polymer block (a), it has been found that the above-mentioned correlation is represented by the following formula:

os value-0.012 (Ns value)²+1.8(Ns value) -13.0

In the present invention, when the Ns value is obtained by this NMR method, the obtained Ns value is converted into the Os value by using the above-mentioned formula representing the correlation between the Os value and the Ns value.

There is no particular limitation on the content of the hydrogenated copolymer block (B) in the hydrogenated copolymer. However, when the hydrogenated copolymer does not contain the hydrogenated polymer block (C), it is preferred that the content of the hydrogenated copolymer block (B) in the hydrogenated copolymer is from 30 to 95% by weight, more advantageously from 40 to 92% by weight, still more advantageously from 50 to 90% by weight, based on the weight of the hydrogenated copolymer, from the viewpoint of the scratch resistance of the hydrogenated copolymer. On the other hand, when the hydrogenated copolymer contains the hydrogenated polymer block (C), it is preferred that the content of the hydrogenated copolymer block (B) in the hydrogenated copolymer is from 30 to 90% by weight, more advantageously from 40 to 88% by weight, still more advantageously from 50 to 86% by weight, based on the weight of the hydrogenated copolymer.

As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units. The amount of the hydrogenated copolymer block (B) is obtained from the amounts of the conjugated diene monomer and the vinyl aromatic monomer used for producing the unhydrogenated random copolymer block. The content of the hydrogenated copolymer block (B) in the hydrogenated copolymer is approximately equal to the content of the unhydrogenated random copolymer block in the base unhydrogenated copolymer. Therefore, the content of the unhydrogenated random copolymer block in the base unhydrogenated copolymer is used as the content of the hydrogenated copolymer block (B) in the hydrogenated copolymer.

There is no particular limitation on the content of the hydrogenated polymer block (C) in the hydrogenated copolymer of the present invention. However, from the viewpoint of flexibility and abrasion resistance of the hydrogenated copolymer, the content of the hydrogenated polymer block (C) in the hydrogenated copolymer is preferably from 0 to 50% by weight, more preferably from 10 to 50% by weight, still more preferably from 12 to 45% by weight, still more preferably from 15 to 40% by weight, based on the weight of the hydrogenated copolymer.

As described above, the hydrogenated polymer block (C) is obtained by hydrogenating an unhydrogenated polymer block of conjugated diene monomer units. The amount of the hydrogenated polymer block (C) can be obtained from the amount of the conjugated diene monomer used for producing the unhydrogenated polymer block. The content of the hydrogenated polymer block (C) in the hydrogenated copolymer is approximately equal to the content of the unhydrogenated polymer block (of conjugated diene monomer units) in the base unhydrogenated copolymer. Therefore, the content of the unhydrogenated polymer block (of the conjugated diene monomer units) in the base unhydrogenated copolymer is used as the content of the hydrogenated polymer block (C) in the hydrogenated copolymer.

The hydrogenated copolymer of the present invention has a weight average molecular weight of 30,000-1,000,000. Due to this characteristic, the hydrogenated copolymer of the present invention has a good balance of mechanical strength or scratch resistance and processability. From the viewpoint of a good balance of the mechanical strength or scratch resistance and processability of the hydrogenated copolymer, it is preferred that the weight average molecular weight of the hydrogenated copolymer is 50,000-800,000, more advantageously 100,000-500,000, still more advantageously 150,000-400,000. When the hydrogenated copolymer contains the hydrogenated polymer block (C), it is preferred that the weight average molecular weight of the hydrogenated copolymer is from more than 100,000 to 1,000,000, more advantageously 120,000-800,000, still more advantageously 140,000-500,000, from the viewpoint of processability of the hydrogenated copolymer.

As for the molecular weight distribution (Mw/Mn) (i.e., the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the hydrogenated copolymer of the present invention, it is preferable that the Mw/Mn is 10 or less, more favorably 1.05 to 8, still more favorably 1.1 to 5. When it is particularly desired to achieve excellent processability, it is preferred that the Mw/Mn of the hydrogenated copolymer is from 1.3 to 5, more advantageously from 1.5 to 5, still more advantageously from 1.6 to 4.5, still more advantageously from 1.8 to 4.

The weight average molecular weight of the hydrogenated copolymer is approximately equal to the weight average molecular weight of the base unhydrogenated copolymer. Therefore, the weight average molecular weight of the base unhydrogenated copolymer is used as the weight average molecular weight of the hydrogenated copolymer. The weight average molecular weight of the base unhydrogenated copolymer was measured by Gel Permeation Chromatography (GPC) using a calibration curve obtained for a commercially available standard monodisperse polystyrene having a predetermined molecular weight. The number average molecular weight of the hydrogenated copolymer can be obtained in the same manner as in the case of the weight average molecular weight of the base unhydrogenated copolymer. The molecular weight distribution of the hydrogenated copolymer can be obtained by calculating the ratio of the weight average molecular weight to the number average molecular weight.

As described above, the hydrogenated copolymer of the present invention is obtained by hydrogenating an unhydrogenated copolymer (i.e., a base unhydrogenated copolymer) comprising conjugated diene monomer units and vinyl aromatic monomer units. The hydrogenated copolymer has a hydrogenation ratio of 75% to 100% as measured for the double bonds in the conjugated diene monomer units, and due to this characteristic, the hydrogenated copolymer of the present invention has excellent properties in terms of abrasion resistance and handling properties (anti-blocking properties). From the viewpoint of the abrasion resistance and handling property (anti-blocking property) of the hydrogenated copolymer, it is preferred that the hydrogenation ratio of the hydrogenated copolymer measured with respect to the double bonds in the conjugated diene monomer units is from 80 to 100%, more advantageously from 85 to 100%, still more advantageously from 90 to 100%.

The hydrogenation ratio of the hydrogenated copolymer measured with respect to the vinyl aromatic monomer units is not particularly limited. However, the hydrogenation ratio of the hydrogenated copolymer measured for the vinyl aromatic monomer units is preferably 50% or less, more preferably 30% or less, still more preferably 20% or less.

The above hydrogenation ratio can be measured by means of a nuclear magnetic resonance apparatus.

In the dynamic viscoelasticity spectrum obtained for the hydrogenated copolymer of the present invention, at least one peak of loss tangent (tan. delta.) is observed at-10 to 80 ℃, preferably at 0 to 70 ℃, more preferably at 5 to 50 ℃. In the dynamic viscoelasticity spectrum, the peak of loss tangent observed at-10 to 80 ℃ is ascribed to the hydrogenated copolymer block (B) (i.e., a hydrogenated copolymer block obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units). The occurrence of at least one peak of loss tangent in the range of-10 to 80 ℃ is essential to achieve a good balance of abrasion resistance and flexibility of the hydrogenated copolymer.

In the dynamic viscoelasticity spectrum obtained for the hydrogenated copolymer of the present invention, there is no particular limitation with respect to the presence or absence of a peak of loss tangent ascribed to the polymer block (A). However, in general, the peak of loss tangent ascribed to the polymer block (A) is present at a temperature in the range from more than 80 ℃ to 150 ℃.

The measurement of the peak of loss tangent (tan. delta.) in the dynamic viscoelasticity spectrum was measured at a frequency of 10Hz using a dynamic viscoelasticity spectrum analyzer.

As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units. There is no particular limitation on the weight ratio of conjugated diene monomer units/vinyl aromatic monomer units in the unhydrogenated random copolymer block. However, in view of the above requirement that at least one peak of loss tangent is observed in the dynamic viscoelasticity spectrum obtained for the hydrogenated copolymer at-10 to 80 ℃, it is preferred that the weight ratio of conjugated diene monomer units/vinyl aromatic monomer units in the unhydrogenated random copolymer block is from 45/55 to 10/90, more advantageously from 40/60 to 13/87, still more advantageously from 35/65 to 16/84.

As described above, the hydrogenated copolymer block (B) is obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units. The microstructure of the conjugated diene monomer units in the unhydrogenated random copolymer block (i.e., the amount of cis-bonds, trans-bonds, and vinyl bonds) can be appropriately controlled by using the following polar compounds and the like. When 1, 3-butadiene is used as the conjugated diene monomer, the 1, 2-vinyl bond content is preferably 5 to 50%, more preferably 10 to 40%. When isoprene or a combination of 1, 3-butadiene and isoprene is used as the conjugated diene monomer, the total content of 1, 2-vinyl bonds and 3, 4-vinyl bonds is preferably 3 to 75%, more preferably 5 to 60%. From the viewpoint of the abrasion resistance of the hydrogenated copolymer, the vinyl bond content is preferably 5 to 35%, more preferably 8 to 25%, still more preferably 10 to 20%.

Hereinafter, the vinyl bond content refers to the total content of 1, 2-vinyl bonds and 3, 4-vinyl bonds, with the proviso that when only 1, 3-butadiene is used as the conjugated diene monomer, the vinyl bond content refers to the content of 1, 2-vinyl bonds.

As described above, the hydrogenated polymer block (C) is obtained by hydrogenating an unhydrogenated polymer block of conjugated diene monomer units, wherein the unhydrogenated polymer block of conjugated diene monomer units has a vinyl bond content of less than 30%. The vinyl bond content of the unhydrogenated polymer block is preferably from 8 to 25%, more preferably from 10 to 25%, still more preferably from 12 to 20%, from the viewpoint of abrasion resistance, crosslinkability and handling properties (anti-blocking property) of the hydrogenated copolymer.

The vinyl bond content was measured for the base unhydrogenated copolymer using an infrared spectrophotometer.

As described above, the hydrogenated copolymer of the present invention comprises at least one polymer block belonging to the hard segment and at least one copolymer block belonging to the soft segment. When the hydrogenated copolymer of the present invention contains at least two polymer blocks belonging to the hard segment, the hydrogenated copolymer exhibits only a small tensile permanent set. The tensile permanent set of the hydrogenated copolymer is preferably 50% or less, more preferably 30% or less, still more preferably 25% or less, still more preferably 20% or less, or 50% or less, more preferably 30% or less, still more preferably 25% or less, or more preferably 20% or less. The tensile permanent set of the hydrogenated copolymer is defined as follows. A sample of the hydrogenated copolymer was subjected to a tensile test in which the sample was stretched until the sample broke. The elongation at break of the sample and the residual elongation of the sample at a time point of 24 hours after the break thereof were measured. The tensile set is defined as a value (%) obtained by dividing the residual elongation by the elongation at break.

The structure of the hydrogenated copolymer of the present invention is not particularly limited. As an example of the hydrogenated copolymer of the present invention, there can be mentioned a hydrogenated copolymer comprising at least one hydrogenated polymer block (C), at least one hydrogenated copolymer block (B) and optionally at least one polymer block (A). Specific examples of such hydrogenated copolymers include those having the formula:

(C-B)_n，C-(B-C)_n，B-(C-B)_n，[(C-B)_n]_m-X，[(B-C)_n-B]_m-X，[(C-B)_n-C]_m-X，C-(B-A)_n，C-(A-B)_n，C-(A-B-A)_n，

C-(B-A-B)_n，A-C-(B-A)_n，A-C-(A-B)_n，A-C-(B-A)_n-B，

[(A-B-C)_n]_m-X，[A-(B-C)_n]_m-X，[(A-B)_n-C]_m-X，

[(A-B-A)_nC]_m-X，[(B-A-B)_n-C]_m-X，[(C-B-A)_n]_m-X，

[C-(B-A)_n]_m-X，[C-(A-B-A)_n]_m-X, and [ C- (B-A-B)_n]_m-X。

As another example of the hydrogenated copolymer of the present invention, there can be mentioned a hydrogenated copolymer comprising at least two polymer blocks (A) and at least one hydrogenated copolymer block (B). Specific examples of such hydrogenated copolymers include those having the formula:

(A-B)_n+1，A-(B-A)_nB-(A-B)_n+1，[(A-B)_n]_m-X，

[(B-A)_n-B]_m-X, and [ (A-B)_n-A]_m-X。

In the above structural formula, each a independently represents a polymer block of a vinyl aromatic monomer unit. Each B independently represents a hydrogenated copolymer block obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units. Each C independently represents a hydrogenated polymer block obtained by hydrogenating an unhydrogenated polymer block of conjugated diene monomer units, wherein the unhydrogenated polymer block of conjugated diene monomer units has a vinyl bond content of less than 30%. It is not necessary that the boundaries between the polymer blocks be sharp. In each of the hydrogenated copolymer blocks B, which is obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units, the vinyl aromatic monomer units may be uniformly distributed or may be distributed in a tapered configuration. Further, each hydrogenated copolymer block B may have a plurality of segments in which the vinyl aromatic monomer units are uniformly distributed, and/or may have a plurality of segments in which the vinyl aromatic monomer units are distributed in a tapered configuration. Further, each hydrogenated copolymer block B may have a plurality of segments having different contents of the vinyl aromatic monomer units. In the above structural formulae, each n is independently an integer of 1 or more, preferably 1 to 5, and each m is independently an integer of 2 or more, preferably 2 to 11. Each X independently represents the residue of a coupling agent or the residue of a polyfunctional polymerization initiator. Examples of the coupling agent include the following di-or poly-functionalized coupling agents. Examples of the polyfunctional polymerization initiator include a reaction product of diisopropenylbenzene and sec-butyllithium, and a reaction product obtained by reacting divinylbenzene, sec-butyllithium and a small amount of 1, 3-butadiene.

The hydrogenated copolymer of the present invention may be a mixture of a plurality of copolymers having structures selected from those shown by the above formula. The hydrogenated copolymer of the present invention may also be a mixture of the following polymers: a hydrogenated copolymer having one structure selected from the structures represented by the above formulae, and at least one polymer selected from the group consisting of a polymer comprising a vinyl aromatic monomer unit, a copolymer having a structure represented by the formula A-B, and a copolymer having a structure represented by the formula B-A-B.

As described above, it is required that at least one peak of loss tangent (tan. delta.) is observed in the dynamic viscoelasticity spectrum obtained for the hydrogenated copolymer of the present invention at a temperature in the range of-10 to 80 ℃, wherein the peak of loss tangent observed in the above-mentioned temperature range is attributed to the hydrogenated copolymer block (B) (which is obtained by hydrogenating an unhydrogenated random copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units). In a temperature range outside the above temperature range, a peak of loss tangent (tan δ) may or may not be observed. For example, the hydrogenated copolymer of the present invention may have a polymer block which shows a peak of loss tangent at a temperature outside the range of-10 to 80 ℃. Examples of such polymer blocks include: a hydrogenated copolymer block obtained by hydrogenating an unhydrogenated copolymer block composed of conjugated diene monomer units and vinyl aromatic monomer units, wherein the unhydrogenated copolymer block has a conjugated diene monomer unit content of 45% by weight or more than 45% by weight; and a hydrogenated polymer block obtained by hydrogenating an unhydrogenated polymer block of conjugated diene monomer units, wherein the unhydrogenated polymer block has a vinyl bond content of 30% or more. When the hydrogenated copolymer contains at least one of these polymer blocks, it is preferred that substantially no crystallization peak is observed in a Differential Scanning Calorimetry (DSC) chart obtained for the hydrogenated copolymer at-20 to 80 ℃, preferably at-50 to 100 ℃.

In the present invention, the conjugated diene monomer is a diene having a pair of conjugated double bonds. Examples of conjugated diene monomers include 1, 3-butadiene, 2-methyl-1, 3-butadiene (i.e., isoprene), 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-pentadiene, and 1, 3-hexadiene. Among these conjugated diene monomers, 1, 3-butadiene and isoprene are preferred. These conjugated diene monomers may be used alone or in combination.

Examples of vinyl aromatic monomers include styrene, alpha-methylstyrene, p-methylstyrene, divinylbenzene, 1, 1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene and N, N-diethyl-p-aminoethylstyrene. These vinyl aromatic monomers may be used alone or in combination.

As described above, the hydrogenated copolymer of the present invention is obtained by hydrogenating an unhydrogenated copolymer comprising conjugated diene monomer units and vinyl aromatic monomer units. With respect to the method for producing the unhydrogenated copolymer, there is no particular limitation, and any conventional method can be used. For example, the unhydrogenated copolymer can be produced by living anionic polymerization in a hydrocarbon as a solvent in the presence of a polymerization initiator such as an organic alkali metal compound. Examples of the hydrocarbon as the solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene.

Examples of the polymerization initiator include aliphatic hydrocarbon-alkali metal compounds, aromatic hydrocarbon-alkali metal compounds, and organic amino-alkali metal compounds, which have living anionic polymerization activities for the conjugated diene monomer and the vinyl aromatic monomer. Examples of the alkali metal include lithium, sodium and potassium. As preferred examples of the organic alkali metal compounds, mention may be made of those mentioned at C₁-C₂₀A lithium compound having at least one lithium atom in a molecule of an aliphatic or aromatic hydrocarbon (e.g., a monolithium compound, a dilithium compound, a trilithium compound, and a tetralithium compound). Specific examples of lithium compounds include n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, the reaction product of diisopropenylbenzene and sec-butyllithium, and lithium compounds derived from divinylbenzene, sec-butyllithium, and mixtures thereofButyl lithium and a small amount of 1, 3-butadiene. Other examples of lithium compounds include the organoalkali metal compounds described in U.S. Pat. No.5,708,092, GB patent No.2,241,239, and U.S. Pat. No.5,527,753.

In the present invention, when the copolymerization of the conjugated diene monomer and the vinyl aromatic monomer is carried out in the presence of an organic alkali metal compound as a polymerization initiator, a tertiary amine or an ether-based compound may be used as a vinyl bond formation controlling agent for controlling the amount of vinyl bonds (i.e., 1, 2-vinyl bonds and 3, 4-vinyl bonds) formed by the conjugated diene monomer and/or for controlling the random copolymerization of the conjugated diene monomer and the vinyl aromatic monomer.

Examples of tertiary amines include those of the formula R¹R²R³A compound represented by N, wherein R¹，R²And R³Each of which independently represents C₁-C₂₀Hydrocarbon group or C substituted by tertiary amino₁-C₂₀A hydrocarbon group. Specific examples of tertiary amines include trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ' -tetraethylethylenediamine, 1, 2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ', N ' -pentamethylethylenetriamine and N, N ' -dioctyl-p-phenylenediamine.

Examples of the ether compound include linear ether compounds and cyclic ether compounds. Examples of the linear ether compound include dimethyl ether; diethyl ether; diphenyl ether; ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dibutyl ether; and diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dibutyl ether. Examples of the cyclic ether compound include tetrahydrofuran, dioxane, 2, 5-dimethyloxolane, 2,2, 5, 5-tetramethyloxolane, 2, 2-bis (2-oxolanyl) propane and alkyl ethers of furfuryl alcohol.

In the present invention, the copolymerization of the conjugated diene monomer and the vinyl aromatic monomer in the presence of the organic alkali metal compound as a polymerization initiator may be carried out in a batch manner or in a continuous manner. Further, the copolymerization may be carried out in a manner in which a batch operation and a continuous operation are used in combination. From the viewpoint of adjusting the molecular weight distribution to obtain excellent processability, it is desirable that the copolymerization is carried out in a continuous manner. The reaction temperature for the copolymerization is generally between 0 and 180 ℃ and preferably between 30 and 150 ℃. The reaction time for the copolymerization will vary depending on other various conditions, but is generally within 48 hours, preferably between 0.1 and 10 hours. Preferably, the atmosphere of the copolymerization reaction system is an inert gas such as nitrogen. There is no particular limitation on the copolymerization reaction pressure, as long as the pressure is sufficient to maintain the monomers and the solvent in a liquid state at the reaction temperature within the above range. In addition, care must be taken to prevent the intrusion of impurities (such as water, oxygen and carbon dioxide) into the copolymerization system, which deactivate the catalyst and/or the active polymer.

