CN100500760C

CN100500760C - Polymer composition

Info

Publication number: CN100500760C
Application number: CNB2007100021243A
Authority: CN
Inventors: 久保伸明; 草乃濑康弘; 中岛滋夫; 松田孝昭; 高山茂树; 白木利典
Original assignee: Asahi Kasei Chemicals Corp
Current assignee: Asahi Kasei Corp
Priority date: 2001-07-18
Filing date: 2002-07-18
Publication date: 2009-06-17
Anticipated expiration: 2022-07-18
Also published as: CN1978520A; CN1974610A; CN1974656A; CN100503654C; CN100503719C; ES2366577T3

Abstract

A secondarily modified block copolymer which is obtained by reacting: a primarily modified block copolymer which comprises a base block copolymer comprising at least one polymer block consisting mainly of vinylaromatic hydrocarbon monomer units and at least one polymer block consisting mainly of conjugated diene monomer units and functional-group-containing primary modifier groups bonded to the base block copolymer; with a secondary modifier having a specific functional group reactive with the functional groups of the primary modifier groups contained in the primarily modified block copolymer. Also provided is a polymer composition which comprises the secondarily modified block copolymer in combination with a thermoplastic resin and/or a rubbery polymer.

Description

Polymer composition

This application is filed as a divisional application with the title "modified block copolymer" on application number 0.2813151.7, application date 2002, 7/18/h.

Technical Field

The present invention relates to a modified block copolymer suitable for preparing a polymer composition excellent in balance of rigidity and impact resistance. More specifically, the present invention relates to a modified block copolymer (hereinafter often referred to as "secondary modified block copolymer") formed by reacting a half-modified block copolymer (hereinafter often referred to as "primary modified block copolymer") comprising a base block copolymer and a primary modifier group having a functional group bonded to the base block copolymer, with a secondary modifier having another specific functional group, wherein the base block copolymer comprises at least one polymer block mainly containing a vinyl aromatic hydrocarbon monomer unit and at least one polymer block mainly containing a conjugated diene monomer unit. The present invention also relates to a polymer composition containing a secondary modified block copolymer obtained by adding the secondary modified block copolymer (hereinafter, sometimes referred to as "modified block copolymer") to a thermoplastic resin and/or a rubbery polymer. The polymer composition containing the above-mentioned secondary modified block copolymer exhibits an excellent balance of rigidity and impact resistance. The above-mentioned polymer composition containing the secondary modified block copolymer of the present invention can be processed into molded articles of various shapes by injection molding, extrusion molding, etc., and can be advantageously used for various applications such as automobile parts (automobile interior materials, automobile exterior materials), various containers such as food packaging containers, household electric appliances, medical machine parts, industrial parts, toys, etc.

The present invention also relates to a polymer composition comprising the above-mentioned primary modified block copolymer and a thermoplastic resin and/or a rubbery polymer, and the above-mentioned secondary modifier. By melt kneading the above polymer composition, a polymer composition containing the above secondary modified block copolymer can also be obtained.

Background

Conventionally, attempts have been made to use a composition or a laminate composed of a plurality of components for applications such as sheets, films, and molded articles made of a polymer material, to impart sufficient strength, to improve the processability, and to reduce the cost of the product. However, when different kinds of polymer substances are mixed with each other to form a composition, the number of the components having good compatibility is not large. Further, the composition of a polymer substance having poor compatibility may not be sufficiently effective in modification by mixing because of poor non-uniformity of mixing properties and delamination of different polymer substances.

As is well known, as one component of a composition excellent in properties obtained by mixing high molecular substances, a styrene-butadiene block copolymer or a hydrogenated product thereof, a styrene-isoprene block copolymer or a hydrogenated product thereof, and the like can be used. However, these block copolymers have poor compatibility with polymers having polar functional groups, such as polyamide, polyester, and polyurethane, and therefore cannot sufficiently exhibit the effect of modification by mixing, and thus cannot give useful mixed compositions.