After the copolymerization is completed, a coupling agent having two or more functionalities may be added to the copolymerization system to perform the coupling reaction. There is no particular limitation on the coupling agent having two or more functional groups, and any conventional coupling agent may be used. Examples of the bifunctional coupling agent include dihalides such as dimethyldichlorosilane and dimethyldibromosilane; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate and phthalic acid esters. Examples of the coupling agent having three or more functional groups include polyols having three or more hydroxyl groups; polyvalent epoxy compounds such as epoxidized soybean oil and glycidoxy bisphenol a; polyhalogenated compounds, e.g. of formula R_4-nSiX_nA halogenated silicon compound represented by (I), wherein each R independently represents C₁-C₂₀A hydrocarbon group, each X independently represents a halogen atom, and n is 3 or 4; and is represented by the formula R_1-nSnX_nA halogenated tin compound represented by (I), wherein each R independently represents C₁-C₂₀A hydrocarbon group, each X independently represents a halogen atom, and n is 3 or 4. Halogenated siliconizationSpecific examples of compounds include methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride and bromination products thereof. Specific examples of the halogenated tin compound include methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. In addition, dimethyl carbonate, diethyl carbonate, or the like can be used as the polyfunctional coupling agent.

The hydrogenated copolymer of the present invention can be produced by hydrogenating the unhydrogenated copolymer produced above in the presence of a hydrogenation catalyst. There is no particular limitation on the hydrogenation catalyst, and any conventional hydrogenation catalyst may be used. Examples of hydrogenation catalysts include:

(1) a supported heterogeneous hydrogenation catalyst comprising a carrier (such as carbon black, silica, alumina or diatomaceous earth) on which a metal such as Ni, Pt, Pd or Ru is supported;

(2) a so-called ziegler-type hydrogenation catalyst in which a transition metal salt (for example, an organic acid salt or an acetylacetone salt of a metal such as Ni, Co, Fe, or Cr) is used in combination with a reducing agent such as an organoaluminum compound; and

(3) homogeneous hydrogenation catalysts, such as the so-called organometallic complexes, for example, organometallic compounds containing metals such as Ti, Ru, Rh or Zr.

Specific examples of the hydrogenation catalyst include those described in examined Japanese patent application publication Nos. Showa 42-8704, Showa 43-6636, Showa 63-4841 (corresponding to U.S. Pat. No.4,501,857), Hei 1-37970 (corresponding to U.S. Pat. No.4,673,714), Hei 1-53851 and Hei 2-9041. As preferred examples of the hydrogenation catalyst, a titanocene compound and a mixture of a titanocene compound and a reducing organometallic compound can be mentioned.

Examples of the titanocene compound include those described in unexamined Japanese patent application laid-open Specification No. Hei 8-109219. As specific examples of the titanocene compound, there can be mentioned compounds having at least one ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton (for example, biscyclopentadienyltitanium dichloride and monopentamethylcyclopentadienyltitanium trichloride). Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium compounds; an organic magnesium compound; an organoaluminum compound; an organoboron compound; and an organozinc compound.

The hydrogenation reaction to produce the hydrogenated copolymer of the present invention is generally carried out at 0 to 200 ℃ and preferably at 30 to 150 ℃. The hydrogen pressure in the hydrogenation reaction is generally in the range of 0.1 to 15MPa, preferably 0.2 to 10MPa, more preferably 0.3 to 5 MPa. The hydrogenation reaction time is generally between 3 minutes and 10 hours, preferably between 10 minutes and 5 hours. The hydrogenation reaction may be carried out in a batch manner or in a continuous manner. Further, the hydrogenation reaction may be carried out in a manner in which a batch operation and a continuous operation are used in combination.

By the above-mentioned method, the hydrogenated copolymer is obtained in the form of a solution thereof in a solvent. The hydrogenated copolymer was separated from the obtained solution. If desired, the catalyst residue can be separated from the solution before the isolation of the hydrogenated copolymer. Examples of the method for separating the hydrogenated copolymer from the solution include: a method in which a polar solvent, which is a poor solvent for the hydrogenated copolymer, such as acetone or alcohol, is added to a solution containing the hydrogenated copolymer, thereby precipitating the hydrogenated copolymer, followed by recovering the hydrogenated copolymer; a method in which a solution containing a hydrogenated copolymer is added to hot water while stirring, and then the solvent is removed by stripping to recover the hydrogenated copolymer; and a method in which a solution containing the hydrogenated copolymer is directly heated to distill off the solvent.

The hydrogenated copolymer of the present invention may have incorporated therein at least one stabilizer. Examples of the stabilizer include phenol type stabilizers, phosphorus type stabilizers, sulfur type stabilizers and amine type stabilizers.

The first-order modified, hydrogenated copolymer of the present invention is explained below. The first-order modified, hydrogenated copolymer of the present invention comprises the hydrogenated copolymer of the present invention and a first-order modifier group having a functional group bonded to the hydrogenated copolymer. The first-order modifier group having a functional group is bonded to at least one terminal of the hydrogenated copolymer.

Examples of the functional group-containing primary modifier group include modifier groups having at least one functional group selected from the following: a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxyl group, a thiocarboxyl group, an aldehyde group, a thioaldehyde group, a carboxylate group, an amide group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphoester group, an amino group, an imino group, a cyano group, a pyridyl group, a quinolyl group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilane group, a tin halide group, an alkoxy tin group and a phenyl tin group. Among the above functional groups, preferred are hydroxyl, epoxy, amino, silanol and alkoxysilane groups.

As preferable examples of the first-order modifier group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group, there can be mentioned modifier groups having at least one functional group selected from the group consisting of functional groups represented by the following formulae (1) to (14):

(1)-NR¹-R⁵-OH ，

(2)-N[R⁵-OH]₂ ，

(3)-NR¹-R⁵-Si(OR⁶)₃ ，

(4)-N[R⁵-Si(OR⁶)₃]₂ ，

(10)-O-R⁵-Si(OR⁶)₃ ，

and

wherein, in formulae (1) to (14):

each R⁶Independently represent a hydrogen atom or C₁-C₈An alkyl group.

As the modifier of the above-mentioned first-order modifier group used for forming the first-order modified, hydrogenated copolymer (hereinafter, this modifier is often referred to as "first-order modifier"), there can be mentioned a general compound having at least one of the above-mentioned functional groups or capable of forming at least one of the above-mentioned functional groups. As examples of such compounds, there can be mentioned terminal modifiers described in examined Japanese patent application publication No. Hei 4-39495 (corresponding to U.S. Pat. No.5,115,035). Specific examples of the modifier are listed below.

Specific examples of the modifying agent having a functional group represented by the formulae (1) to (6) include tetraglycidyl-m-xylylenediamine, tetraglycidyl-1, 3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyl diaminodiphenylmethane, diglycidylaniline, diglycidylo-toluidine, N- (1, 3-dibutylbutylidene) -3-triethoxysilyl-1-propylamine, 4-bis (. beta. -trimethoxysilylethyl) aminostyrene, 4-bis (. beta. -triethoxysilylethyl) aminostyrene, 4-bis (. gamma. -trimethoxysilylpropyl) aminostyrene, and 4-bis (. gamma. -triethoxysilylpropyl) aminostyrene.

Specific examples of the modifying agent having a functional group represented by formula (7) include cyclic lactones such as epsilon-caprolactone, delta-valerolactone, butyrolactone, gamma-caprolactone and gamma-valerolactone.

Specific examples of the modifier having a functional group represented by formula (8) include 4-methoxy-benzophenone, 4-ethoxy benzophenone, 4, 4' -bis (methoxy) benzophenone, 4, 4, -bis (ethoxy) benzophenone, γ -glycidoxyethyltrimethoxysilane and γ -glycidoxypropyltrimethoxysilane.

Specific examples of the modifier having the functional groups represented by the formulae (9) and (10) include gamma-glycidoxybutyltrimethoxysilane, gamma-glycidoxypropyl-triethoxysilane, gamma-glycidoxypropyltripropoxysilane and gamma-glycidoxytrimethoxysilane.

Other specific examples of the modifier having the functional groups represented by the formulae (9) and (10) include γ -glycidoxypropyltriphenoxysilane, γ -glycidoxypropylmethyldimethoxysilane, γ -glycidoxypropylethyldimethoxysilane, γ -glycidoxypropylethyldiethoxysilane, γ -glycidoxypropylmethyldiethoxysilane, γ -glycidoxypropylmethyldipropoxysilane, γ -glycidoxypropylmethyldibutoxysilane, γ -glycidoxypropylmethyldiphenoxysilane, γ -glycidoxypropyldimethylmethoxysilane, γ -glycidoxypropyldiethylethoxysilane and γ -glycidoxypropyldimethylethoxysilane.

Other specific examples of the modifier having the functional groups represented by the formulae (9) and (10) also include γ -glycidoxypropyl dimethylphenoxysilane, γ -glycidoxypropyl diethylmethoxysilane, γ -glycidoxypropyl methyldiisopropenyloxysilane, bis (γ -glycidoxypropyl) dimethoxysilane, bis (γ -glycidoxypropyl) diethoxysilane, bis (γ -glycidoxypropyl) dipropoxysilane, bis (γ -glycidoxypropyl) dibutoxysilane, bis (γ -glycidoxypropyl) diphenoxysilane, bis (γ -glycidoxypropyl) methylmethoxysilane and bis (γ -glycidoxypropyl) methylethoxysilane.

Other specific examples of the modifying agent having the functional groups represented by the formulae (9) and (10) also include bis (γ -glycidoxypropyl) methylpropoxysilane, bis (γ -glycidoxypropyl) methylbutoxysilane, bis (γ -glycidoxypropyl) methylphenoxysilane, tris (γ -glycidoxypropyl) methoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -methacryloxypropyltriethoxysilane, γ -methacryloxymethyltrimethoxysilane, γ -methacryloxyethyltriethoxysilane, bis (γ -methacryloxypropyl) dimethoxysilane, tris (γ -methacryloxypropyl) methoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-trimethoxysilane and β - (3, 4-epoxycyclohexyl) ethyl-triethoxysilane.

Other specific examples of the modifying agent having the functional groups represented by the formulae (9) and (10) include:

beta- (3, 4-epoxycyclohexyl) ethyl-tripropoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-tributoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-triphenoxysilane, beta- (3, 4-epoxycyclohexyl) propyl-trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-methyldimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-methyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-methyldipropoxysilane, and beta- (3, 4-epoxycyclohexyl) ethyl-methyldibutyloxysilane.

Other specific examples of the modifying agent having the functional groups represented by the formulae (9) and (10) also include:

beta- (3, 4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-diethylethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-dimethylethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-diethylmethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyl-methyldiisopropenoxysilane.

Specific examples of the modifying agent having a functional group represented by formula (11) include 1, 3-dimethyl-2-imidazolidinone and 1, 3-diethyl-2-imidazolidinone.

Specific examples of the modifying agent having a functional group represented by formula (12) include N, N' -dimethylpropyleneurea and N-methylpyrrolidone.

The first-order modified, hydrogenated copolymer having attached thereto a modifier group having a functional group represented by formula (13) can be obtained by hydrogenating a modified, unhydrogenated copolymer obtained using a modifier having a functional group represented by formula (11). The first-order modified, hydrogenated copolymer having attached thereto a modifier group having a functional group represented by the formula (14) can be obtained by hydrogenating a modified, unhydrogenated copolymer obtained using a modifier having a functional group represented by the formula (12).

The first-order modified, hydrogenated copolymer of the present invention can be produced by modifying the hydrogenated copolymer of the present invention. Alternatively, the first-order modified, hydrogenated copolymer of the present invention may be produced by modifying a base unhydrogenated copolymer, followed by hydrogenation.

For example, when the first-order modified, hydrogenated copolymer is produced by modifying the base unhydrogenated copolymer and then hydrogenating it, the production of the first-order modified, hydrogenated copolymer is carried out as follows. The base unhydrogenated copolymer having active terminals is produced by the above-described method using an organolithium compound as a polymerization initiator. The living terminal of the base unhydrogenated copolymer is reacted with the above-mentioned first-order modifier to obtain a first-order modified, unhydrogenated copolymer, which is subsequently hydrogenated, thereby obtaining a first-order modified, hydrogenated copolymer of the present invention.

As another method for producing the first-order modified, hydrogenated copolymer of the present invention, there can be mentioned a method in which a base unhydrogenated copolymer having no active terminal is reacted with an organic alkali metal compound (e.g., an organolithium compound) (this reaction is referred to as "metallation reaction") to thereby obtain a copolymer having an alkali metal bonded to the terminal, and the obtained copolymer is subsequently reacted with a first-order modifier. In this process, the base unhydrogenated copolymer may be hydrogenated prior to the metallation reaction and the subsequent reaction of the copolymer with the first-order modifier may be carried out.

When the base unhydrogenated copolymer is reacted with the primary modifier, it is possible to convert a hydroxyl group, an amino group, or the like contained in the primary modifier into its organometallic salt, depending on the type of the primary modifier. In this case, the organic metal salt can be converted into a hydroxyl group, an amino group, or the like by reacting the organic metal salt with a compound containing active hydrogen, such as water or alcohol.

In any of the above modification methods, the modification reaction temperature is preferably between 0 and 150 ℃, more preferably between 20 and 120 ℃. The modification reaction time will vary depending on other conditions, but is preferably within 24 hours, more preferably between 0.1 and 10 hours.

The first-order modified, hydrogenated copolymer of the present invention obtained by reacting the living terminal of the base unhydrogenated copolymer with a first-order modifier, followed by hydrogenation, may contain an unmodified copolymer fraction. The amount of such an unmodified copolymer fraction in the first-order modified, hydrogenated copolymer is preferably not more than 70% by weight, more preferably not more than 60% by weight, still more preferably not more than 50% by weight, based on the weight of the first-order modified, hydrogenated copolymer.

As for the second-order modified, hydrogenated copolymer of the present invention, the following is explained. The second-order modified, hydrogenated copolymer of the present invention is obtained by reacting the first-order modified, hydrogenated copolymer of the present invention with a second-order modifier having a functional group reactive with the functional group of the first-order modifier group of the first-order modified, hydrogenated copolymer.

As preferable examples of the functional group of the second-order modifier, there can be mentioned a functional group comprising at least one group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group. It is particularly preferred that the functional groups of the secondary modifier comprise at least two functional groups selected from the above functional groups, wherein, when the at least two functional groups comprise anhydride groups, it is preferred that only one of the at least two functional groups is an anhydride group.

When the first-order modified, hydrogenated copolymer is reacted with the second-order modifier, the amount of the second-order modifier is generally from 0.3 to 10mol, preferably from 0.4 to 5mol, more preferably from 0.5 to 4mol, relative to one equivalent of the functional group of the first-order modifier group of the first-order modified, hydrogenated copolymer.

There is no particular limitation on the method of reacting the first-order modified, hydrogenated copolymer with the second-order modifier, and conventional methods may be used. Examples of the conventional methods include a method using melt-kneading (described below) and a method in which the components are reacted with each other in a state of being dissolved or dispersed in a solvent together with them (described below). In the latter method, the solvent is not particularly limited as long as it can dissolve or disperse each of these components. Examples of the solvent include hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons; a halogen-containing solvent; an ester solvent; and an ether solvent. In the method in which the components are dissolved or dispersed together in a solvent, the temperature at which the first-order modified, hydrogenated copolymer is reacted with the second-order modifier is generally from-10 to 150 ℃, preferably from 30 to 120 ℃. In this process, the reaction time will vary depending on other conditions, but is generally within 3 hours, preferably within a range of several seconds to 1 hour. As a particularly preferred method for producing the second-order modified, hydrogenated copolymer, there can be mentioned a method in which a second-order modifier is added to a solution of the first-order modified, hydrogenated copolymer to carry out a reaction, thereby obtaining a second-order modified, hydrogenated copolymer. In this method, the solution of the first-order modified, hydrogenated copolymer may be subjected to a neutralization treatment before the second-order modifier is added to the solution of the first-order modified, hydrogenated copolymer.

Examples of the secondary modifier are listed below. Examples of the secondary modifier having a carboxyl group include aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbalic acid, cyclohexanedicarboxylic acid and cyclopentanedicarboxylic acid; and aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid and pyromellitic acid.

Examples of the second-order modifier having an acid anhydride group include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1, 2-dicarboxylic anhydride, 1,2, 4, 5-benzenetetracarboxylic dianhydride, and 5- (2, 5-dioxy-tetrahydroxyfuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.

Examples of the secondary modifier having an isocyanate group include toluene diisocyanate, diphenylmethane diisocyanate and polyfunctional aromatic isocyanates.

Examples of the second-order modifier having an epoxy group include tetraglycidyl-1, 3-bisaminomethylcyclohexane, tetraglycidyl-m-xylylenediamine, diglycidylaniline, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, terephthalic acid diglycidyl ester acrylate, and the above-mentioned epoxy compounds exemplified as the first-order modifier for obtaining the first-order modified, hydrogenated copolymer.

Examples of the secondary modifying agent having a silanol group include the hydrolysis products of the above-mentioned alkoxysilane compounds exemplified as the primary modifying agent for obtaining the primary modified, hydrogenated copolymer.

Examples of the secondary modifier having an alkoxysilane group include bis- (3-triethoxysilylpropyl) -tetrasulfane (tetrasulfane), bis- (3-triethoxysilylpropyl) -disulfane (disulfane), ethoxysiloxane oligomer, and the above silane compounds exemplified as the primary modifier for obtaining the primary modified hydrogenated copolymer.

Particularly preferred examples of the secondary modifier include carboxylic acids having two or more carboxyl groups and anhydrides thereof; and a crosslinking agent having two or more groups selected from an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group. Specific examples of particularly preferred secondary modifiers include maleic anhydride, pyromellitic anhydride, 1,2, 4, 5-benzenetetracarboxylic dianhydride, toluene diisocyanate, tetraglycidyl-1, 3-bisaminomethylcyclohexane, and bis- (3-triethoxysilylpropyl) -tetrasulfane (tetrasulfane).

The hydrogenated copolymer of the present invention, which is unmodified, may be graft-modified with an α, β -unsaturated carboxylic acid or a derivative thereof (such as an anhydride, ester, amide or imide). Specific examples of α, β -unsaturated carboxylic acids and derivatives thereof include maleic anhydride, maleimide, acrylic acid esters, methacrylic acid esters, and endo-cis-bicyclo (2, 2, 1) -5-heptene-2, 3-dicarboxylic acid and anhydrides thereof.

The amount of the α, β -unsaturated carboxylic acid or its derivative is generally in the range of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the hydrogenated copolymer.

When the hydrogenated copolymer of the present invention is graft-modified, the graft modification is preferably carried out at 100-300 ℃ and more preferably at 120-280 ℃.

For details of the graft modification method, see, for example, unexamined Japanese patent application laid-open Specification No. Sho 62-79211.

The oligomer-modified hydrogenated copolymer can be obtained by reacting the first-or second-order modified, hydrogenated copolymer of the present invention with a functional oligomer (having a functional group) reactive with the functional group of the first-or second-order modifier. There is no particular limitation on the functional group of the functionalized oligomer as long as it can react with the functional group of the primary or secondary modifier group of the primary or secondary modified, hydrogenated copolymer. Preferred examples of the functional oligomer include those having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group. The number average molecular weight of the functionalized oligomer is generally between 300 and less than 30,000, preferably 500 to less than 15,000, more preferably 1,000 to less than 20,000. There is no particular limitation on the method for producing the functionalized oligomer, and any conventional method may be used. For example, the functionalized oligomer may be produced by anionic polymerization, cationic polymerization, radical polymerization, polycondensation or polyaddition.

Specific examples of functionalized oligomers include: a butadiene oligomer having at least one of the above functional groups, and a hydrogenated product thereof; isoprene oligomers having at least one of the above functional groups, and hydrogenated products thereof; an ethylene oligomer having at least one of the above functional groups; a propylene oligomer having at least one of the above functional groups; an ethylene oxide oligomer; a propylene oxide oligomer; oligomeric copolymers of ethylene oxide and propylene oxide; saponified products of oligomeric copolymers of ethylene and vinyl acetate; and oligomeric copolymers of a functionalized vinyl monomer (having at least one functional group as described above) and another functionalized vinyl monomer copolymerizable with the functionalized vinyl monomer.

By using the hydrogenated copolymer of the present invention (hereinafter, often referred to as "component (a-0)"), the first-order modified, hydrogenated copolymer of the present invention (hereinafter, often referred to as "component (a-1)") or the second-order modified, hydrogenated copolymer of the present invention (hereinafter, often referred to as "component (a-2)") in combination with a polymer other than the components (a-0), (a-1) and (a-2), a composition suitable as a raw material for producing a shaped article can be obtained. For the composition, the following is explained (hereinafter, the term "component (a)" is often used as a general name of the components (a-0), (a-1) and (a-2)).

The hydrogenated copolymer composition of the present invention comprises:

1 to 99 parts by weight of component (a-0) (i.e., the hydrogenated copolymer of the present invention), and (b) relative to 100 parts by weight of the total amount of components (a-0) and (b)

The first-order modified, hydrogenated copolymer composition of the present invention comprises:

1 to 99 parts by weight of component (a-1) (i.e., the first-order modified, hydrogenated copolymer of the present invention), and (b) relative to 100 parts by weight of the total amount of components (a-1) and (b)

The second-order modified, hydrogenated copolymer composition of the present invention comprises:

1 to 99 parts by weight of component (a-2) (i.e., the second-order modified, hydrogenated copolymer of the present invention), and (b) relative to 100 parts by weight of the total amount of components (a-2) and (b)

In each of the hydrogenated copolymer composition, the first-order modified, hydrogenated copolymer composition and the second-order modified, hydrogenated copolymer composition, the component (a)/component (b) weight ratio is preferably 2/98 to 90/10, more preferably 5/95 to 70/30.

When the component (b) is a thermoplastic resin, each of the hydrogenated copolymer composition, the first-order modified, hydrogenated copolymer composition and the second-order modified, hydrogenated copolymer composition has excellent mechanical properties and excellent abrasion resistance. On the other hand, when the component (b) is a rubbery polymer, each of the hydrogenated copolymer composition, the first-order modified, hydrogenated copolymer composition and the second-order modified, hydrogenated copolymer composition has excellent properties in terms of tensile strength, elongation and abrasion resistance.

Examples of the thermoplastic resin usable as component (b) include block copolymer resins of conjugated diene monomers and vinyl aromatic monomers, and hydrogenated products thereof (other than the hydrogenated copolymer of the present invention); a polymer of a vinyl aromatic monomer; a copolymer resin of a vinyl aromatic monomer and at least one vinyl monomer (other than the vinyl aromatic monomer), such as ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid ester (e.g., methyl acrylate), methacrylic acid ester (e.g., methyl methacrylate), acrylonitrile or methacrylonitrile; rubber-modified styrene resin (HIPS); acrylonitrile/butadiene/styrene copolymer resin (ABS); and methacrylate/butadiene/styrene copolymer resins (MBS).

Other examples of the thermoplastic resin which can be used as component (b) include ethylene polymer resins such as polyethylene, copolymers of ethylene with a comonomer copolymerizable with ethylene wherein the content of the ethylene monomer unit is 50% by weight or more than 50% by weight (for example, ethylene/propylene copolymer, ethylene/butene copolymer, ethylene/hexene copolymer, ethylene/octene copolymer, or ethylene/vinyl acetate copolymer or a hydrolysate thereof), ethylene/acrylic acid ionomers and chlorinated polyethylene; propylene polymer resins such as polypropylene, copolymers of propylene with a comonomer copolymerizable with propylene, wherein the content of the propylene monomer unit is 50% by weight or more than 50% by weight (for example, propylene/ethylene copolymer or propylene/ethyl acrylate copolymer), and chlorinated polypropylene; cyclic olefin type resins such as ethylene/norbornene resins; a butene polymer resin; a vinyl chloride polymer resin; and vinyl acetate polymer resins and hydrolysis products thereof.

Other examples of thermoplastic resins that can be used as component (b) include polymers of acrylic acid, and polymers of its esters or amides; an acrylate polymer resin; polymers of acrylonitrile, polymers of methacrylonitrile, and copolymers of acrylonitrile and methacrylonitrile; a nitrile resin which is a copolymer of an acrylonitrile type monomer and a comonomer copolymerizable with the acrylonitrile type monomer (wherein the content of the acrylonitrile type monomer unit is 50% by weight or more than 50% by weight); polyamide resins such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12 and nylon-6/nylon-12 copolymers; a polyester resin; a thermoplastic polyurethane resin; polycarbonates, such as poly-4, 4 '-dioxybiphenyl-2, 2' -propane carbonate; thermoplastic polysulfones such as polyether sulfones and polyallyl sulfones; an oxymethylene polymer resin; polyphenylene ether resins such as poly (2, 6-dimethyl-1, 4-phenylene) ether; polyphenylene sulfide resins such as polyphenylene sulfide and poly 4, 4' diphenylene sulfide; a polyallylate (polyallylate) resin; a ketone ether homopolymer or copolymer; a polyketone resin; a fluororesin; polyoxybenzoyl-type polymers; a polyimide resin; and butadiene polymer resins such as 1, 2-polybutadiene and trans-polybutadiene.

Among these thermoplastic resins (b), preferred are styrene resins such as polystyrene and rubber-modified styrene resins; ethylene polymer resins such as polyethylene, ethylene/propylene copolymer, ethylene/propylene/butene copolymer, ethylene/hexene copolymer, ethylene/octene copolymer, ethylene/vinyl acetate copolymer, ethylene/acrylate copolymer and ethylene/methacrylate copolymer; propylene polymer resins such as polypropylene and propylene/ethylene copolymers; a polyamide resin; a polyester resin; and a polycarbonate resin.

The number average molecular weight of the thermoplastic resin (b) used in the present invention is generally 1,000 or more, preferably 5,000-5,000,000, more preferably 10,000-1,000,000. The number average molecular weight of the thermoplastic resin (b) can be measured by GPC.

Examples of the rubbery polymer usable as the component (b) include butadiene rubber and its hydrogenated product; styrene/butadiene rubber and its hydrogenated products (other than the hydrogenated copolymer of the present invention); isoprene rubber; acrylonitrile/butadiene rubber and its hydrogenated products; 1, 2-polybutadiene; olefin-type elastomers such as chloroprene rubbers, ethylene/propylene/diene rubbers (EPDM), ethylene/butene/diene rubbers, ethylene/butene rubbers, ethylene/hexene rubbers and ethylene/octene rubbers; butyl rubber; acrylic rubber; a fluororubber; silicone rubber; and chlorinated polyethylene rubber.

Other examples of rubbery polymers that can be used as component (b) include epichlorohydrin rubbers; an α, β -unsaturated nitrile/acrylate/conjugated diene copolymer rubber; a urethane rubber; polysulfide rubber; styrene-type elastomers (e.g., styrene/butadiene block copolymers and hydrogenated products thereof, and styrene/isoprene block copolymers and hydrogenated products thereof); and natural rubber.

Among these rubber polymers (b), preferred are styrene-type elastomers (such as styrene/butadiene block copolymers and hydrogenated products thereof, and styrene/isoprene block copolymers and hydrogenated products thereof); 1, 2-polybutadiene; olefin-type elastomers (e.g., ethylene/butene rubber, ethylene/octene rubber, and ethylene/propylene/diene rubber (EPDM)); and butyl rubber.

Each of these rubbery polymers can be modified by introducing a functional group such as a carboxyl group, a carbonyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an amino group, a silanol group or an alkoxysilane group thereinto.

The number average molecular weight of the rubber-like polymer (b) used in the present invention is generally 10,000 or more, preferably 20,000-1,000,000, more preferably 30,000-800,000. The number average molecular weight of the rubbery polymer (b) can be measured by GPC.

The polymers as component (b) may be used alone or in combination. There is no particular limitation on the combination of the polymers used as component (b). For example, a plurality of thermoplastic resins may be used in combination. Alternatively, a plurality of rubbery polymers may be used in combination. Further, at least one thermoplastic resin and at least one rubbery polymer may be used in combination.

In the case where the component (a) is the first-order modified, hydrogenated copolymer or the second-order modified, hydrogenated copolymer, when at least one polymer selected from the group consisting of a thermoplastic resin having a functional group and a rubbery polymer having a functional group is used as the component (b), the compatibility between the component (a) and the component (b) is remarkably improved. The functional group-containing thermoplastic resin and the functional group-containing rubbery polymer may be selected from the thermoplastic resins and rubbery polymers listed above, respectively. Preferred examples of the thermoplastic resin having a functional group and the rubbery polymer having a functional group include ethylene polymers having a functional group, propylene polymer resins having a functional group, polyester resins, polyamide resins, polycarbonate resins and polyurethane resins.

As an example of the composition comprising the first-order modified, hydrogenated copolymer (i.e., component (a-1)), component (b), and the second-order modifier, there can be mentioned a composition comprising:

1 to 99 parts by weight, preferably 2 to 90 parts by weight, more preferably 5 to 70 parts by weight of the component (a-1) relative to 100 parts by weight of the total amount of the components (a-1) and (b),

99 to 1 part by weight, preferably 98 to 10 parts by weight, more preferably 95 to 30 parts by weight of component (b), and

0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight, more preferably 0.05 to 7 parts by weight of a secondary modifier, relative to 100 parts by weight of the total amount of components (a-1) and (b).

When the component (b) is a thermoplastic resin, the weight ratio of the component (a-1)/the component (b) is preferably 2/98 to 90/10, more preferably 5/95 to 60/40, still more preferably 10/90 to 40/60.

Each of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention may contain at least one additive, if desired. There is no particular limitation on the additive as long as it is generally used in thermoplastic resins or rubbery polymers.

Examples of additives include those described in "Gomu Purasuchikku Haigou Yakuhin (additive for Rubber and plastics)" (Rubber Digest Co., Ltd., Japan). Specific examples of the additives include inorganic fillers such as silica, calcium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, talc, mica, silicic acid (white carbon) and titanium dioxide; pigments such as carbon black and iron oxide; lubricants, such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate and ethylene bis-stearamide; a release agent; plasticizers, such as organopolysiloxanes and mineral oils; antioxidants such as hindered phenol type antioxidants and phosphorus type heat stabilizers; hindered amine-type light stabilizers; benzotriazole type ultraviolet absorbers; a flame retardant; an antistatic agent; reinforcing agents such as organic fibers, glass fibers, carbon fibers and metal whiskers; and a colorant. These additives may be used alone or in combination.

With respect to any of the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention, the method for producing the copolymer composition is not particularly limited, and any ordinary method can be used. For example, the copolymer composition can be produced by a melt-kneading method using a common mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a Ko-kneader or a multi-screw extruder. Alternatively, the composition may be produced by a process in which the components of the copolymer composition are added to a solvent, thus obtaining a solution or dispersion of a mixture of these components in the solvent, followed by heating to remove the solvent. From the viewpoint of productivity of the copolymer composition and uniform mixing of the components of the copolymer composition, a melt kneading method using an extruder is preferred. There are no particular limitations on the form of each of the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention. For example, the copolymer composition may be in the form of pellets, flakes, strands, or crumbs. Further, after the melt-kneading, the formed molten copolymer composition may be directly formed into a shaped article.

The hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention can be used in various fields. For example, each of these copolymers and copolymer compositions is suitable for use in or as (i) a reinforcing filler-containing composition, (ii) a crosslinked product, (iii) a foam, (iv) a shaped article such as a multilayer film or a multilayer sheet, (v) a building material, (vi) vibration damping, sound insulating material, (vii) an electric wire coating, (viii) an adhesive composition, and (ix) an asphalt composition. In particular, each of the copolymer and the copolymer composition can be advantageously used for or as the crosslinked product of the above item (ii), the foam of the above item (iii), the building material of the above item (v), the vibration damping, soundproofing material of the above item (vi), and the electric wire coating material of the above item (vii). Hereinafter, the above-mentioned use of the polymer and copolymer composition is explained. (As mentioned above, the term "component (a)" is often used as the general name of the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, and the second-order modified, hydrogenated copolymer, also hereinafter, the term "component (A)" is often used as the general name of the hydrogenated copolymer composition, the first-order modified, hydrogenated copolymer composition, and the second-order modified, hydrogenated copolymer composition.)

(i) Composition containing reinforcing filler

The reinforcing filler-containing composition can be produced by mixing any one of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention, with at least one reinforcing filler (which will be hereinafter often referred to as "component (c)") selected from silica-type inorganic fillers, metal oxides, metal hydroxides, metal carbonates, and carbon black. The amount of component (c) in the reinforcing filler-containing composition is 0.5 to 100 parts by weight, preferably 5 to 100 parts by weight, more preferably 20 to 80 parts by weight, relative to 100 parts by weight of component (a) or (A). The amount of component (b) in the reinforcing filler-containing composition is preferably 0 to 500 parts by weight, more preferably 5 to 300 parts by weight, still more preferably 10 to 200 parts by weight, relative to 100 parts by weight of component (a).

The silica-type inorganic filler used as reinforcing filler is composed mainly of SiO₂Solid particles of composition. Examples of the silica-type inorganic filler include silica, clay, talc, kaolin, mica, wollastonite, montmorillonite, zeolite and fibrous inorganic substances (e.g., glass fibers). Further, a silica-type inorganic filler whose surface has been imparted with hydrophobicity and a mixture of a silica-type inorganic filler and a non-silica-type inorganic filler can also be used as the reinforcing filler. Among the silica-type inorganic fillers enumerated above, silica and glass fiber are preferred. Specific examples of the silica include white carbon produced by a dry method, white carbon produced by a wet method, synthetic silicate type white carbon and so-called colloidal silica. The average particle size of the silica-type inorganic filler is preferably between 0.01 and 150 μm. The average particle diameter of the silica-type inorganic filler is more preferably between 0.05 and 1 μm, still more preferably between 0.05 and 0.5. mu.m, from the viewpoint that the silica-type inorganic filler is finely dispersed in the composition to achieve the effect of adding the filler.

The metal oxide used as the reinforcing filler is a solid particle mainly composed of MxOy (wherein M represents a metal atom, and each of x and y independently represents an integer of 1 to 6). Examples of the metal oxide include aluminum oxide, titanium oxide, magnesium oxide and zinc oxide. Furthermore, the metal oxide may be used in the form of a mixture thereof with an inorganic filler other than the metal oxide.

The metal hydroxide used as the reinforcing filler is a hydrated type inorganic filler such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, hydrated tin oxide and hydrated inorganic metal compound (e.g., borax). Among these metal hydroxides, preferred are magnesium hydroxide and aluminum hydroxide.

Examples of the metal carbonate used as the reinforcing filler include calcium carbonate and magnesium carbonate.

Further, as the reinforcing filler, various grades of carbon black such as FT, SRF, FEF, HAF, ISAF and SAF can be used. Preferably, the carbon black has a specific surface area (measured by the nitrogen adsorption method) of 50mg/g or more, and a DBP (dibutyl phthalate) oil absorption of 80ml/100g or more.

The reinforcing filler-containing composition may contain a silane coupling agent (which is hereinafter often referred to as "component (d)"). The silane coupling agent is used to enhance the interaction between the copolymer (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) and the reinforcing filler, and is a compound having a group that exhibits affinity or bonding ability to at least one of the copolymer and the reinforcing filler. As a preferred example of the silane coupling agent, there may be mentioned a compound having a polysulfide linkage group containing a silanol group or an alkoxysilane and two or more sulfur atoms, any of which may be present in the form of a mercapto group. Specific examples of the silane coupling agent include bis [3- (triethoxysilyl) propyl ] tetrasulfide, bis [3- (triethoxysilyl) propyl ] disulfide, bis [2- (triethoxysilyl) ethyl ] tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide and 3-triethoxysilylpropylbenzothiazole tetrasulfide. The amount of the silane coupling agent is in the range of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, based on the weight of the reinforcing filler, from the viewpoint of obtaining the intended effect.

The reinforcing filler-containing composition, which comprises component (a) or (A) and a reinforcing filler, may be subjected to a crosslinking reaction in the presence of a crosslinking agent to produce a crosslinked composition. Examples of the crosslinking agent include a radical generator (such as an organic peroxide or an azo compound), an oxime, a nitroso compound, a polyamine, sulfur, a sulfur-containing compound (such as sulfur monochloride, sulfur dichloride, a disulfide compound or a polymeric polysulfide compound). The amount of the crosslinking agent is generally 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, relative to 100 parts by weight of the component (a) or (A).

Examples of the organic peroxide (hereinafter, often referred to as "component (e)") used as the crosslinking agent are preferably, from the viewpoint of low odor and scorch stability (i.e., one property of the crosslinking reaction which does not occur when the components of the composition are mixed with each other, but occurs when the resulting mixture is placed under conditions suitable for crosslinking), including 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 1, 3-bis (t-butylperoxyisopropyl) benzene, 1, 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, n-butyl 4, 4-bis (t-butylperoxy) valerate and di-t-butyl peroxide. Other examples of organic peroxides used as crosslinking agents include dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, t-butyl perbenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide and t-butylperoxycumene.

In the above-mentioned crosslinking reaction, a crosslinking accelerator (hereinafter often referred to as "component (f)") can be used in a desired amount. Examples of the crosslinking accelerator include sulfenamide type accelerators, guanidine type accelerators, thiuram type accelerators, aldehyde-amine type accelerators, aldehyde-ammonia type accelerators, thiazole type accelerators, thiourea type accelerators and dithiocarbamate type accelerators. In addition, co-crosslinking agents, such as zinc white or stearic acid, may also be used in the desired amounts.