As a method for improving the compatibility of a styrene-butadiene block copolymer or a hydrogenated product thereof with a styrene-isoprene block copolymer or a hydrogenated product thereof with a polymer having a polar functional group, for example, a composition of a terminal-modified block copolymer and a thermoplastic resin is disclosed in Japanese examined patent publication No. 4-39495 (corresponding U.S. Pat. No. 5332784). Further, Japanese patent application laid-open No. 7-173390 discloses a composition of a polyamide resin, a graft copolymer in which polyamide is grafted to a hydrogenated block copolymer, and a hydrogenated block copolymer in which an unsaturated carboxylic acid or a derivative thereof is bonded to a predetermined amount. Further, Japanese patent application laid-open No. 2000-219800 discloses a composition of a polyester resin, a polyamide resin and an epoxidized block copolymer, and Japanese patent application laid-open No. 2001-55492 discloses a composition of a polyester resin, an epoxidized block copolymer, a polyfunctional compound and a polyether ester elastomer.

On the other hand, as a method for obtaining a block copolymer having a functional group, jp 59-98106 a (corresponding U.S. Pat. No. 4465809) describes a method for producing a carboxyl group-containing polymer by bringing a polymer-alkali metal composition into contact with an epoxy compound and directly contacting the resultant product with a cyclic acid anhydride. However, the carboxyl group-containing polymer (in which a cyclic acid anhydride having an epoxy compound residue reacted at the terminal of the polymer is bonded) has poor affinity for a thermoplastic resin, a rubbery polymer, an inorganic filler, and the like.

In addition, Japanese patent application laid-open No. Sho 63-238107 (corresponding U.S. Pat. No. 4972023) describes a polymer modified at the chain end with a terminal acid group or a salt thereof through an amide group, a production method thereof and use thereof. However, this modified polymer is actually obtained by a method of modifying with 1, 5-diaza-bicyclo [3.1.0] cyclohexane and derivatives thereof, and Schiff base (Schiff base) derived from an aliphatic amine or an aromatic amine and an aldehyde, and the obtained polymer (modified with a terminal acid group or a salt thereof through an amide group) has poor affinity with a thermoplastic resin and/or a rubbery polymer, an inorganic filler, and the like.

Thus, none of the prior art compositions comprising a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene and a thermoplastic resin and/or a rubbery copolymer have an excellent balance between rigidity and impact resistance.

Disclosure of Invention

Under such circumstances, the present inventors have intensively studied the improvement of the properties of a composition comprising a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene and a thermoplastic resin and/or a rubber-like copolymer in order to solve the above-mentioned problems of the prior art. As a result, it has been unexpectedly found that a second-order modified block copolymer can be obtained by reacting a second-order modifier with a first-order modified block copolymer, wherein the primary modified block copolymer comprises a base block copolymer and a primary modifier group having a functional group bonded to the base block copolymer, the base block copolymer comprises at least one polymer block mainly comprising vinyl aromatic hydrocarbon monomer units and at least one polymer block mainly comprising conjugated diene monomer units, the secondary modifier has a specific functional group reactive with the functional group of the primary modifier group of the primary modified block copolymer, a polymer composition containing the secondary modified block copolymer excellent in the balance between rigidity and impact resistance can be obtained by combining a thermoplastic resin and/or a rubbery polymer with the secondary modified block copolymer. Further, it has been found that a polymer composition containing a secondary modified block copolymer excellent in balance between rigidity and impact resistance can be obtained by melt-kneading a polymer composition comprising the above-mentioned primary modified block copolymer, a thermoplastic resin and/or a rubbery polymer, and the above-mentioned secondary modifier. Further, it has been found that when the above-mentioned secondary modified block copolymer is combined with a component selected from various components such as an inorganic filler, a tackifier and asphalt, a polymer composition having excellent properties suitable for various applications can be obtained from the combination. Based on these findings, the present invention has been completed.

Accordingly, it is an object of the present invention to provide the above-mentioned secondary modified block copolymer, which can be used for producing a polymer composition excellent in balance between rigidity and impact resistance by mixing it with a thermoplastic resin and/or a rubbery polymer.

It is another object of the present invention to provide a polymer composition having excellent characteristics obtained by combining the above-mentioned secondary modified block copolymer with components selected from various components such as an inorganic filler, a tackifier, and asphalt.

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

According to the present invention, there is provided a modified block copolymer comprising:

a base block copolymer comprising at least one polymer block (A) mainly comprising vinyl aromatic hydrocarbon monomer units and at least one polymer block (B) mainly comprising conjugated diene monomer units, the amounts of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units in the base block copolymer being 5 to 95% by weight and 95 to 5% by weight, respectively, based on the total amount of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units, and

a modifier group containing a functional group bonded to the base block copolymer,

wherein the base block copolymer is not hydrogenated or is at least partially hydrogenated,

the modified block copolymer is represented by a formula selected from the group consisting of the following formulae (1) to (5):

(3) C¹—NR³—D¹

(4) C¹—D¹

(5) E¹—F¹

in the above formula, A¹Represents a unit represented by any one of the following formulae (a) and (b),

B¹represents a unit represented by any one of the following formulae (c) to (e),

(d) —R⁴—CHR⁵—CR⁶R⁷—O—X¹

C¹represents any one of the following formulae (f) to (h)The elements shown in the figures are, by way of example,

D¹represents a unit represented by the following formula (i),

(i) —R⁸—NR³—X¹

E¹represents a unit represented by the following formula (j),

(j) —R⁹—P¹

F¹represents a unit represented by any one of the following formulae (k) to (m),

wherein, X¹Selected from the group consisting of units represented by any one of the following formulae (n) to(s),

(q) —Si(OR¹¹)₂—R¹⁹—Si(OR¹¹)₃、

in the above formulae (1) to (3) and formulae (a) to(s),

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

P¹represents a basic block copolymer of a block copolymer of,

R^1ais represented by C_1-48A trivalent aliphatic hydrocarbon group of (a) is,

R^1b、R⁴、R⁸～R¹⁰and R¹³～R²⁰Each independently represents C_1-48The alkylene group of (a) is,

R²、R³and R¹¹Each independently represents C_1-48Alkyl of (C)_6-48Aryl of (5) by C_1-48Alkyl moiety of (2) and C_6-48Alkylaryl of an aryl moiety consisting of C_1-48Alkyl moiety of (2) and C_6-48Aralkyl group consisting of an aryl moiety of, or C_3-48The cycloalkyl group of (a) is,

wherein R is^1a、R^1b、R³、R⁴、R⁸～R¹⁰、R¹³～R¹⁵And R¹⁷～R²⁰Optionally each independently having a hydroxyl group, an epoxy group, an amino group, a silanol group, C_1-24At least one functional group of the alkoxysilane group of (a),

R⁵～R⁷and R¹²Each independently represents a hydrogen atom, C_1-48Alkyl of (C)_6-48Aryl of (5) by C_1-48Alkyl moiety of (2) and C_6-48Alkylaryl of an aryl moiety consisting of C_1-48Alkyl moiety of (2) and C_6-48Aralkyl group consisting of an aryl moiety of, or C_3-48The cycloalkyl group of (a) is,

wherein R is^1a、R^1b、R²～R⁴And R⁸～R²⁰Optionally each independently having bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, said at least one atom being other than hydroxyl, a ringOxy groups, amino groups, silanol groups and alkoxysilane groups,

t, u, v, x are each independently an integer of 0 or more, but t and u are not both 0, and w, y, z, α are each independently an integer of 1 or more.