Further, when the above-mentioned organic peroxide is used for crosslinking a composition containing a reinforcing filler, a crosslinking accelerator may be used in combination with the organic peroxide. Examples of the crosslinking accelerator that can be used in combination with the organic peroxide include sulfur; auxiliaries for peroxide crosslinking agents (hereinafter often referred to as "component (g)"), such as p-quinonedioxime, p, p '-dibenzoyl quinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine and trimethylolpropane-N, N' -m-phenylenedimaleimide; divinylbenzene; triallyl cyanurate; multifunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate; polyfunctional vinyl monomers (hereinafter often referred to as "component (h)") such as vinyl butyrate and vinyl stearate. The amount of the crosslinking accelerator as described above is generally 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, relative to 100 parts by weight of the component (a) or (A).

The above-mentioned crosslinking reaction can be carried out by a conventional method. For example, for the crosslinking reaction temperature, the temperature is 120-200 ℃, preferably 140-180 ℃. The crosslinked reinforcing filler-containing composition has excellent properties in terms of heat resistance, flexibility and oil resistance.

In order to improve the processability of the reinforcing filler-containing composition, a rubber softener (hereinafter often referred to as "component (i)") may be added. As the rubber softener, it is preferable to use mineral oil, or a liquid or low molecular weight synthetic softener. More preferably, a naphthenic and/or paraffinic type process oil or extender oil is used, which is generally used for softening the rubber, for increasing the volume of the rubber or for improving the processability of the rubber. The mineral oil type softener is a mixture of aromatic compounds, cycloalkanes, and paraffins. For mineral oil type softeners, those in which the number of carbon atoms constituting the paraffin chain is 50% or more than 50% (based on the total number of carbon atoms present in the softener) are referred to as "paraffin type softeners"; softeners in which the number of carbon atoms constituting the cycloalkane ring is 30 to 45% (based on the total number of carbon atoms present in the softener) are referred to as "cycloalkane softeners"; and softeners in which the number of carbon atoms constituting the aromatic ring is greater than 30% (based on the total number of carbon atoms present in the softener) are referred to as "aromatic-type softeners". The compositions containing reinforcing fillers may also contain synthetic softeners, such as polyisobutylene, low molecular weight polybutadiene or liquid paraffin. However, the above-mentioned mineral oil type softening agent is more preferable. The amount of the rubber softener in the reinforcing filler-containing composition is in the range of 0 to 100 parts by weight, preferably 10 to 90 parts by weight, more preferably 30 to 90 parts by weight, relative to 100 parts by weight of the component (a) or (A). When the amount of the rubber softener exceeds 100 parts by weight, the rubber softener is likely to bleed out from the composition, thus causing a risk: the surface of the composition may develop tackiness.

The reinforcing filler-containing composition comprising the component (a) or (A) and a reinforcing filler can be used as a building material, a wire coating material, a vibration damping material and the like. Furthermore, the compositions containing reinforcing fillers in crosslinked form can be used for the production of tires, rubber bumpers, belts, industrial articles, rubber shoes, foams and the like, making use of their properties.

(ii) Crosslinked product

The hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention can be crosslinked in the presence of a crosslinking agent to obtain a crosslinked product (i.e., a crosslinked hydrogenated copolymer, a crosslinked first-order modified, hydrogenated copolymer, a crosslinked second-order modified, hydrogenated copolymer, a crosslinked hydrogenated copolymer composition, a crosslinked first-order modified, hydrogenated copolymer composition, and a crosslinked second-order modified, hydrogenated copolymer composition, respectively). By crosslinking these copolymers and copolymer compositions, the heat resistance (evaluated in terms of high temperature C-Set) and flexibility of the copolymers and copolymer compositions can be improved. In each of the above crosslinked products, the component (a)/component (b) weight ratio, that is, the weight ratio of the component (a) (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) to the component (b), is generally in the range of 10/90 to 100/0, preferably 20/80 to 90/10, more preferably 30/70 to 80/20.

In the present invention, with respect to any one of the copolymer and the copolymer composition, the crosslinking method thereof is not particularly limited. However, it is preferred to use the so-called "dynamic crosslinking" method. In this dynamic crosslinking method, the components of the desired crosslinked product (including the crosslinking agent) are melt-kneaded at a temperature at which the crosslinking reaction occurs, and thus the mixing of the components and the crosslinking reaction are simultaneously performed. Details of this method are described in a.y.coran et al, rub.chem.and technol., vol 53, p 141 (1980). In the dynamic crosslinking process, the crosslinking reaction is generally carried out by using a closed kneader such as a Banbury mixer or a pressure kneader, or a single-screw or twin-screw extruder. The kneading temperature is generally between 130 and 300 ℃ and preferably between 150 ℃ and 250 ℃. The kneading time is generally between 1 and 30 minutes. Examples of the crosslinking agent used in the dynamic crosslinking method include organic peroxides and phenolic resin type crosslinking agents. The amount of the crosslinking agent is generally between 0.01 and 15 parts by weight, preferably between 0.04 and 10 parts by weight, relative to 100 parts by weight of component (a) or (A).

As the organic peroxide used as a crosslinking agent in the dynamic crosslinking method, the above-mentioned component (e) can be used. When the crosslinking reaction is carried out by using an organic peroxide, the above-mentioned component (f) may be used as a crosslinking accelerator, wherein, if desired, the component (f) may be used in combination with the above-mentioned component (g) and/or the above-mentioned component (h). The amount of the crosslinking accelerator is generally in the range of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, relative to 100 parts by weight of the component (a) or (A).

Each of the crosslinked products of the present invention may further contain an additive, if desired, as long as the properties of the crosslinked product are not adversely affected. Examples of the additives include softening agents, heat stabilizers, antistatic agents, weathering stabilizers, antioxidants, fillers, colorants and lubricants. The above-mentioned component (i) can be used as a softener for adjusting hardness and fluidity of the final product. The softening agent may be added just before or during the kneading of the components of the crosslinked product, or incorporated into the copolymer (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) during the production process, to thereby obtain the copolymer in the form of an oil extended rubber. The amount of the softening agent is generally between 0 and 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight, relative to 100 parts by weight of the component (a) or (A). The above-mentioned component (c) may be used as a filler in the crosslinked product. The amount of the filler is generally between 0 and 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight, relative to 100 parts by weight of component (a) or (A).

As in the case of the crosslinked form of the reinforcing filler-containing composition of item (i) above, the crosslinked product of the present invention can be advantageously used for the production of tires, rubber bumpers, belts, industrial articles, rubber shoes, foams and the like. In addition, the crosslinked product can also be desirably used as a raw material for medical equipment and a packaging material for food.

(iii) Foam body

Each of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention can also be used in the form of a foam. Each of the foams of the present invention is generally produced by a method in which a filler (which will be hereinafter often referred to as "component (i)") is added to the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, or the second-order modified, hydrogenated copolymer composition of the present invention, thereby producing a composition, followed by foaming. The amount of component (b) in the foam is generally between 5 and 95% by weight, preferably between 5 and 90% by weight, more preferably between 5 and 80% by weight, based on the weight of component (a).

The amount of filler (j) is generally between 5 and 95% by weight, preferably between 10 and 80% by weight, more preferably between 20 and 70% by weight, based on the weight of the foam.

Examples of the filler (j) used for producing the foam of the present invention include inorganic fillers such as the above-mentioned reinforcing filler (component (c)), calcium sulfate, barium sulfate, potassium titanate fiber whisker, mica, graphite and carbon fiber; and organic fillers such as wood chips, wood powder and pulp. There is no particular limitation on the form of the filler. For example, the filler may be in the form of flakes, spheres, granules or powder, or may have an irregular configuration. The above fillers may be used alone or in combination. Before use, the filler may be treated with the above-mentioned silane coupling agent (component (d)).

As the foaming method for obtaining each of the foams of the present invention, chemical methods and physical methods can be mentioned. In each of these methods, cells are distributed throughout the composition by the addition of a chemical blowing agent (such as an organic blowing agent or an inorganic blowing agent) or a physical blowing agent (hereinafter, both of the above-described chemical blowing agent and physical blowing agent are often referred to as "component (k)").

Each of the foams of the present invention can be desirably used to produce shaped articles having light weight, improved flexibility, improved design, and the like. Examples of the inorganic foaming agent include sodium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrite, azide compounds, sodium borohydride and metal powders. Examples of the organic blowing agent include azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate, N, N '-dinitrosopentamethylenetetramine, N, N' -dinitroso-N, N '-dimethylterephthalamide, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p, p' -oxybisbenzenesulfonylhydrazide and p-toluenesulfonylsemicarbazide. Examples of physical blowing agents include hydrocarbons, such as pentane, butane or hexane; halogenated hydrocarbons such as methyl chloride or methylene chloride; gases, such as nitrogen or air; and fluorinated hydrocarbons such as trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, chlorodifluoroethane or hydrofluorocarbons. The above-mentioned foaming agents may be used alone or in combination. The amount of the blowing agent is generally in the range of 0.1 to 8 parts by weight, preferably 0.3 to 6 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the component (a) or (A).

Each of the foams of the present invention may further contain additives, if desired. There is no particular limitation on the type of the additive, and any additive commonly used in thermoplastic resins or rubbery polymers can be used. Examples of the additives include those described in the above-mentioned "additive to Rubber and plastic" of Gomu Purasuchikukuhaiou Yakuhin (Rubber and plastic) "(Rubber Digest Co., Ltd., Japan).

In addition, the foams of the present invention may be crosslinked, if desired. Examples of the crosslinking method include a chemical crosslinking method by addition of a crosslinking agent (such as peroxide or sulfur) and optionally a co-crosslinking agent; and a physical crosslinking method using electron beam, radiation, or the like. The crosslinking may be performed in a static manner in which the crosslinking reaction is caused by radiation without stirring the crosslinking reaction system or in a dynamic manner in which the crosslinking reaction system is stirred. Specifically, for example, a crosslinked foam can be produced as follows. The copolymer or mixture of copolymer compositions, blowing agent and crosslinking agent is formed into a sheet. The sheet was heated at about 160 ℃ to cause foaming and crosslinking simultaneously, thereby obtaining a crosslinked foam. As the crosslinking agent, the above-mentioned component (e) (organic peroxide) and the above-mentioned component (f) (crosslinking accelerator) can be used. Furthermore, the above-mentioned components (g) and (h) may also be used in combination with the crosslinking agent. The amount of the crosslinking agent is generally in the range of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, relative to 100 parts by weight of the component (a) or (A).

Each of the foams of the present invention can be advantageously used as various shaped articles such as sheets and films. In particular, the foam of the present invention can be desirably used as a packaging material or a food container (e.g., a packaging material for fruits or eggs, a meat tray or a lunch box), which is required to exhibit high flexibility. As examples of foams to be used as packaging materials or food containers, mention may be made of foams produced by foaming a composition comprising: olefin resins (such as PP (polypropylene)); a vinyl aromatic polymer (such as PS (polystyrene)) or a rubber-modified styrene resin (such as HIPS); component (a); and optionally a block copolymer (composed of a conjugated diene monomer and a vinyl aromatic monomer) or a hydrogenated product thereof (other than the hydrogenated copolymer of the present invention).

Further, each of the foams of the present invention can be used in a cushioning hybrid article comprising a hard resin shaped article in combination with a foam. Such a cushion hybrid article is produced by an injection molding method such as the insert/cavity expansion method disclosed in unexamined japanese patent application laid-open specification No. hei 6-234133.

(iv) Multilayer film and multilayer sheet

Each of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention can also be used for producing multilayer films and multilayer sheets. Films comprising any of the above-described copolymers and copolymer compositions of the present invention have excellent properties in terms of heat resistance, shrinkage properties, heat sealability, transparency and fogging resistance. By laminating a resin layer on a film, the resulting multilayer film can be provided with various additional properties without sacrificing the above-described excellent properties of the film. With this lamination, various forms of multilayer films and sheets can be obtained, which have excellent properties, which are blocking resistance, tear growth resistance, puncture resistance, mechanical strength (e.g., elongation at break), extensibility, furling properties (i.e., the property by which a rolled film or sheet can be easily unrolled), elastic recovery properties, puncture-induced tear resistance, distortion recovery properties, and gas barrier properties.

In each of the multilayer film and the multilayer sheet, the weight ratio of component (a)/component (b), that is, the weight ratio of component (a) (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) to component (b), is generally in the range of 100/0 to 5/95, preferably 100/0 to 20/80, more preferably 100/0 to 40/60.

There is no particular limitation on the use of each of the multilayer film and the multilayer sheet. For example, the multilayer film or multilayer sheet may be used to produce wrapping films, bags, pouches, and the like. For a multilayer film having excellent stretching properties, such a multilayer film can be advantageously used as a stretch film for wrapping food, a palette (palette) stretch film, a protective film, and the like. On the other hand, for a multilayer film having excellent gas barrier properties, such a multilayer film can be advantageously used as a packaging material for foods, beverages, precision machines, medicines, and the like. Further, for heat shrinkable multilayer films, such multilayer films may be advantageously used as shrink wrap, shrink label, and the like.

(v) Building material

Each of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention can also be used as a building material. Preferably, each of the building materials of the present invention contains a filler and/or a flame retardant. The building material of the present invention has excellent properties in terms of abrasion resistance, scratch resistance and tensile properties, and is suitable as an indoor floor material, a wall material, a ceiling material and a sealing material. Furthermore, the building material of the present invention may be used in the form of a foam.

In each of the building materials of the present invention, the component (a)/component (b) weight ratio, that is, the weight ratio of the component (a) (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) to the component (b), is generally in the range of 100/0 to 5/95, preferably 95/5 to 10/90, more preferably 95/5 to 20/80.

Examples of fillers used in building materials include those listed as the component (j) of the "foam" in the above item (iii).

Examples of the flame retardant (hereinafter often referred to as "component (1)") used in the building material include: halogen type flame retardants such as bromine-containing compounds; phosphorus-type flame retardants, such as phosphorus-containing aromatic compounds; and inorganic flame retardants such as metal hydroxides.

Examples of halogen-type flame retardants include tetrabromoethane, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, tribromoneopentyl alcohol, hexabromobenzene, decabromodiphenylethane, tris (tribromophenoxy) -S-triazine, tris (2, 3-dibromopropyl) isocyanurate, bis (tribromophenoxy) ethane, ethylenebis (tetrabromophthalimide), tetrabromobisphenol A/carbonate oligomer, tetrabromobisphenol A/bisphenol A oligomer, tetrabromobisphenol S, chlorinated polyethylene, tetrabromophthalic anhydride, and tetrachlorophthalic anhydride.

However, in the present invention, it is preferable to use a flame retardant containing substantially no halogen. Specific examples of such flame retardants include phosphorus-type flame retardants such as triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tolyldiphenyl phosphate, xylyldiphenyl phosphate, resorcinol-bis (diphenyl phosphate), 2-ethylhexyl diphenyl phosphate, dimethyl methyl phosphate, triallyl phosphate, condensation products of these phosphates, ammonium phosphate and condensation products thereof, and diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate; magnesium hydroxide; aluminum hydroxide; zinc borate; barium borate; kaolin-clay; calcium carbonate; alunite; basic magnesium carbonate; calcium hydroxide; red phosphorus; a guanidine compound; a melamine compound; antimony trioxide; antimony pentoxide; sodium antimonite and silicone.

In recent years, inorganic flame retardants have been mainly used as flame retardants from the viewpoint of avoiding environmental problems. Representative examples of preferred inorganic flame retardants include aqueous metal compounds such as metal hydroxides (e.g., magnesium hydroxide, aluminum hydroxide, and calcium hydroxide), metal oxides (e.g., zinc borate and barium borate), calcium carbonate, clay, basic magnesium carbonate, and hydrotalcite. Among the above-listed inorganic flame retardants, a metal hydroxide (such as magnesium hydroxide) is more preferable from the viewpoint of effectively improving the flame retardancy of the building material. Further, the above-listed flame retardants include so-called auxiliary flame retardants which themselves have a weak ability to improve flame retardancy, but show a synergistic effect when used in combination with another flame retardant.

The amount of filler and/or flame retardant is generally between 5 and 95% by weight, preferably between 10 and 80% by weight, more preferably between 20 and 70% by weight, based on the weight of component (a) or (A). Fillers and flame retardants may be used in combination if desired. Specifically, two or more different fillers may be used in combination. Alternatively, two or more different flame retardants may be used in combination. Furthermore, at least one filler and at least one flame retardant may be used in combination. When at least one filler and at least one flame retardant are used in combination, it is preferred that the total amount of the filler and the flame retardant is within the above range.

Each of the building materials of the present invention may be used in the form of a foam (i.e., a foamed building material). The foamed building material is advantageous in that it has light weight, improved flexibility, improved design, and the like. Examples of methods for obtaining foamed building materials include chemical methods using chemical blowing agents such as inorganic blowing agents or organic blowing agents; and physical methods using physical blowing agents. In each of these methods, cells are distributed throughout the building material by the addition of a blowing agent. Examples of the blowing agent include those enumerated in item (iii) above as component (k) of the "foam". The amount of the blowing agent is generally in the range of 0.1 to 8 parts by weight, preferably 0.3 to 6 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the component (a) or (A).

Each of the building materials of the present invention can be advantageously used as various shaped articles such as sheets and films. In order to improve various properties (such as form, abrasion resistance, weather resistance and scratch resistance) of a formed article of a building material, the surface of the formed article may be treated by printing, coating, embossing, and the like.

There is no particular limitation on the use of any of the building materials of the present invention. For example, when the building material is used as an indoor floor material, a wall material or a ceiling material, the building material may be used in the form of a coating material for coating the surface of a structural material composed of concrete, metal, wood or the like. In this case, the building material is provided in the form of a sheet, film, tile, board, or the like, and is fixed to a substrate such as a structural material by using an adhesive, an adhesive material, nails, screws, or the like. In addition, the building material may be used as a sealing material, such as a gasket for improving sealability. Examples of specific uses of the building material include indoor floor materials (e.g., tiles), interior wall materials, materials for the inner wall of ceiling, and window frame gaskets, which are used in general houses, office buildings, commercial buildings, or municipal facilities, and the like.

(vi) Vibration damping, sound insulating material

Each of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention can also be used as a vibration damping, soundproofing material. Preferably, each of the vibration damping, soundproofing materials of the present invention contains a filler and/or a flame retardant. The vibration damping, sound insulating material of the present invention has excellent properties with respect to flexibility, vibration damping property, sound insulating property, abrasion resistance, scratch resistance, strength, and the like.

In each of the vibration damping, soundproofing materials of the present invention, the component (a)/component (b) weight ratio, i.e., the weight ratio of the component (a) (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) to the component (b), is generally in the range of 100/0 to 5/95, preferably 95/5 to 10/90, more preferably 95/5 to 20/80.

Examples of the filler used in the vibration damping, soundproofing material include those enumerated in item (iii) above as the component (i) of the "foam". Examples of the flame retardant used in the vibration damping, soundproofing material include those enumerated in item (v) above as the component (l) of the "building material". Preferred flame retardants are the same as those mentioned above for the building materials.

The amount of filler and/or flame retardant is generally between 5 and 95% by weight, preferably between 10 and 80% by weight, more preferably between 20 and 70% by weight, based on the weight of component (a) or (A). The filler and the flame retardant may be used in combination, if desired. Specifically, two or more different fillers may be used in combination. Alternatively, two or more different flame retardants may be used in combination. Furthermore, at least one filler and at least one flame retardant may be used in combination. When at least one filler and at least one flame retardant are used in combination, it is preferred that the total amount of the filler and the flame retardant is within the above range.

Each of the vibration damping, soundproofing materials of the present invention may be in the form of a foam (i.e., a foamed vibration damping, soundproofing material). The foamed vibration damping, sound insulating material is advantageous in that it has a light weight, improved flexibility, improved design, and the like. Examples of methods for obtaining a foamed vibration damping, soundproofing material include chemical methods using chemical foaming agents such as inorganic foaming agents or organic foaming agents; and physical methods using physical blowing agents. In each of these methods, cells are distributed throughout the vibration damping, acoustical insulation by the addition of a blowing agent. Examples of the blowing agent include those enumerated in item (iii) above as component (k) of the "foam". The amount of the blowing agent is generally in the range of 0.1 to 8 parts by weight, preferably 0.3 to 6 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the component (a) or (A).

Each of the vibration damping, soundproofing materials of the present invention can be advantageously used as various shaped articles such as sheets and films. In order to improve various properties (e.g., morphology, abrasion resistance, weather resistance and scratch resistance) of a shaped article of the vibration damping, sound insulating material, the surface of the shaped article may be treated by printing, coating, embossing, or the like.

(vii) Electric wire coating

Each of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention can also be used as an electric wire coating material. Preferably, each of the electric wire coatings of the present invention contains a filler and/or a flame retardant. The electric wire coating material of the present invention has excellent properties in terms of heat insulating properties, flexibility and peelability, and therefore the electric wire coating material is suitable for use as a coating material for electric wires, power cables, communication cables, power transmission lines and the like.

In each of the electric wire coatings of the present invention, the component (a)/component (b) weight ratio, i.e., the weight ratio of the component (a) (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) to the component (b), is generally in the range of 100/0 to 5/95, preferably 95/5 to 10/90, more preferably 95/5 to 20/80.

Examples of the filler used in the electric wire coating material include those exemplified in item (iii) above as the component (i) of the "foam". Examples of the flame retardant used in the electric wire coating material include those enumerated in the above item (v) as the component (l) of the "building material". Preferred examples of the flame retardant used in the electric wire coating material are the same as the preferred flame retardants listed in the above item (v) for the "building material".

(viii) Adhesive composition

The adhesive composition can be prepared by adding a tackifier (hereinafter often referred to as "component (n)") to any one of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention. The adhesive composition of the present invention exhibits an excellent balance of adhesive properties such as adhesive strength and exhibits excellent stability in melt viscosity at high temperatures, and therefore the adhesive composition can be advantageously used as a raw material for an adhesive layer of an adhesive tape, sheet or film and a surface protective sheet or film of an adhesive label, and as an adhesive.

In each of the adhesive compositions of the present invention, the amount of the tackifier is generally in the range of 20 to 400 parts by weight, preferably 50 to 350 parts by weight, relative to 100 parts by weight of the component (a) or (A). When the amount of the tackifier is less than 20 parts by weight, the adhesive composition may not necessarily exhibit satisfactory adhesive properties. On the other hand, when the amount of the tackifier is more than 400 parts by weight, the softening point of the adhesive composition becomes lower. Therefore, in either case, the adhesive properties of the adhesive composition tend to be impaired.

In each of the adhesive compositions of the present invention, the component (a)/component (b) weight ratio, that is, the weight ratio of the component (a) (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) to the component (b), is generally in the range of 50/50 to 97/3, preferably 60/40 to 95/5, more preferably 70/30 to 90/10.

The tackifier is not particularly limited, and any of the conventional resins imparting adhesive properties may be used. Examples of common adhesion property-imparting resins include polyterpene resins, hydrogenated rosin terpene resins, terpene/phenol resins, and alicyclic hydrocarbon resins. These tackifiers may be used alone or in combination. Specific examples of tackifiers include those described in the above-mentioned "additive for Rubber and plastic" of Gomu Purasuchikuku HaigouYakuhin (Rubber and plastic) "(Rubber Digest Co., Ltd. Japan), such as Clearon P105 (polyterpene resin), Clearon P125 (polyterpene resin), Arkon P-90 (alicyclic hydrocarbon resin) and Arkon P-115 (alicyclic hydrocarbon resin).

Each of the adhesive compositions may contain conventional softening agents, such as naphthenic processing oils, paraffinic processing oils, or mixtures thereof. Specific examples of the softening agent include rubber-softening agents exemplified as the component (i) of the "reinforcing filler-containing composition" in the above item (i). The incorporation of softeners in the adhesive composition will advantageously result in a reduction of the viscosity of the adhesive composition, and thus an improvement of the processability and adhesion properties of the adhesive composition. The amount of the softener is preferably in the range of 0 to 200 parts by weight, more preferably 0 to 150 parts by weight, relative to 100 parts by weight of the component (a) or (A). When the amount of the softening agent is more than 200 parts by weight, the retention of the adhesive property of the adhesive composition tends to be significantly impaired.

In addition, each of the adhesive compositions may contain a stabilizer, if desired. Examples of the stabilizer include antioxidants, light stabilizers and ultraviolet absorbers described in the above-mentioned "additive for Rubber and plastics" of Gomu Purasuchikuku Haigou Yakuhin (Rubber and plastics) "(Rubber Digest Co., Ltd., Japan). Meanwhile, the adhesive composition may contain at least one selected from the following: pigments such as iron oxide red and titanium dioxide; waxes, such as paraffin wax, microcrystalline wax, and low molecular weight polyethylene wax; olefinic thermoplastic resins (e.g., amorphous polyolefins and ethylene/ethyl acrylate copolymers) and low molecular weight vinyl aromatic thermoplastic resins; natural rubber; synthetic rubbers such as polyisoprene rubber, polybutadiene rubber, styrene/butadiene rubber, ethylene/propylene rubber, chloroprene rubber, acrylic rubber, isoprene/isobutylene rubber, polypentenamer rubber, styrene/butadiene block copolymers, hydrogenated block copolymers obtained by hydrogenating styrene/butadiene block copolymers, styrene/isoprene block copolymers, and hydrogenated block copolymers obtained by hydrogenating styrene/isoprene block copolymers.

There is no particular limitation on the method for producing each adhesive composition. For example, the adhesive composition may be produced by a method in which the components are uniformly mixed while being heated by using a common mixer or kneader.

Each adhesive composition exhibits not only excellent melt viscosity and excellent adhesive strength, but also excellent stability in melt viscosity. That is, the adhesive composition exhibits an excellent balance of various adhesive properties. By virtue of these excellent properties, the adhesive composition can be used as a raw material for tapes and labels, pressure-sensitive laminates, pressure-sensitive sheets, surface protection sheets and films, back-coating adhesives for fixing lightweight plastic shaped articles, back-coating adhesives and adhesives for fixing carpets or tiles. In particular, the adhesive composition can be advantageously used as a raw material for adhesive tapes, adhesive sheets and films, adhesive labels, surface protection sheets and films, and adhesives.

(ix) Asphalt composition

The asphalt composition can be prepared by adding asphalt (hereinafter, often referred to as "component (o)") to any one of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, and the second-order modified, hydrogenated copolymer of the present invention. The asphalt composition of the present invention exhibits an excellent balance of asphalt properties such as ductility and storage stability at high temperatures. By virtue of these excellent properties, the asphalt composition can be advantageously used as a raw material for road paving materials, roofing sheets, waterproof sheets, sealants, and the like.

Examples of the asphalt to be used in each of the asphalt compositions of the present invention include petroleum asphalt (i.e., asphalt by-produced from oil refining), a mixture thereof with petroleum, natural asphalt, and a mixture thereof with petroleum. Each of the above asphalts contains asphaltenes as its main component. Specific examples of bitumens include straight-run bitumens, semi-blown bitumens, blown-blown bitumens, tars, pitch tars, cutback bitumens (i.e. a mixture of bitumen and oil), and emulsified bitumens. These bitumens may be used alone or in combination.

As a preferable example of the asphalt, there can be mentioned straight asphalt having a penetration of 30 to 300, preferably 40 to 200, more preferably 45 to 150, wherein the penetration of the asphalt is measured in accordance with JIS K2207.

In each of the asphalt compositions of the present invention, the amount of the component (a) (i.e., the hydrogenated copolymer, the first-order modified, hydrogenated copolymer, or the second-order modified, hydrogenated copolymer) is generally in the range of 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, relative to 100 parts by weight of the asphalt contained in the asphalt composition.

Each of the bitumen compositions may contain additives, if desired. Examples of the additives include inorganic fillers such as calcium carbonate, magnesium carbonate, talc, silica, alumina, titanium dioxide, glass fibers and glass beads; organic reinforcing agents, such as organic fibers and coumarone/indene resins; crosslinking agents such as organic peroxides and inorganic peroxides; pigments such as titanium white, carbon black and iron oxide; a dye; a flame retardant; an antioxidant; an ultraviolet absorber; an antistatic agent; a lubricant; softeners, such as paraffinic processing oils, naphthenic processing oils, aromatic processing oils, paraffins, organopolysiloxanes, and mineral oils; a plasticizer; resins that impart adhesive properties, such as coumarone/indene resins and terpene resins.

Other examples of additives include olefin resins such as atactic polypropylene and ethylene/ethyl acrylate copolymers; a low molecular weight vinyl aromatic thermoplastic resin; natural rubber; synthetic rubbers such as polyisoprene rubber, ethylene/propylene rubber, chloroprene rubber, acrylic rubber, isoprene/isobutylene rubber, styrene/butadiene block copolymer and hydrogenated product thereof (other than the hydrogenated copolymer of the present invention), and styrene/isoprene block copolymer and hydrogenated product thereof (other than the hydrogenated copolymer of the present invention); vulcanizing agents, such as sulfur; an auxiliary vulcanizing agent; and a filler. These additives may be used alone or in combination. When it is desired to use the asphalt composition as a raw material for paving, the composition is generally used in the form of a mixture thereof with an aggregate such as mineral-type crushed stone, sand or slag.

As described above, each of the hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, the second-order modified, hydrogenated copolymer of the present invention, the hydrogenated copolymer composition of the present invention, the first-order modified, hydrogenated copolymer composition of the present invention, and the second-order modified, hydrogenated copolymer composition of the present invention can be used in various fields. When it is desired to use the copolymer or copolymer composition of the present invention in the form of a shaped article, its molding process may be carried out by a method selected from the following methods: extrusion molding, injection molding, blow molding, air pressure molding, vacuum molding, foam molding, extrusion of multiple layers, injection molding of multiple layers, high frequency fusion molding, slush molding, and calender molding. Examples of shaped articles include sheets, films, tubes, nonwovens, fibrous shaped articles, and synthetic leather substitutes. The shaped article of the copolymer or copolymer composition of the present invention can be desirably used as a packaging material for foods; materials for medical devices; household appliances and parts thereof, electronic devices and parts thereof, automobile parts, industrial parts, raw materials for household appliances and toys; rubber shoes, fiber and adhesive raw materials; and an asphalt modifier. Specific examples of the automobile parts include a side hammer (side ball), a grommet (grommet), a button, a weather strip, a window frame and its seal, an armrest, a door grip, a steering wheel handle, a panel box (container box), a headrest, an instrument panel, a bumper, a deflector (spoeller), and a storage cover for air bag equipment. Specific examples of medical devices include blood bags, bags for storing platelets, infusion bags, bags for artificial dialysis, medical tubing, and catheters. Further, the copolymer or copolymer composition of the present invention can be used for a substrate of an adhesive tape, sheet or film; a base material for a surface protective film; an adhesive for a surface protective film; carpet adhesive, stretch wrap film; a heat shrinkable film; coating the steel pipe; and a sealant.

Best Mode for Carrying Out The Invention

Hereinafter, the present invention will be described in more detail with reference to the following reference examples, examples and comparative examples, which should not be construed as limiting the scope of the present invention.

In the following examples and comparative examples, unhydrogenated copolymers were thus hydrogenated to obtain hydrogenated copolymers. As mentioned above, the unhydrogenated copolymer is often referred to as the "base unhydrogenated copolymer".

The characteristics and properties of the copolymer were measured by the following methods.

I. Various hydrogenated copolymers

I-1) styrene content:

the styrene content of the base unhydrogenated copolymer was measured by using an ultraviolet spectrophotometer (trade name: UV-2450; manufactured and sold by Shimadzu Corporation, Japan). The styrene content of the base unhydrogenated copolymer was used as the styrene content of the hydrogenated copolymer.

On the other hand, when the hydrogenated copolymer is directly subjected to measurement, the measurement is carried out using a Nuclear Magnetic Resonance (NMR) apparatus (trade name: DPX-400; manufactured and sold by BRUKER, Germany).

I-2) styrene Polymer Block content (Os value):

the styrene polymer block content of the base unhydrogenated copolymer was determined by the osmium tetroxide degradation method described in i.m.kolthoff et al, j.polym.sci., volume 1, page 429 (1946). For the degradation of the unhydrogenated copolymer, a solution obtained by dissolving 0.1g of osmic acid in 125ml of tert-butanol was used. (the value of the styrene polymer block content obtained by the osmium tetroxide degradation method is referred to as "Os value").

Also, the styrene polymer block content of the hydrogenated copolymer was directly measured by the method described in Y.tanaka et al, RUBBER CHEMISTRY and TECHNOLOGY, Vol.54, p.685 (1981), by using a Nuclear Magnetic Resonance (NMR) apparatus (trade name: JMN-270 WB; manufactured and sold by JEOL LTD., Japan). Specifically, by dissolving 30mg of the hydrogenated copolymer in 1g of deuterated chloroform, and subjecting the sample solution to¹Analysis of H-NMR spectra to obtain hydrogenated copolymers¹H-NMR spectrum. From¹An integrated value of total, an integrated value of chemical shift in the range of 6.9 to 6.3ppm, and an integrated value of chemical shift in the range of 7.5 to 6.9ppm were obtained in the H-NMR spectrum. Using these integrated values, the styrene polymer block content (Ns value) of the hydrogenated copolymer was obtained. The Ns value is then converted to the Os value. The Os value is obtained by the following calculation:

strength of styrene block (St) ((6.9 to 6.3 ppm) integrated value)/2

Random styrene (St) Strength (7.5 to 6.9 ppm) integral-3 (Block St Strength)

Ethylene/butene (EB) intensity (total integrated value) -3{ (block St intensity) + (random St intensity) }/8

Styrene polymer block content (Ns value) 104 (block St strength)/[ 104{ (block St strength) + (random St strength) } +56(EB strength) ]

Os value-0.012 (Ns)²+1.8(Ns)-13.0

I-3) content of hydrogenated copolymer block (B) obtained by hydrogenating unhydrogenated random copolymer block:

the content of the unhydrogenated random copolymer block in the base unhydrogenated copolymer is obtained from the amounts of the conjugated diene monomer and the vinyl aromatic monomer used to produce the unhydrogenated random copolymer block. The content of the unhydrogenated random copolymer block in the base unhydrogenated copolymer is used as the content of the hydrogenated copolymer block (B) in the hydrogenated copolymer.

I-4) content of hydrogenated polymer block (C) obtained by hydrogenating unhydrogenated conjugated diene polymer block:

the content of the unhydrogenated conjugated diene polymer block in the base unhydrogenated copolymer is obtained from the amount of the conjugated diene monomer used to produce the unhydrogenated conjugated diene polymer block. The content of the unhydrogenated conjugated diene polymer block in the base unhydrogenated copolymer is used as the content of the hydrogenated polymer block (C) in the hydrogenated copolymer.

I-5) vinyl bond content:

the vinyl bond content of the conjugated diene polymer block (homopolymer block) in the base unhydrogenated copolymer was calculated by the Morello method based on the measurement result using an infrared spectrophotometer (trade name: FT/IR-230; manufactured and sold by Japan Spectroscopic Co., Ltd.). On the other hand, the vinyl bond content of the conjugated diene/styrene copolymer block in the base unhydrogenated copolymer was calculated by the Hampton method based on the measurement results using the above-mentioned infrared spectrophotometer.

When the hydrogenated copolymer was directly subjected to measurement, the measurement was carried out using a Nuclear Magnetic Resonance (NMR) apparatus (trade name: DPX-400; manufactured and sold by BRUKER, Germany).

I-6) weight average molecular weight and molecular weight distribution:

the weight average molecular weight of the hydrogenated copolymer is approximately equal to the weight average molecular weight of the base unhydrogenated copolymer. Therefore, the weight average molecular weight of the base unhydrogenated copolymer is used as the weight average molecular weight of the hydrogenated copolymer.

The weight average molecular weight of the base unhydrogenated copolymer was measured by Gel Permeation Chromatography (GPC) under conditions in which tetrahydrofuran was used as a solvent and the measurement temperature was 35 ℃, by using a GPC device (manufactured and sold by waters corporation, u.s.a.). The measurement of the weight average molecular weight from the GPC chromatogram was performed by using a calibration curve obtained for a commercially available standard monodisperse polystyrene sample having a predetermined molecular weight, wherein the calibration curve was obtained by using a standard type polystyrene gel column (trade name: Shodex; manufactured and sold by Showa Denko co., ltd., Japan). The weight average molecular weight of the base unhydrogenated copolymer was obtained from the GPC chromatogram.

The number average molecular weight of the unhydrogenated copolymer was also obtained from the GPC chromatogram.

The molecular weight distribution is defined as the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

I-7) modification ratio:

the modified copolymer was adsorbed on a silica gel column but not on a polystyrene gel column. Based on such unique properties of the modified copolymer, the modification ratio of the modified copolymer is determined by the following method. A sample solution containing a modified copolymer sample and a low-molecular weight internal standard polystyrene was prepared, and the prepared sample solution was subjected to GPC using the same standard type polystyrene gel column as used in item I-6) above. On the other hand, another chromatogram was obtained by subjecting the same sample solution to GPC in the same manner as described above except that a silica gel column (trade name: Zorbax; manufactured and sold by DuPont de Nemours & Company Inc., U.S. A) was used in place of the standard type polystyrene gel column. The amount of the copolymer fraction (contained in the modified copolymer) adsorbed on the silica gel column was determined from the difference between the chromatogram obtained using the polystyrene gel column and the chromatogram obtained using the silica gel column. The modification ratio of the modified copolymer was obtained from the measured amount of the copolymer fraction.

I-8) hydrogenation ratio of double bonds in conjugated diene monomer units:

the hydrogenation ratio was measured using a Nuclear Magnetic Resonance (NMR) apparatus (trade name: DPX-400; manufactured and sold by BRUKER, Germany).

I-9) temperature at which the peak of loss tangent (tan. delta.) is observed:

a dynamic viscoelasticity spectrum was obtained using a dynamic viscoelasticity spectrum analyzer (model: DVE-VE; manufactured and sold by rhelogy co., ltd. in japan), wherein the analysis was performed at a frequency of 10 hz.