1. A modified block copolymer comprising:

(3) C¹—NR³—D¹

(4) C¹—D¹

(5) E¹—F¹

in the above formula, A¹Represented by the following formula (a) and formula(b) Any one of the elements represented by (a),

(d) —R⁴a CHR⁵—CR⁶R⁷—O—X¹

C¹Represents a unit represented by any one of the following formulae (f) to (h),

D¹represents a unit represented by the following formula (i),

(i) —R⁸—NR³—X¹

E¹represents a unit represented by the following formula (j),

(j) —R⁹—P¹

(q) —Si(OR¹¹)₂—R¹⁹—Si(OR¹¹)₃

in the above formulae (1) to (3) and formulae (a) to(s),

P¹represents a basic block copolymer of a block copolymer of,

R^1ais represented by C_1-48A trivalent aliphatic hydrocarbon group of (a) is,

wherein R is^1a、R^1b、R²～R⁴And R⁸～R²⁰Optionally each independently having bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, said at least one atom being bonded in a manner different from that of a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group,

2. The modified block copolymer of the above 1 represented by the formula (1).

3. The modified block copolymer of the above 1 represented by the formula (2).

4. The modified block copolymer of the above 1, which is represented by the formula (3).

5. The modified block copolymer of the above 1, which is represented by the formula (4).

6. The modified block copolymer of the above 1, which is represented by the formula (5).

7. A polymer composition comprising: 1 to 99% by weight of the modified block copolymer component (I) of any one of the above 1 to 6 based on the total amount of the component (I) and the component (II), and 99 to 1% by weight of the polymer component (II) of at least one selected from the group consisting of a thermoplastic resin and a rubbery polymer based on the total amount of the component (I) and the component (II).

8. The polymer composition according to the above 7, wherein the thermoplastic resin in the component (II) is a functional group-containing thermoplastic resin, and the rubbery polymer in the component (II) is a functional group-containing rubbery polymer.

9. The polymer composition according to the above 8, wherein the thermoplastic resin having functional groups comprises at least one selected from the group consisting of polyester resins, polyamide resins, polycarbonate resins, polyurethane resins, polyphenylene ether resins and polyoxymethylene resins,

the rubber-like polymer having a functional group comprises at least one member selected from the group consisting of an olefinic elastomer and a styrenic elastomer, wherein each of the elastomers has at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group and an amino group.

10. A polymer composition comprising:

a half-modified block copolymer component (I-1) in an amount of 1 to 99 wt% based on the total amount of the component (I-1) and the component (II), the half-modified block copolymer comprising:

a base block copolymer comprising at least one polymer block (A) mainly comprising vinyl aromatic hydrocarbon monomer units and at least one polymer block (B) mainly comprising conjugated diene monomer units, wherein the amounts of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units in the base block copolymer are 5 to 95 wt% and 95 to 5 wt%, respectively, based on the total amount of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units, and

the semi-modified block copolymer is represented by a formula selected from the group consisting of the following formulae (6) to (10); and

a polymer component (II) comprising 99 to 1 wt% of at least one selected from the group consisting of thermoplastic resins and rubbery polymers, based on the total amount of the component (I-1) and the component (II); and

0.01 to 20 parts by weight of a secondary modifier (III) having a functional group reactive with the functional group of the primary modifier group of the half-modified block copolymer (I-1), relative to 100 parts by weight of the total of the component (I-1) and the component (II);

(8) C²—NR³—D²

(9) C²—D²

(1O) E²—F²

in the above-mentioned formula, the compound of formula,

A²represents a unit represented by any one of the following formulae (a-1) and (b-1),

B²represents a unit represented by the following formula (c-1),

C²represents a unit represented by any one of the following formulae (d-1) and (e-1),

D²represents a unit represented by the following formula (f-1),

(f—1) —R⁸—NHR³

E²represents a unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

F²represents a unit represented by any one of the following formulae (h-1) to (j-1),

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the above formulae (6) to (8) and formulae (a-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

R^1ais represented by C_1-48A trivalent aliphatic hydrocarbon group of (a) is,

wherein R is^1a、R^1b、R³、R⁴、R⁸～R¹⁰And R¹³～R¹⁵Optionally each independently having a hydroxyl group, an epoxy group, an amino group, a silanol group, C_1-24At least one functional group of the alkoxysilane group of (a),

wherein R is^1a、R^1b、R²～R⁴And R⁸～R¹⁵Each independently having bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, the at least one atom being bonded in a manner other than a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group,

t, u, v, and x are each independently an integer of 0 or more, but t and u are not simultaneously 0, and w is an integer of 1 or more.