I-10) crystallization Peak and Heat at the crystallization Peak:

the crystallization peak of the hydrogenated copolymer and the amount of heat at the crystallization peak were measured using a Differential Scanning Calorimeter (DSC) (trade name: DSC 3200S; manufactured and sold by MAC Science Co., Ltd. of Japan). Specifically, the measurement was performed by the following method. The hydrogenated copolymer was added to a differential scanning calorimeter. The internal temperature of the differential scanning calorimeter was raised from room temperature to 150 ℃ at a rate of 30 ℃/min, and then, decreased from 150 ℃ to-100 ℃ at a rate of 10 ℃/min, thereby obtaining a DSC chart (i.e., a crystallization curve) of the hydrogenated copolymer. The presence or absence of a crystalline peak was confirmed from the obtained DSC chart. When a crystallization peak is observed in a DSC chart, the temperature at which the crystallization peak is observed is defined as the crystallization peak temperature and the quantity of heat at the crystallization peak is measured.

I-11) tensile strength, flexibility and tensile permanent set:

as to a sample of the hydrogenated copolymer, its tensile strength and the stress required for stretching the sample by 100% were measured in accordance with JIS K6251 under the conditions of a drawing rate of 500 mm/min and a temperature of 23 ℃ (this stress value is hereinafter referred to as "100% modulus"). The 100% modulus is used as an index of the flexibility of the hydrogenated copolymer. The smaller the 100% modulus, the higher the flexibility. It is preferable that the 100% modulus of the hydrogenated copolymer is 120kg/cm²Or lower.

The tensile permanent set of the hydrogenated copolymer is defined as follows. A sample of the hydrogenated copolymer was subjected to a tensile test (described in JIS K6262), in which the sample was stretched at a rate of 200 mm/min and at a temperature of 23 ℃ until the sample was broken. The elongation at break of the sample was measured, and the residual elongation of the sample at a time point of 24 hours after the break thereof. The tensile permanent set (%) is defined by the following formula:

tensile permanent set (%) - (L2/L1). times.100

Where L1 represents the distance between the two reticles when the sample fractured, and L2 represents the distance between the two reticles at a 24 hour time point after the fracture of the sample.

I-12) abrasion resistance:

the leather particulate surface of the sheet obtained by molding the hydrogenated copolymer was rubbed with a Rubbing cloth (canequ No.3) under a load of 500g 10,000 times by using a Color fast Rubbing Tester (trade name: AB-301; manufactured and sold by TESTER SANGYO CO., LTD., Japan). The reduction in sheet volume caused by 10,000 rubs of the sheet was measured and used as a measure of the abrasion resistance of the hydrogenated copolymer. Specifically, the abrasion resistance of the hydrogenated copolymer was evaluated by the following criteria:

very good: the volume reduction of the sheet caused by 10,000 rubs of the sheet was 0.01ml or less.

O: the volume reduction of the tablet caused by 10,000 rubs of the tablet is higher than 0.01ml to 0.05 ml.

And (delta): the reduction in volume of the tablet caused by 10,000 rubs of the tablet is above 0.05ml to 0.10 ml.

X: the reduction in volume of the tablet caused by 10,000 rubs of the tablet was above 0.10 ml.

I-13) impact scratch resistance:

the scratch resistance of the hydrogenated copolymer was evaluated by the following method. To a compression-molded sample of the hydrogenated copolymer (sheet having a thickness of 2 mm), a wedge (weight: 500g) having a pointed end of 10mm in length and 1mm in width was dropped from a point 10cm higher than the sample, thereby forming a scratch on the sample. The surface of the compression-processed sample was scanned with a laser using a surface structure measuring instrument (manufactured and sold by TOKYO SEIMITSU co., japan), thereby measuring the depth (unit: μm) of scratches on the sample. When the depth of scratches on the sample was 40 μm or less, this means that the hydrogenated copolymer exhibited excellent scratch resistance against impact. The values described in tables 1 and 4 below indicate the depth (unit: μm) of scratches on the sample.

I-14) adhesive Properties:

the adhesive strength of the hydrogenated copolymer is measured by a T-type peel strength test and is used as a measure of the adhesive properties of the hydrogenated copolymer. The greater the adhesive strength, the better the adhesive performance.

The T-peel strength test was performed under the following conditions:

adhesion conditions when preparing samples: the sample copolymer and adherend were preheated at 160 ℃ for five minutes and, then, at 1kg/cm²Was pressurized for five minutes under load, thus obtaining a sample.

Conditions for carrying out the peel strength test: the peel strength test was performed at a pull rate of 200 mm/min.

The adherend used for preparing the sample was an aluminum plate (thickness: 100 μm) or a PET film (thickness: 50 μm).

The hydrogenation catalysts I and II used in the hydrogenation of the unmodified or modified copolymers in the following examples and comparative examples were prepared by the following methods.

Reference example 1 (preparation of hydrogenation catalyst I)

The reaction vessel was purged with nitrogen. 1 l of dried, purified cyclohexane was added to the reaction vessel, followed by 100mmol of bis (. eta.5-cyclopentadienyl) titanium dichloride. While the resultant mixture was thoroughly stirred in the reaction vessel, 200mmol of trimethylaluminum in n-hexane was added to the reaction vessel, and the reaction was carried out at room temperature for about 3 days, thereby obtaining a hydrogenation catalyst I (which contained titanium).

Reference example 2 (preparation of hydrogenation catalyst II)

The reaction vessel was purged with nitrogen. Two liters of dried, purified cyclohexane were charged to the reaction vessel followed by 40mmol of bis (. eta.5-cyclopentadienyl) titanium di (p-tolyl) and 150g of 1, 2-polybutadiene having a molecular weight of about 1,000 and a 1, 2-vinyl bond content of about 85%. To the resulting solution was added a cyclohexane solution containing 60mmol of n-butyllithium, and the reaction was carried out at room temperature for 5 minutes. To the resulting reaction mixture was immediately added 40mmol of n-butanol, followed by stirring, thereby obtaining a hydrogenation catalyst II.

Example 1

The unhydrogenated copolymer was produced by conducting continuous polymerization by a method in which two reaction vessels (i.e., a first reaction vessel and a second reaction vessel) each having an internal volume of 10 liters and equipped with a stirrer and a jacket were used.

A cyclohexane solution of butadiene (butadiene concentration: 24% by weight), and a cyclohexane solution of N-butyllithium (which contained 0.110% by weight of N-butyllithium based on the total weight of the monomers (i.e., the total weight of butadiene fed to the two reaction vessels and styrene fed to the second reaction vessel)) were fed into the bottom of the first reaction vessel at feed rates of 2.06 liters/hour and 1.3 liters/hour, respectively, while a cyclohexane solution of N, N, N ', N' -Tetramethylethylenediamine (TMEDA) was fed into the bottom of the first reaction vessel at a feed rate such that the amount of TMEDA was 0.08mol per mol of the above-mentioned N-butyllithium, whereby continuous polymerization was conducted at 70 ℃ to obtain a polymerization reaction mixture containing a polymer. In the continuous polymerization, the reaction temperature was adjusted by controlling the jacket temperature. The temperature at the bottom of the first reaction vessel was about 69 ℃ and the temperature at the top of the first reaction vessel was about 70 ℃. The average residence time of the polymerization reaction mixture in the first reaction vessel was about 145 minutes. The conversion of butadiene was about 100%. A sample of the polymer in the first reaction vessel is analyzed. As a result, it was found that the polymer had a vinyl bond content of 16% as measured with respect to the butadiene monomer unit in the polymer.

The polymer solution was withdrawn from the first reaction vessel and added to the bottom of the second reaction vessel. Simultaneously with the feeding of the polymer solution, a cyclohexane solution of butadiene (butadiene concentration: 24% by weight) and a cyclohexane solution of styrene (styrene concentration: 24% by weight) were fed to the bottom of the second reaction vessel at feed rates of 3.03 liters/hr and 7.68 liters/hr, respectively, while a cyclohexane solution of TMEDA was fed to the bottom of the second reaction vessel at a feed rate such that the amount of TM EDA was 0.30mol per mol of n-butyllithium fed to the first reaction vessel, whereby continuous polymerization was conducted at 90 ℃ to obtain an unhydrogenated copolymer. The conversions of butadiene and styrene measured at the outlet of the second reaction vessel were about 100% and 98%, respectively.

The obtained unhydrogenated copolymer was analyzed by the method described above. As a result, it was found that the unhydrogenated copolymer had a styrene content of 63% by weight, a styrene polymer block content of 0% by weight, and a vinyl bond content of 14.8% by weight as measured with respect to the butadiene monomer units of the copolymer. From this calculation, it was also found that the random copolymer block of the unhydrogenated copolymer had a vinyl bond content of 14% as measured with respect to the butadiene monomer units in the random copolymer block.

The unhydrogenated copolymer had a weight average molecular weight of 170,000 and a molecular weight distribution of 1.8.

Then, the above-mentioned hydrogenation catalyst I was added to the unhydrogenated copolymer in an amount of 100ppm by weight (based on the weight of the unhydrogenated copolymer) in terms of the amount of titanium, and the hydrogenation reaction was carried out under conditions in which the hydrogen pressure was 0.7MPa and the reaction temperature was 65 ℃. After completion of the hydrogenation reaction, methanol was added to the second reaction vessel, followed by adding octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer in an amount of 0.3 parts by weight relative to 100 parts by weight of the unhydrogenated copolymer, thereby obtaining a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 1").

Polymer 1 had a hydrogenation ratio of 98%. Further, the styrene content of the polymer 1 was measured by using an NMR apparatus and was determined to be 63 wt%. That is, the content of styrene monomer units in the hydrogenated copolymer (polymer 1) was equivalent to the content of styrene monomer units in the base unhydrogenated copolymer.

The characteristics and properties of polymer 1 are shown in table 1 below.

Example 2

An unhydrogenated copolymer was produced by carrying out substantially the same continuous polymerization as in example 1, except for the following changes: the feed rates of the cyclohexane solution of butadiene and the cyclohexane solution of n-butyllithium to the first reaction vessel were changed to 4.13 liters/hr and 1.60 liters/hr, respectively; the feeding rate of the cyclohexane solution of TMEDA to the first reaction vessel was changed to a rate such that the amount of TMEDA was 0.10mol per mol of n-butyllithium; the feed rates of the cyclohexane solution of butadiene and the cyclohexane solution of styrene to the second reaction vessel were changed to 2.61 l/hr and 6.21 l/hr, respectively; the feeding rate of the cyclohexane solution of TMEDA to the second reaction vessel was changed to a rate such that the amount of TMEDA was 0.30mol per mol of n-butyllithium.

Using the produced unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 2") was produced by performing substantially the same hydrogenation reaction as in example 1. The characteristics and properties of polymer 2 are shown in table 1.

Example 3

By using the first reaction vessel used in example 1, an unhydrogenated copolymer was produced by carrying out batch polymerization as follows.

To the reaction vessel was added 20 parts by weight of a cyclohexane solution of butadiene (butadiene concentration: 24% by weight). Then, n-butyllithium was added in an amount of 0.08% by weight based on the total weight of the monomers (i.e., the total weight of butadiene and styrene added to the reaction vessel), and TMEDA was added in an amount of 0.12mol per mol of the above-mentioned n-butyllithium in the reaction vessel, and the polymerization reaction was carried out at 70 ℃ for 1 hour. Then, a sample of the formed polymer in the reaction vessel is analyzed. As a result, it was found that the polymer had a vinyl bond content of 20%. A cyclohexane solution of 25 parts by weight of butadiene and 55 parts by weight of styrene (total concentration of butadiene and styrene: 24% by weight) was added to the reaction vessel, and polymerization was carried out at 70 ℃ for 1 hour to obtain an unhydrogenated copolymer. The obtained unhydrogenated copolymer had a styrene content of 55% by weight, a styrene polymer block content of 0% by weight, a vinyl bond content of 20% by weight (measured with respect to the butadiene monomer units in the copolymer), a weight average molecular weight of 150,000 and a molecular weight distribution of 1.1.

Using the obtained unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 3") was produced by performing substantially the same hydrogenation reaction as in example 1. Polymer 3 had a hydrogenation ratio of 99%. The characteristics and properties of polymer 3 are shown in table 1.

Example 4

To the reaction vessel was added 15 parts by weight of a cyclohexane solution of butadiene (butadiene concentration: 24% by weight). Then, n-butyllithium was added in an amount of 0.09% by weight based on the total weight of the monomers (i.e., the total weight of butadiene and styrene charged into the reaction vessel), and TMEDA was added in an amount of 0.10mol per mol of the above-mentioned n-butyllithium, and the polymerization reaction was carried out at 70 ℃ for 1 hour. A cyclohexane solution of 20 parts by weight of butadiene and 50 parts by weight of styrene (total concentration of butadiene and styrene: 24% by weight) was added to the reaction vessel, and polymerization was carried out at 70 ℃ for 1 hour. Further, a cyclohexane solution of 15 parts by weight of styrene (styrene concentration: 24% by weight) was added to the reaction vessel, and polymerization was carried out at 70 ℃ for 1 hour to obtain an unhydrogenated copolymer.

The obtained unhydrogenated copolymer had a styrene content of 65% by weight, a styrene polymer block content of 15% by weight, a vinyl bond content of 18% by weight (measured with respect to the butadiene monomer units in the copolymer), a weight average molecular weight of 145,000 and a molecular weight distribution of 1.1.

Using the obtained unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 4") was produced by performing substantially the same hydrogenation reaction as in example 1. The characteristics and properties of polymer 4 are shown in table 1.

Example 5

A continuous polymerization was conducted in substantially the same manner as in example 2 to produce an unhydrogenated copolymer. After the continuous polymerization was completed, 1, 3-dimethyl-2-imidazolidinone as a modifier was added to the living polymer formed in an amount equimolar to the n-butyllithium used in the continuous polymerization, thus obtaining a modified copolymer. The modified copolymer had a modification ratio of 75%.

Using the modified copolymer, a modified, hydrogenated copolymer (hereinafter, this modified, hydrogenated copolymer is referred to as "polymer 5") was produced by carrying out substantially the same hydrogenation reaction as in example 1, except that the above-mentioned hydrogenation catalyst II was used in place of the above-mentioned hydrogenation catalyst I. Polymer 5 exhibited excellent flexibility, excellent abrasion resistance and excellent impact scratch resistance properties, comparable to those of polymer 2. It was also found that polymer 5 had excellent adhesive properties. Specifically, polymer 5 exhibited an adhesive strength of 70gf/cm on an aluminum plate and an adhesive strength of 40gf/cm on a PET film.

Comparative example 1

By using the first and second reaction vessels used in example 1, an unhydrogenated copolymer was produced by conducting continuous polymerization as follows.

A cyclohexane solution of butadiene (butadiene concentration: 24% by weight), a cyclohexane solution of styrene (styrene concentration: 24% by weight), and a cyclohexane solution of n-butyllithium (which contained 0.077% by weight of n-butyllithium based on the total weight of the monomers (i.e., the total weight of the butadiene fed to the first reaction vessel and the styrene fed to the two reaction vessels)) were fed into the bottom of the first reaction vessel at feed rates of 4.51 liters/hr, 2.06 liters/hr and 2.0 liters/hr, respectively, while the cyclohexane solution of TMEDA was fed into the bottom of the first reaction vessel at a feed rate such that the amount of TMEDA was 0.44mol per mol of the above-mentioned n-butyllithium, thereby conducting a continuous polymerization reaction at 90 ℃. In the continuous polymerization, the reaction temperature was adjusted by controlling the jacket temperature.

The polymer solution was withdrawn from the first reaction vessel and added to the bottom of the second reaction vessel. Simultaneously with the feeding of the polymer solution, a cyclohexane solution of styrene (styrene concentration: 24% by weight) was fed to the bottom of the second reaction vessel at a feeding rate of 1.37 liters/hour, thereby conducting continuous polymerization at 90 ℃ to obtain an unhydrogenated copolymer.

The obtained unhydrogenated copolymer was analyzed by the method described above. As a result, it was found that the unhydrogenated copolymer had a styrene content of 45% by weight, a styrene polymer block content of 18% by weight, and a vinyl bond content of 15% by weight (as measured with respect to the butadiene monomer units in the copolymer), a weight average molecular weight of 202,000 and a molecular weight distribution of 1.9.

Using the obtained unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 6") was produced by performing substantially the same hydrogenation reaction as in example 1. The characteristics and properties of polymer 6 are shown in table 1.

Comparative example 2

To the reaction vessel was added 20 parts by weight of a cyclohexane solution of butadiene (butadiene concentration: 24% by weight). Then, n-butyllithium was added in an amount of 0.07% by weight based on the total weight of the monomers (i.e., the total weight of butadiene and styrene fed into the reaction vessel), and TMEDA was added in an amount of 0.20mol per mol of the above-mentioned n-butyllithium, and the polymerization was carried out at 70 ℃ for 1 hour. Then, a sample of the formed polymer in the reaction vessel is analyzed. As a result, it was found that the polymer had a vinyl bond content of 25%. To the reaction vessel were added a cyclohexane solution of 50 parts by weight of butadiene and 30 parts by weight of styrene (total concentration of butadiene and styrene: 24% by weight), and TMEDA in an amount of 0.07mol per mol of the above n-butyllithium, and polymerization was carried out at 70 ℃ for 1 hour to obtain an unhydrogenated copolymer. The obtained unhydrogenated copolymer had a styrene content of 30% by weight, a styrene polymer block content of 0% by weight, a vinyl bond content of 37% by weight (measured with respect to the butadiene monomer units in the copolymer), a weight average molecular weight of 190,000 and a molecular weight distribution of 1.1.

Using the obtained unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 7") was produced by performing substantially the same hydrogenation reaction as in example 1. The characteristics and properties of polymer 7 are shown in table 1.

Comparative example 3

To the reaction vessel was added 20 parts by weight of a cyclohexane solution of butadiene (butadiene concentration: 24% by weight). Then, n-butyllithium was added in an amount of 0.08% by weight based on the total weight of the monomers (i.e., the total weight of butadiene and styrene fed into the reaction vessel), and TMEDA was added in an amount of 0.10mol per mol of the above-mentioned n-butyllithium, and the polymerization was carried out at 70 ℃ for 1 hour. Then, a sample of the formed polymer in the reaction vessel is analyzed. As a result, it was found that the polymer had a vinyl bond content of 18%. To the reaction vessel were added a cyclohexane solution of 55 parts by weight of butadiene and 20 parts by weight of styrene (total concentration of butadiene and styrene: 24% by weight), and TMEDA in an amount of 0.30mol per mol of the above n-butyllithium, and polymerization was carried out at 70 ℃ for 1 hour. Further, a cyclohexane solution of 5 parts by weight of styrene (styrene concentration: 24% by weight) was added to the reaction vessel, and polymerization was carried out at 70 ℃ for 1 hour to obtain an unhydrogenated copolymer.

The obtained unhydrogenated copolymer had a styrene content of 25% by weight, a styrene polymer block content of 5% by weight, a vinyl bond content of 22% by weight (measured with respect to the butadiene monomer units in the copolymer), a weight average molecular weight of 165,000 and a molecular weight distribution of 1.1.

Using the obtained unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 8") was produced by performing substantially the same hydrogenation reaction as in example 1. The characteristics and properties of polymer 8 are shown in table 1.

Comparative example 4

Various properties of a commercially available flexible polyvinyl chloride (PVC) (trade name: SUMIFLEX K580C F1; manufactured and sold by Sumitomo Bakelite co., ltd., japan) were measured. The results are shown in Table 1.

Various types of hydrogenated copolymer compositions

In the following examples 6 to 9, hydrogenated copolymer compositions were produced. The components used and the method of measuring the properties of the hydrogenated copolymer composition are as follows:

II-1) tensile Properties:

tensile properties (specifically, tensile strength and elongation at break) were measured in substantially the same manner as described in item I-11) above, except that the pulling rate was changed to 500 mm/min.

II-2) abrasion resistance:

the abrasion resistance was measured by substantially the same method as described in the above item I-12).

Thermoplastic resin

PP-1: propylene homopolymer (trade name: PM 801A; manufactured and sold by SunAllomer Ltd., Japan);

PP-2: random copolymer of propylene monomer units (trade name: PC 630A; manufactured and sold by SunAllomer Ltd. of Japan)

Rubbery Polymer

SEBS: a hydrogenated block copolymer obtained by hydrogenating a styrene/butadiene block copolymer (trade name: TUFTEC H1221; manufactured and sold by Japan ASAHI KASEI CORPORATION)

Examples 6 to 9

In each of examples 6 to 9, the hydrogenated copolymer, the thermoplastic resin and the rubbery polymer, in which the types and amounts of these components are shown in Table 2 below, were melt-kneaded and extruded using a twin-screw extruder (trade name: PCM 30; manufactured and sold by Ikegai Corporation, Japan) under conditions of a barrel temperature of 230 ℃ and a screw rotation speed of 300rpm, followed by pelletization, thereby obtaining a hydrogenated copolymer composition in the form of pellets. The obtained composition was subjected to compression molding to obtain a sheet having a thickness of 2 mm. Using the sheet, the above properties of the polymer composition were measured. The results are shown in Table 2.

Properties of dynamically crosslinked hydrogenated copolymer

In the following examples 10 and 11, dynamically crosslinked hydrogenated copolymers were produced. The components used and the method of measuring the properties of the copolymers are as follows:

thermoplastic resin

PP-2: the PC630A

Rubbery Polymer

SEBS: TUFTEC H1221 described above

III-1) tensile Strength and elongation at Break:

the tensile strength and elongation at break were measured by substantially the same methods as described in item II-1) above.

III-2) abrasion resistance:

the abrasion resistance was measured by substantially the same method as described in item II-2) above.

III-3) compression set:

the compression set test was carried out at 70 ℃ for 22 hours in accordance with JIS K6262. The smaller the compression set, the better the heat resistance.

Examples 10 and 11

In each of examples 10 and 11, a hydrogenated copolymer, a thermoplastic resin, a rubbery polymer and an organic peroxide (wherein the types and amounts of these components are shown in the following Table 3, and the organic peroxide is "PERHEXA 25B", manufactured and sold by NOF Corporation of Japan) were melt-kneaded and extruded using the above-mentioned twin-screw extruder, followed by pelletization, thereby obtaining a hydrogenated copolymer composition in the form of pellets. The melt-kneading in example 10 was conducted under the conditions that the barrel temperature was 210 ℃ and the screw rotation speed was 250rpm, and the melt-kneading in example 11 was conducted under the conditions that the barrel temperature was 230 ℃ and the screw rotation speed was 250 rpm. In each of examples 10 and 11, the hydrogenated copolymer composition was compression-molded by using a hydraulic molding machine (manufactured and sold by Shoji co., ltd., japan; output: 36 tons), thereby obtaining a sheet having a thickness of 2 mm. Using the sheet, the above properties of the hydrogenated copolymer composition were measured. The results are shown in Table 3.

In each of the following examples 12 to 18 and comparative example 5, an unmodified or modified copolymer having at least two styrene polymer blocks was produced. The properties of the unmodified or modified copolymer are measured by substantially the same methods as described in item I above.

Example 12

Using the first reaction vessel used in example 1, an unhydrogenated copolymer was produced by carrying out polymerization as follows.

10 parts by weight of cyclohexane was charged into the reaction vessel, and the internal temperature of the reaction vessel was adjusted to 70 ℃. N-butyllithium was added to the reaction vessel in an amount of 0.072% by weight, based on the total weight of the monomers (i.e., the total weight of butadiene and styrene charged to the reaction vessel), and TMEDA was added in an amount of 0.8mol per mol of the above-mentioned n-butyllithium. Then, a cyclohexane solution of 10 parts by weight of styrene (styrene concentration: 22% by weight) was added to the reaction vessel over about 3 minutes, and the polymerization reaction was carried out for 30 minutes while maintaining the internal temperature of the reaction vessel at about 70 ℃.

Then, a cyclohexane solution of 35 parts by weight of butadiene and 45 parts by weight of styrene (total concentration of butadiene and styrene: 22% by weight) was continuously added to the reaction vessel at a constant rate over 60 minutes while maintaining the internal temperature of the reaction vessel at about 70 ℃.

Then, a cyclohexane solution of 10 parts by weight of styrene (styrene concentration: 22% by weight) was further added to the reaction vessel over about 3 minutes, and the polymerization reaction was conducted for 30 minutes while maintaining the internal temperature of the reaction vessel at about 70 ℃, thereby obtaining an unhydrogenated copolymer. The obtained unhydrogenated copolymer had a styrene content of 65% by weight and a styrene polymer block content of 20% by weight.

Then, the above-mentioned hydrogenation catalyst I was added to the obtained unhydrogenated copolymer in an amount of 100ppm by weight (based on the weight of the unhydrogenated copolymer) in terms of the amount of titanium, and the hydrogenation reaction was carried out under conditions in which the hydrogen pressure was 0.7MPa and the reaction temperature was 65 ℃. After completion of the hydrogenation reaction, methanol was added to the reaction vessel, followed by addition of octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer in an amount of 0.3% by weight relative to the weight of the unhydrogenated copolymer, thereby obtaining a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 9"). Polymer 9 had a hydrogenation ratio of 97%. In the DSC chart obtained with polymer 9, no crystallization peak was observed. The characteristics and properties of polymer 9 are shown in table 4 below.

70 parts by weight of polymer 9, 30 parts by weight of the above-mentioned PC630A as a polypropylene resin, 25 parts by weight of calcium carbonate and 0.4 part by weight of microcrystalline wax were mixed together using a Henschel mixer. The resulting mixture was melt-kneaded under conditions of a barrel temperature of 230 ℃ and a screw rotation speed of 250rpm by the above-mentioned twin-screw extruder, thereby obtaining a composition.

Example 13

10 parts by weight of cyclohexane was charged into the reaction vessel and the internal temperature of the reaction vessel was adjusted to 70 ℃. N-butyllithium was added to the reaction vessel in an amount of 0.25% by weight, based on the total weight of the monomers (i.e., the total weight of butadiene and styrene fed to the reaction vessel), and TMEDA was added in an amount of 0.7mol per mol of the above-mentioned n-butyllithium. Then, a cyclohexane solution of 22 parts by weight of styrene (styrene concentration: 22% by weight) was added to the reaction vessel over about 3 minutes, and the polymerization reaction was carried out for 30 minutes while maintaining the internal temperature of the reaction vessel at about 70 ℃.

Then, a cyclohexane solution of 34 parts by weight of butadiene and 44 parts by weight of styrene (total concentration of butadiene and styrene: 22% by weight) was continuously fed into the reaction vessel at a constant rate over 60 minutes while maintaining the internal temperature of the reaction vessel at about 70 ℃ to obtain a living polymer of an unhydrogenated copolymer.

Then, silicon tetrachloride as a coupling agent was added to the living polymer of the unhydrogenated copolymer in an amount of 1/4mol per mol of n-butyllithium used in the polymerization, and a reaction was conducted to obtain an unhydrogenated copolymer. The obtained unhydrogenated copolymer had a styrene content of 66% by weight and a styrene polymer block content of 22% by weight.

Then, by using the unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 10") was produced by performing substantially the same hydrogenation reaction as in example 12. Polymer 10 had a hydrogenation ratio of 98%. In the DSC chart obtained with the polymer 10, no crystallization peak was observed. The characteristics and properties of polymer 10 are shown in table 4 below.

30 parts by weight of polymer 10, 35 parts by weight of a polypropylene resin (i.e., the above-mentioned PC630A), 35 parts by weight of the above-mentioned TUFTEC H1221 (obtained by hydrogenating a styrene/butadiene block copolymer) as a hydrogenated block copolymer, 50 parts by weight of calcium carbonate and 0.5 parts by weight of erucic acid amide were mixed together using a Henschel mixer. The resulting mixture was melt-kneaded under conditions of a barrel temperature of 230 ℃ and a screw rotation speed of 250rpm by the above-mentioned twin-screw extruder, thereby obtaining a composition.

Comparative example 5

Using the first reaction vessel used in example 1, an unhydrogenated copolymer was produced by conducting polymerization as follows.

10 parts by weight of cyclohexane was charged into the reaction vessel, and the internal temperature of the reaction vessel was adjusted to 70 ℃. Adding 0.0041 parts by weight of potassium tert-butoxide and 0.07 parts by weight of n-butyllithium to the reaction vessel, each relative to 100 parts by weight of the total weight of the monomers (i.e., the total weight of butadiene and styrene charged to the reaction vessel); thus, the molar ratio n-butyllithium/potassium tert-butoxide is 30. Then, 70 parts by weight of a cyclohexane solution of a mixture of butadiene and styrene (butadiene/styrene weight ratio: 20/80; total concentration of butadiene and styrene: 22% by weight) was added to the reaction vessel, and polymerization was carried out for 3 hours while maintaining the internal temperature of the reaction vessel at about 70 ℃.

Subsequently, 30 parts by weight of a cyclohexane solution of a mixture of butadiene and styrene (butadiene/styrene weight ratio: 70/30; total concentration of butadiene and styrene: 22% by weight) was fed into the reaction vessel, and polymerization was carried out for 3 hours while maintaining the internal temperature of the reaction vessel at about 70 ℃ to obtain an unhydrogenated copolymer. The unhydrogenated copolymer had a styrene content of 65% by weight and a styrene polymer block content of 8% by weight.

Then, by using the obtained unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 11") was produced by performing substantially the same hydrogenation reaction as in example 12.

Polymer 11 had a hydrogenation ratio of 97%. In the DSC chart obtained for the polymer 11, a crystallization peak was observed at 35 ℃ wherein the quantity of heat at 35 ℃ was 4.7J/g. The characteristics and properties of polymer 11 are shown in table 4.

Example 14

Using the first and second reaction vessels used in example 1, an unhydrogenated copolymer was produced by conducting continuous polymerization as follows.

A cyclohexane solution of styrene (styrene concentration: 24% by weight) and a cyclohexane solution of n-butyllithium (which contained 0.15% by weight of n-butyllithium based on the total weight of the monomers (i.e., the total weight of styrene fed to the two reaction vessels and butadiene fed to the second reaction vessel)) were fed into the bottom of the first reaction vessel at feed rates of 2.38 liters/hour and 2.0 liters/hour, respectively, while a cyclohexane solution of TM EDA was fed into the bottom of the first reaction vessel at a feed rate such that the amount of TMEDA was 0.44mol per mol of the above-mentioned n-butyllithium, thereby conducting a continuous polymerization at 70 ℃.

The polymer solution was withdrawn from the first reaction vessel and added to the bottom of the second reaction vessel. Simultaneously with the feeding of the polymer solution, a cyclohexane solution of butadiene (butadiene concentration: 24% by weight) and a cyclohexane solution of styrene (styrene concentration: 24% by weight) were fed into the bottom of the second reaction vessel at feeding rates of 4.51 liter/hr and 5.97 liter/hr, respectively, thereby conducting continuous polymerization to obtain a solution of a living polymer. In the continuous polymerization, the reaction temperature was adjusted by controlling the jacket temperature. The temperature at the bottom of the second reaction vessel was about 88 deg.c and the temperature at the top of the second reaction vessel was about 90 deg.c. The solution of the living polymer was discharged from the second reaction vessel. To the solution of the living polymer discharged from the second reaction vessel, ethyl benzoate was added in an equimolar amount to n-butyllithium added to the first reaction vessel, and a coupling reaction was conducted, thereby obtaining an unhydrogenated copolymer.

Using the obtained unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 12") was produced by performing substantially the same hydrogenation reaction as in example 13.

Polymer 12 had a styrene content of 67 wt%. For the styrene polymer block content of polymer 12, the Os value measured by the osmium tetroxide degradation method for the unhydrogenated copolymer was 20% by weight, and the Os value calculated from the Ns value measured by the NMR method for polymer 12 (i.e., hydrogenated copolymer) using the above formula was also 20% by weight. The vinyl bond content of polymer 12 was 14% by weight as measured for the butadiene monomer units in polymer 12. The vinyl bond content measured for the unhydrogenated copolymer and the vinyl bond content measured for the polymer 12 (i.e., the hydrogenated copolymer) were the same as each other (14% by weight). Polymer 12 had a hydrogenation ratio of 96%. In the dynamic viscoelasticity spectrum obtained for polymer 12, a peak of tan δ was observed at 8 ℃, wherein the peak was assigned to the styrene/butadiene random copolymer block. Further, in the DSC chart obtained for the polymer 12, no crystallization peak was observed at-50 ℃ to 100 ℃, and the quantity of heat was 0.

It was found that polymer 12 was a hydrogenated copolymer having excellent properties in terms of flexibility, tensile strength and abrasion resistance and exhibiting only a small tensile permanent set.

Example 15

Into the reaction vessel was charged 135g of a cyclohexane solution of styrene (styrene concentration: 24% by weight); a cyclohexane solution of n-butyllithium (which contains 0.065 wt% of n-butyllithium based on the total weight of the monomers (i.e., the total weight of styrene and butadiene charged to the reaction vessel)); and a cyclohexane solution of TMEDA containing 0.75mol of TMEDA per mol of n-butyllithium. Then, the polymerization reaction was carried out at about 70 ℃ for 30 minutes. Subsequently, the internal temperature of the reaction vessel was raised to 90 ℃. Then, a cyclohexane solution of 990g of styrene and 240g of butadiene (total concentration of styrene and butadiene: 24% by weight) was continuously fed into the reaction vessel at a constant rate over 1 hour, thereby carrying out polymerization while maintaining the internal temperature of the reaction vessel at about 90. + -. 3 ℃. Subsequently, 135g of a cyclohexane solution of styrene (styrene concentration: 24% by weight) was fed into the reaction vessel at a constant rate over 5 minutes, and polymerization was carried out at about 90 ℃ to thereby obtain an unhydrogenated copolymer.

Using the obtained unhydrogenated copolymer, a hydrogenated copolymer (hereinafter, this hydrogenated copolymer is referred to as "polymer 13") was produced by performing substantially the same hydrogenation reaction as in example 13. Polymer 13 had a styrene content of 84 wt%, a styrene polymer block content of 18 wt%, a vinyl bond content of 11% (measured for butadiene monomer units in polymer 13) and a hydrogenation ratio of 98%. In the dynamic viscoelasticity spectrum obtained for polymer 13, a peak of tan δ was observed at 45 ℃, wherein the peak was assigned to the styrene/butadiene random copolymer block. Further, in the DSC chart obtained for the polymer 13, no crystallization peak was observed at-50 ℃ to 100 ℃, and the quantity of heat was 0.

It was found that polymer 13 was a hydrogenated copolymer having excellent properties in terms of flexibility, tensile strength and abrasion resistance and exhibiting only a small tensile permanent set.

Example 16

A first-order modified, hydrogenated copolymer (hereinafter, this first-order modified, hydrogenated copolymer is referred to as "polymer 14") was prepared by carrying out substantially the same operation as in example 14, except for the following changes: to the solution of the living polymer discharged from the second reaction vessel, tetraglycidyl-1, 3-bisaminomethylcyclohexane (hereinafter referred to as "first-order modifier M1") as a modifier was added in an amount of 0.5mol per mol of n-butyllithium used in the polymerization; and in the hydrogenation reaction, hydrogenation catalyst II is used instead of hydrogenation catalyst I. Polymer 14 had a modification of about 75%.

Maleic anhydride (hereinafter referred to as "secondary modifier D1") was added to the solution of the polymer 14 in an amount of 1mol relative to 1 equivalent of the functional group bonded to the polymer 14 (derived from the primary modifier M1), followed by reaction at about 60 ℃ to thereby obtain a secondary modified, hydrogenated copolymer (hereinafter referred to as "polymer 15").

It was found that polymer 15 was a second-order modified, hydrogenated copolymer having excellent properties in terms of flexibility, tensile strength and abrasion resistance and exhibiting only a small tensile permanent set.

Example 17

A first-order modified, hydrogenated copolymer (hereinafter, this first-order modified, hydrogenated copolymer is referred to as "polymer 16") was prepared by carrying out substantially the same operation as in example 15, except for the following changes: to the living polymer produced in the reaction vessel, 1, 3-dimethyl-2-imidazolidinone (hereinafter referred to as "primary modifier M2") as a modifier was added in an equimolar amount to n-butyllithium used for the polymerization; and in the hydrogenation reaction, hydrogenation catalyst II is used instead of hydrogenation catalyst I. Polymer 16 had a modification of about 80%, i.e., the amount of unmodified copolymer fraction in polymer 16 was about 20% by weight, based on the weight of polymer 16.

The secondary modifier D1 was added to the polymer 16 in an amount of 2.1mol, relative to 1 equivalent of the functional group bonded to the polymer 16 (derived from the primary modifier M2), and the resulting mixture was melt-kneaded by means of the above-mentioned twin-screw extruder under conditions of a barrel temperature of 210 ℃ and a screw rotation speed of 100rpm, thereby obtaining a secondary modified, hydrogenated copolymer (hereinafter referred to as "polymer 17").

It was found that polymer 17 was a second-order modified, hydrogenated copolymer having excellent properties in terms of flexibility, tensile strength and abrasion resistance and exhibiting only a small tensile permanent set.

Example 18

A first-order modified, hydrogenated copolymer (hereinafter, this first-order modified, hydrogenated copolymer is referred to as "polymer 18") was produced by carrying out substantially the same operation as in example 17 except that gamma-glycidoxypropyltriethoxysilane was used as the first-order modifier. By using the produced polymer 18, a second-order modified, hydrogenated copolymer (hereinafter, this second-order modified, hydrogenated copolymer is referred to as "polymer 19") was produced in substantially the same operation as in example 17.

It was found that polymer 19 was a second-order modified, hydrogenated copolymer having excellent properties in terms of flexibility, tensile strength and abrasion resistance and exhibiting only a small tensile permanent set.

In each of examples 19 and 20 below, a hydrogenated copolymer composition comprising a hydrogenated copolymer having at least two styrene polymer blocks (A) was produced.

The thermoplastic resin and the rubbery copolymer used and the method for measuring the properties of the composition are the same as in item II above.

Examples 19 and 20

In each of examples 19 and 20, the hydrogenated copolymer, the thermoplastic resin and the rubbery polymer in which the types and amounts of these components are shown in Table 5 below were melt-kneaded and extruded under conditions of a barrel temperature of 230 ℃ and a screw rotation speed of 300rpm using the above-mentioned twin-screw extruder, followed by pelletization, thereby obtaining a hydrogenated copolymer composition in the form of pellets. The composition was subjected to compression molding to obtain a sheet having a thickness of 2 mm. Using the sheet, the above properties of the polymer composition were measured. The results are shown in Table 5.