11. The polymer composition according to the above 10, wherein the thermoplastic resin in the component (II) is a functional group-containing thermoplastic resin, and the rubbery polymer in the component (II) is a functional group-containing rubbery polymer.

12. The polymer composition according to the above 11, wherein the thermoplastic resin having functional groups comprises at least one member selected from the group consisting of polyester resins, polyamide resins, polycarbonate resins, polyurethane resins, polyphenylene ether resins and polyoxymethylene resins,

13. The polymer composition according to the above 11 or 12, wherein the functional group of the secondary modifier (III) is reactive with both the functional group of the primary modifier group of the half-modified block copolymer (I-1) and the functional group of the component (II).

14. The polymer composition according to any one of the above 10 to 13, wherein the functional group of the secondary modifier (III) comprises at least one selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group and an alkoxysilane group.

15. A flame retardant polymer composition comprising

100 parts by weight of the modified block copolymer (I) of any one of 1 to 6,

10 to 2000 parts by weight of an inorganic filler (VI), and

0 to 1000 parts by weight of an olefin polymer.

16. A flame-retardant polymer composition comprising 100 parts by weight of the polymer composition of 7 above and 10 to 2000 parts by weight of an inorganic filler (VI).

17. A flame-retardant polymer composition comprising 100 parts by weight of the above-mentioned 10 polymer composition and 10 to 2000 parts by weight of an inorganic filler (VI).

18. A crosslinked product obtained by melt-kneading a crosslinkable material in the presence of a vulcanizing agent, wherein the crosslinkable material comprises:

10 to 100 wt% of the modified block copolymer component (I) of any one of the above 1 to 6 based on the total amount of the component (I) and the component (II), and

at least one polymer component (II) selected from the group consisting of thermoplastic resins and rubbery polymers in an amount of 90 to 0 wt% based on the total amount of the components (I) and (II).

19. A crosslinked product obtained by melt-kneading the polymer composition of 10 above in the presence of a vulcanizing agent.

20. An adhesive composition comprising:

100 parts by weight of the modified block copolymer (I) of any one of 1 to 6, and 20 to 400 parts by weight of a tackifier (VIII).

21. An adhesive composition comprising

100 parts by weight of a half-modified block copolymer (I-1) comprising:

a primary modifier group containing a functional group bonded to the base block copolymer,

the semi-modified block copolymer (I-1) is represented by a formula selected from the group consisting of the following formulae (6) to (10);

20 to 400 parts by weight of a tackifier (VIII); and

0.01 to 20 parts by weight of a secondary modifier (III) having a functional group reactive with the functional group of the primary modifier group of the half-modified block copolymer (I-1);

(8) C²—NR³—D²

(9) C²—D²

(10) E²—F²

in the above-mentioned formula, the compound of formula,

B²represents a unit represented by the following formula (c-1),

D²is represented by the following formula (The unit represented by f-1) is,

(f—1) —R⁸—NHR³

E²represents a bonding unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the above formulae (6) to (8) and formulae (a-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

R^1ais represented by C_1-48A trivalent aliphatic hydrocarbon group of (a) is,

wherein R is^1a、R^1b、R³、R⁴、R⁸～R¹⁰And R¹³～R¹⁵Optionally each independently having a group selected from hydroxyl, epoxy, amino, silanol and C_1-24At least one functional group of the alkoxysilane group of (a),

wherein R is^1a、R^1b、R²～R⁴And R⁸～R¹⁵Optionally each independently having bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, the at least one atom being bonded in a manner different from that of a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group,

22. The adhesive composition according to the above 21, wherein the functional group of the secondary modifier (III) comprises at least one selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group and an alkoxysilane group.