Examples 21 and 22

The hydrogenated copolymer composition was produced in the form of a foam according to the formulation given in Table 6 below. It has been found that each of the foams exhibits the excellent properties sought by the present invention.

Examples 23 to 28

The hydrogenated copolymer composition was produced in the form of a foam according to the formulation given in Table 7 below. It has been found that each of the compositions exhibits the excellent properties sought by the present invention.

The invention has been described in detail with reference to the specific embodiments described above. However, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention.

The present application is based on Japanese patent application Nos. 2002-.

TABLE 1 characteristics and Properties of hydrogenated copolymer (1)

	Polymer numbering	Structure of the copolymer
		Structure of the copolymer					Hydrogenated conjugated diene Polymer Block (C)		Hydrogenated random copolymer Block (B)		Content of styrene Polymer Block (A) (% by weight)
		Vinyl bond content (%)	C Block content (% by weight)	Vinyl bond content (%)	B Block content (% by weight)		Hydrogenated conjugated diene Polymer Block (C)		Hydrogenated random copolymer Block (B)
		Vinyl bond content (%)	C Block content (% by weight)	Vinyl bond content (%)	B Block content (% by weight)	Example 1	Polymer 1	16	15	14		85	0
Example 2	Polymer 2	20	30	16	70	Example 1	Polymer 1	16	15	14	0	85	0
Example 2	Polymer 2	20	30	16	70	Example 3	Polymer 3	20	20	20	0	80	0
Example 4	Polymer 4	18	15	18	70	Example 3	Polymer 3	20	20	20	15	80	0
Example 4	Polymer 4	18	15	18	70	Comparative example 1	Polymer 6	-	0	15	15	82	18
Comparative example 2	Polymer 7	25	20	40	80	Comparative example 1	Polymer 6	-	0	15	0	82	18
Comparative example 2	Polymer 7	25	20	40	80	Comparative example 3	Polymer 8	18	20	25	0	75	5
Comparative example 4	PVC	-	-	-	-	Comparative example 3	Polymer 8	18	20	25	-	75	5

TABLE 1 characteristics and Properties (1) of the hydrogenated copolymer (continuous)

	Polymer numbering	Structure of the copolymer					Properties of the copolymer
		Structure of the copolymer					Properties of the copolymer			Styrene content (% by weight)	Weight average molecular weight (. times.10,000)	Molecular weight distribution (Mw/Mn)	Hydrogenation ratio (%)	Peak of tan. delta. (. degree. C.)	100% modulus (kg/cm)²)	Wear resistance	Impact scratch resistance (μm)
		Example 1	Polymer 1	63	17.0	1.8	98	27	32	Styrene content (% by weight)	Weight average molecular weight (. times.10,000)	Molecular weight distribution (Mw/Mn)	Hydrogenation ratio (%)	Peak of tan. delta. (. degree. C.)	100% modulus (kg/cm)²)	Wear resistance	Impact scratch resistance (μm)	◎	16
Example 2	Polymer 2	Example 1	Polymer 1	63	17.0	1.8	98	27	32	51	15.5	1.9	98	25	28	◎	5	◎	16
Example 2	Polymer 2	Example 3	Polymer 3	55	15.0	1.1	99	18	30	51	15.5	1.9	98	25	28	◎	5	◎	14
Example 4	Polymer 4	Example 3	Polymer 3	55	15.0	1.1	99	18	30	65	14.5	1.1	99	21	42	◎	20	◎	14
Example 4	Polymer 4	Comparative example 1	Polymer 6	45	20.2	1.9	98	-40	7	65	14.5	1.1	99	21	42	◎	20	×	nd
Comparative example 2	Polymer 7	Comparative example 1	Polymer 6	45	20.2	1.9	98	-40	7	30	19.0	1.1	99	-32	6	×	nd	×	nd
Comparative example 2	Polymer 7	Comparative example 3	Polymer 8	25	16.5	1.1	98	-50	6	30	19.0	1.1	99	-32	6	×	nd	×	nd
Comparative example 4	PVC	Comparative example 3	Polymer 8	25	16.5	1.1	98	-50	6	-	-	-	-	-	47	○	40	×	nd

And (4) supplementary notes: "nd" refers to the measurement not taken.

TABLE 2 Properties of the copolymer compositions

			Example 6	Example 7	Example 8	Example 9
			Example 6	Example 7	Example 8	Example 9	Formulation (parts by weight)	Hydrogenated copolymer	Polymer 2	80	80	70	40
Thermoplastic resin	PP-1	20	-	-	-			Hydrogenated copolymer	Polymer 2	80	80	70	40
	PP-1	20	-	-	-	PP-2		-	-	15	30
	Rubbery polymer	SEBS	-	20	15	PP-2		-	-	15	30	30
Performance of	Rubbery polymer	SEBS	-	20	15	Tensile Strength (kg/cm)²)		180	200	160	160	30
	Elongation at Break (%)		420	440	460	Tensile Strength (kg/cm)²)		180	200	160	160	500
	Elongation at Break (%)		420	440	460	Wear resistance		○	○	○	○	500

TABLE 3 Properties of the crosslinked product

			Example 10	Example 11
			Example 10	Example 11	Formulation (parts by weight)	Hydrogenated copolymer	Polymer 2	100	40
Thermoplastic resin	PP-2		30			Hydrogenated copolymer	Polymer 2	100	40
Thermoplastic resin	PP-2		30	Rubber compositionPolymer in the form of a polymer		SEBS		30
Organic peroxides	PERHEXA 25B	1	0.3	Rubber compositionPolymer in the form of a polymer		SEBS		30
Organic peroxides	PERHEXA 25B	1	0.3	Performance of		Tensile Strength (kg/cm)²)		155	100
Elongation at Break (%)		480	900			Tensile Strength (kg/cm)²)		155	100
Elongation at Break (%)		480	900		Wear resistance		◎	○
Compression set (%)		70	75		Wear resistance		◎	○

TABLE 4 characteristics and Properties of the hydrogenated copolymer (2)

	Polymer numbering	Structure of the copolymer
		Structure of the copolymer						Styrene content (% by weight)	Styrene Polymer Block content (% by weight)	Vinyl bond content (% by weight)	Weight average molecular weight (. times.10,000)	Molecular weight distribution (Mw/Mn)	Hydrogenation ratio (%)
		Example 12	Polymer 9	65	20	20	16.2	Styrene content (% by weight)	Styrene Polymer Block content (% by weight)	Vinyl bond content (% by weight)	Weight average molecular weight (. times.10,000)	Molecular weight distribution (Mw/Mn)	Hydrogenation ratio (%)	1.1	97
Example 13	Polymer 10	Example 12	Polymer 9	65	20	20	16.2	66	22	18	18.0	1.3	98	1.1	97
Example 13	Polymer 10	Comparative example 5	Polymer 11	65	8	15	18.5	66	22	18	18.0	1.3	98	1.1	97

(wait for)

TABLE 4 characteristics and Properties of hydrogenated copolymer (2)

(continuation)

	Polymer numbering	Structure of the copolymer		Properties of the copolymer
		Structure of the copolymer		Properties of the copolymer				Peak of tan. delta. (. degree. C.)	Peak of crystallization^*	Tensile Strength (kg/cm)²)	100% modulus (kg/cm)²)	Wear resistance	Impact scratch resistance (μm)
		Example 12	Polymer 9	1	Is absent from	280	22	Peak of tan. delta. (. degree. C.)	Peak of crystallization^*	Tensile Strength (kg/cm)²)	100% modulus (kg/cm)²)	Wear resistance	Impact scratch resistance (μm)	◎	10
Example 13	Polymer 10	Example 12	Polymer 9	1	Is absent from	280	22	2	Is absent from	250	20	◎	15	◎	10
Example 13	Polymer 10	Comparative example 5	Polymer 11	0	Presence (4.7)	240	160	2	Is absent from	250	20	◎	15	△	98

^*: when a crystallization peak is present, the number represents the heat (J/g).

TABLE 5 Properties of the Polymer compositions

			Example 19	Example 20
			Example 19	Example 20	Formulation (parts by weight)	Hydrogenated copolymer	Polymer 9	30	-
Polymer 10	-	40					Polymer 9	30	-
Polymer 10	-	40	Thermoplastic resin	PP-2			20	20
Rubbery polymer	SEBS	50	Thermoplastic resin	PP-2		40	20	20
Rubbery polymer	SEBS	50	Performance of	Tensile Strength (kg/cm)²)		40	130	140
Elongation at Break (%)		790		Tensile Strength (kg/cm)²)		700	130	140
Elongation at Break (%)		790		Wear resistance		700	○	○

TABLE 6 foam formulation

		Components	Example 21	Example 22
		Components	Example 21	Example 22	Formulation (parts by weight)	Hydrogenated copolymer	Polymer 9	20	40
Thermoplastic resin	EVA^*1	80	60			Hydrogenated copolymer	Polymer 9	20	40
Thermoplastic resin	EVA^*1	80	60	Additive agent		Talc	10	10
Peroxides and their use in the preparation of pharmaceutical preparations^*2	0.7	0.7				Talc	10	10
	0.7	0.7	Auxiliary crosslinking agent^*3			0.3	0.3
Zinc oxide	1.5	1.5	Auxiliary crosslinking agent^*3			0.3	0.3
Zinc oxide	1.5	1.5	Stearic acid			0.5	0.5
Zinc stearate	0.3	0.3	Stearic acid			0.5	0.5
Zinc stearate	0.3	0.3	Foaming agent^*4			2.5	2.5

^*1: ethylene/vinyl acetate copolymer having a vinyl acetate content of 18% by weight (product name: EVA 460; manufactured by E.I. DuPont de Nemours, USA)&Manufactured and sold by Company inc

^*2: dicumyl peroxide

^*3: triallylisocyanurate

^*4: azodicarbonamide (azodicarbonamide)

TABLE 7 formulation of various compositions

		Components	Example 23	Example 24	Example 25	Example 26	Example 27	Example 28
		Components	Example 23	Example 24	Example 25	Example 26	Example 27	Example 28	Formulation (parts by weight)	Hydrogenated copolymer	Polymer 2	-	-	-	-	40	-
Polymer 9	30	30	30	30	-	40					Polymer 2	-	-	-	-	40	-
Polymer 9	30	30	30	30	-	40	Thermoplastic resin	PP-2			20	5	5	5	-	-
ABS	-	20	-	-	-	-		PP-2			20	5	5	5	-	-
ABS	-	20	-	-	-	-		PPE		-	-	20	-	-	-
PC	-	-	-	20	-	-		PPE		-	-	20	-	-	-
PC	-	-	-	20	-	-		PE		-	-	-	-	60	60
Rubbery polymer	SEBS-2	40	30	30	30	-		PE		-	-	-	-	60	60	-
Rubbery polymer	SEBS-2	40	30	30	30	-	Oil	Paraffin oil		10	15	15	15	-	-	-
Another additive	Silicone oil	1	1	1	1	-	Oil	Paraffin oil		10	15	15	15	-	-	-

The components used were:

PP-2: random propylene copolymer PC 630A; manufactured and sold by Sun Allomer Ltd. of Japan

ABS: ABS resin (STYLAC ABS 121: manufactured and sold by Japan ASAHI KASEI CORPORATION)

PPE: polyphenylene ether resin (poly (2, 6-dimethyl-1, 4-phenylene) ether) having a reduced viscosity of 0.54

PC: PC resin (PC-110; manufactured and sold by Japan ASAHI KASEI CORPORATION)

PE: LDPE (Suntec L2340; manufactured and sold by Japan ASAHI KASEI CORPORATION)

SEBS-2: hydrogenated product of styrene/butadiene Block copolymer (TUFTEC 1272; manufactured and sold by Japan ASAHI KASEI CORPORATION)

Paraffin oil: diana process oil PW-380 (manufactured and sold by Idemitsu Kosan Ltd. in Japan)

Silicone oil: SH200-100CS (manufactured and sold by Toray Silicone Co., Ltd., Japan)

Industrial applicability

The hydrogenated copolymer of the present invention, the first-order modified, hydrogenated copolymer of the present invention, and the second-order modified, hydrogenated copolymer of the present invention have excellent properties in terms of flexibility, tensile strength, abrasion resistance, impact scratch resistance, and crosslinkability. Further, a hydrogenated copolymer composition comprising any one of the first-order and second-order modified, hydrogenated copolymers and at least one polymer selected from the group consisting of a thermoplastic resin and a rubbery polymer; and the crosslinked product of the above copolymer or copolymer composition has excellent properties in terms of mechanical properties, abrasion resistance and the like. Because of these excellent properties, each of the above-mentioned copolymer, copolymer composition and crosslinked product can be advantageously used in or as a reinforcing filler-containing composition, a foam, a multilayer film or multilayer sheet, a building material, a vibration damping, soundproofing material, a multilayer shaped article (such as a multilayer injection molded article), an electric wire coating material, a high-frequency fusing composition, a slush molding material, an adhesive composition, an asphalt composition and the like. Also, by subjecting the above-mentioned copolymer, composition and material to molding (e.g., injection molding or extrusion molding) or the like, shaped articles having various forms can be obtained, which can be advantageously used in the field of automobile parts (e.g., interior and exterior parts of automobiles), various containers (e.g., packaging containers for foods), household electric appliances, medical instruments, industrial parts, toys and the like.

Claims

the hydrogenated copolymer has the following characteristics (1) to (6):

(3) the hydrogenated copolymer has a weight average molecular weight of 30,000-1,000,000,

2. A hydrogenated copolymer according to claim 1, which comprises at least one hydrogenated polymer block (C), at least one hydrogenated copolymer block (B) and optionally at least one polymer block (A),

3. The hydrogenated copolymer according to claim 2, wherein substantially no crystallization peak ascribed to the at least one hydrogenated copolymer block (B) is observed in a Differential Scanning Calorimetry (DSC) chart obtained for the hydrogenated copolymer at-20 to 80 ℃.

4. A hydrogenated copolymer according to claim 1, which comprises at least two polymer blocks (A) and at least one hydrogenated copolymer block (B),

5. A hydrogenated copolymer according to claim 1, which is a foam.

6. The hydrogenated copolymer according to claim 1, which is a building material, a vibration damping, sound insulating material or a wire coating material.

7. A crosslinked hydrogenated copolymer obtained by subjecting the hydrogenated copolymer of claim 1 to a crosslinking reaction in the presence of a crosslinking agent.

8. A hydrogenated copolymer composition comprising:

1 to 99 parts by weight of the (a-0) hydrogenated copolymer of claim 1, relative to 100 parts by weight of the total amount of the components (a-0) and (b), and

9. The hydrogenated copolymer composition according to claim 8, which is a foam.

10. The hydrogenated copolymer composition according to claim 8, which is a building material, a vibration damping, sound insulating material or an electric wire coating material.

11. A crosslinked hydrogenated copolymer composition obtained by subjecting the hydrogenated copolymer composition of claim 8 to a crosslinking reaction in the presence of a crosslinking agent.

12. An adhesive composition comprising:

100 parts by weight of the hydrogenated copolymer (a-0) of claim 1, and

20 to 400 parts by weight of a tackifier (n).

13. A bitumen composition comprising:

0.5 to 50 parts by weight of the hydrogenated copolymer (a-0) of claim 1, and

100 parts by weight of asphalt (o).

14. A first-order modified, hydrogenated copolymer comprising the hydrogenated copolymer of claim 1 and a functional group-containing first-order modifier group bonded to the hydrogenated copolymer.

15. The first-order modified, hydrogenated copolymer according to claim 14, wherein the first-order modifier group has at least one functional group selected from the group consisting of: a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxyl group, a thiocarboxyl group, an aldehyde group, a thioaldehyde group, a carboxylate group, an amide group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphoester group, an amino group, an imino group, a cyano group, a pyridyl group, a quinolyl group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilane group, a tin halide group, an alkoxy tin group and a phenyl tin group.

16. The first-order modified, hydrogenated copolymer according to claim 15, wherein the first-order modifier group has at least one functional group selected from the group consisting of functional groups represented by the following formulae (1) to (14):

(1) -NR¹-R⁵-OH ，

(2) -N[R⁵-OH]₂ ，

(3) -NR¹-R⁵-Si(OR⁶)₃ ，

(4) -N[R⁵-Si(OR⁶)₃]₂ ，

(10) -O-R⁵-Si(OR⁶)₃ ，

and

wherein, in formulae (1) to (14):

each R⁶Independently represent a hydrogen atom or C₁-C₈An alkyl group.

17. The first-order modified, hydrogenated copolymer according to claim 14, which is a foam.

18. A crosslinked, first-order modified, hydrogenated copolymer obtained by subjecting the first-order modified, hydrogenated copolymer of claim 14 to a crosslinking reaction in the presence of a crosslinking agent.

19. A first-order modified, hydrogenated copolymer composition comprising:

1 to 99 parts by weight of (a-1) the first-order modified, hydrogenated copolymer of claim 14, relative to 100 parts by weight of the total amount of components (a-1) and (b), and

20. The first-order modified, hydrogenated copolymer composition according to claim 19, which is a foam.

21. A crosslinked, first-order modified, hydrogenated copolymer composition obtained by subjecting the first-order modified, hydrogenated copolymer composition of claim 19 to a crosslinking reaction in the presence of a crosslinking agent.

22. An adhesive composition comprising:

100 parts by weight of the first-order modified, hydrogenated copolymer (a-1) of claim 14, and

20 to 400 parts by weight of a tackifier (n).

23. A bitumen composition comprising:

0.5 to 50 parts by weight of the first-order modified, hydrogenated copolymer (a-1) of claim 14, and

100 parts by weight of asphalt (o).

24. A second-order modified, hydrogenated copolymer obtained by reacting the first-order modified, hydrogenated copolymer of claim 14 with a second-order modifier, wherein the second-order modifier has a functional group reactive with the functional group of the first-order modifier group of the first-order modified, hydrogenated copolymer.

25. The second-order modified, hydrogenated copolymer according to claim 24, wherein the functional group of the second-order modifier comprises at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group.

26. The second-order modified, hydrogenated copolymer according to claim 24, which is a foam.

27. A crosslinked, second-order modified, hydrogenated copolymer obtained by subjecting the second-order modified, hydrogenated copolymer of claim 24 to a crosslinking reaction in the presence of a crosslinking agent.

28. A second-order modified, hydrogenated copolymer composition comprising:

1 to 99 parts by weight of (a-2) the second-order modified, hydrogenated copolymer of claim 24, relative to 100 parts by weight of the total amount of components (a-2) and (b), and

29. The second-order modified, hydrogenated copolymer composition according to claim 28, which is a foam.

30. A crosslinked, second-order modified, hydrogenated copolymer composition obtained by subjecting the second-order modified, hydrogenated copolymer composition of claim 28 to a crosslinking reaction in the presence of a crosslinking agent.

31. An adhesive composition comprising:

100 parts by weight of the second-order modified, hydrogenated copolymer (a-2) of claim 24, and

20 to 400 parts by weight of a tackifier (n).

32. A bitumen composition comprising:

0.5 to 50 parts by weight of the second-order modified, hydrogenated copolymer (a-2) of claim 24, and

100 parts by weight of asphalt (o).