23. An adhesive film for surface protection obtained by forming an adhesive layer on a resin film, wherein the adhesive layer comprises an adhesive composition comprising:

100 parts by weight of the modified block copolymer (I) of any one of 1 to 6, and 3 to 200 parts by weight of a tackifier (VIII).

24. An adhesive film for surface protection obtained by forming an adhesive layer on a resin film, wherein the adhesive layer comprises an adhesive composition comprising:

100 parts by weight of a half-modified block copolymer (I-1) comprising:

3 to 200 parts by weight of a tackifier (VIII); and

0.01 to 20 parts by weight of a secondary modifier (III), wherein the secondary modifier (III) has a functional group reactive with the functional group of the primary modifier group of the half-modified block copolymer (I-1);

(8) C²—NR³—D²

(9) C²—D²

(10) E²—F²

in the above-mentioned formula, the compound of formula,

A²represents a compound represented by any one of the following formulae (a-1) and (b-1)The unit cell is a unit cell, which is composed of a plurality of unit cells,

B²represents a unit represented by the following formula (c-1),

D²represents a unit represented by the following formula (f-1),

(f—1) —R⁸—NHR³

E²represents a unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the above formulae (6) to (8) and formulae (a-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

R^1ais represented by C_1-48A trivalent aliphatic hydrocarbon group of (a) is,

R⁵～R⁷and R¹²Each independently represents a hydrogen atom, C_1-48Alkyl of (C)_6-48Aryl of (5) by C_1-48Alkyl moiety of (2) and C_6-48Alkylaryl of an aryl moiety consisting of C_1-48Alkyl moiety of (2) and C_6-48Aralkyl group consisting of an aryl moiety of, or C_3-48In which R is^1a、R^1b、R²～R⁴And R⁸～R¹⁵Optionally each independently having bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, the at least one atom being bonded in a manner different from that of a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group,

25. An asphalt composition comprising:

0.5 to 50 parts by weight of the modified block copolymer (I) of any one of 1 to 6 described above, and 100 parts by weight of asphalt (IX).

26. An asphalt composition comprising:

0.5 to 50 parts by weight of a half-modified block copolymer (I-1) comprising:

100 parts by weight of bitumen (IX); and

0.01 to 5 parts by weight of a secondary modifier (III), wherein the secondary modifier (III) has a functional group reactive with the functional group of the primary modifier group of the half-modified block copolymer (I-1);

(8) C²—NR³—D²

(9) C²—D²

(10) E²—F²

in the above-mentioned formula, the compound of formula,

B²represents a unit represented by the following formula (c-1),

D²represents a unit represented by the following formula (f-1),

(f—1) —R⁸—NHR³

E²represents a unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the above formulae (6) to (8) and formulae (a-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

R^1ais represented by C_1-48A trivalent aliphatic hydrocarbon group of (a) is,

wherein R is^1a、R^1b、R²～R⁴And R⁸～R¹⁵And necessarily each independently has bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, the at least one atom being bonded in a manner different from a hydroxyl group, an epoxy group, an amino group, a silanol group, an alkoxysilane group,

27. A water-drainage road surface comprising a road and a water-drainage road surface layer having a plurality of water-drainage pores formed thereon, the water-drainage road surface layer comprising a plurality of aggregates and a binder, the binder comprising the asphalt composition of 25 above.

28. The water-repellent road surface of 27 above, wherein the water-repellent road surface layer has a porosity of 5 to 35%.

29. A water-drainage road surface comprising a road and a water-drainage road surface layer having a plurality of water-drainage pores formed thereon, the water-drainage road surface layer being composed of a plurality of aggregates and a binder, the binder containing the asphalt composition of 26 above.

30. The water-draining road surface layer of 29, wherein the water-draining road surface layer has a porosity of 5 to 35%.

31. A process for producing the modified block copolymer of the above 1, which comprises

(1) Providing a once-modified block copolymer comprising:

a base block copolymer comprising at least one polymer block (A) mainly comprising vinyl aromatic hydrocarbon monomer units and at least one polymer block (B) mainly comprising conjugated diene monomer units, wherein the amounts of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units in the base block copolymer are 5 to 95 wt% and 95 to 5 wt%, respectively, with respect to the total amount of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units, and

the first-order modified block copolymer is prepared by the following method: preparing a base block copolymer having a living end by living anionic polymerization, and obtaining a first-order modified block copolymer by addition-bonding a first-order modifier having a functional group to the living end of the base block copolymer, optionally followed by partially or completely hydrogenating the first-order modified block copolymer, wherein the first-order modified block copolymer is represented by a formula selected from the group consisting of the following formulae (6) to (10), and

(2) reacting a primary-modified block copolymer with a secondary modifier, wherein the secondary modifier has a functional group reactive with the functional group of the primary modifier group of the primary-modified block copolymer, and wherein the secondary modifier is used in an amount of 0.3 to 10 moles with respect to 1 equivalent of the functional group of the primary modifier group of the primary-modified block copolymer,

thereby obtaining a second-order modified block copolymer,

(8) C²—NR³—D²

(9) C²—D²

(10) E²—F²

in the above-mentioned formula, the compound of formula,

B²represents a unit represented by the following formula (c-1),

D²represents a unit represented by the following formula (f-1),

(f—1) —R⁸—NHR³

E²represents a unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the above formulae (6) to (8) and formulae (a-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

R^1ais represented by C_1-48A trivalent aliphatic hydrocarbon group of (a) is,

wherein R is^1a、R^1b、R³、R⁴、R⁸～R¹⁰And R¹³～R¹⁵Optionally each independently of the others a group selected from the group consisting of hydroxyl, epoxy, amino, silane, C_1-24At least one functional group of the alkoxysilane group of (a),

32. The method of the above 31, wherein in (1), after the primary modifier having a functional group is addition-bonded to the active end of the base block copolymer, the obtained primary modified block copolymer is allowed to react with an active hydrogen-containing compound,

wherein, when the optional hydrogenation of the primary modified block copolymer is carried out, the reaction with the active hydrogen-containing compound may be carried out before or simultaneously with the hydrogenation.

In this case, when the primary modified block copolymer is optionally hydrogenated, the reaction with the active hydrogen-containing compound may be carried out before or simultaneously with the hydrogenation.

The present invention will be described in detail below.

The once-modified block copolymer of the present invention is a modified block copolymer comprising:

a base block copolymer comprising a base block copolymer of at least one polymer block (a) mainly comprising vinyl aromatic hydrocarbon monomer units and at least one polymer block (B) mainly comprising conjugated diene monomer units, and a modifier group having a functional group bonded to the base block copolymer, wherein the base block copolymer is not hydrogenated or is at least partially hydrogenated, and the primary modified block copolymer is represented by a formula selected from the group consisting of the above-mentioned formulae (6) to (10). On the other hand, the second-order modified block copolymer of the present invention is a modified block copolymer obtained by reacting the first-order modified block copolymer 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 block copolymer, and the second-order modified block copolymer is represented by a formula selected from the group consisting of the above-mentioned formulae (1) to (5).

The content of the vinyl aromatic hydrocarbon monomer units in the base block copolymer of the present invention is 5 wt% or more in terms of rigidity relative to the total amount of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units, and is 95 wt% or less, more preferably 10 to 90 wt%, and still more preferably 15 to 85 wt%, in terms of the impact resistance-improving effect. The vinyl aromatic hydrocarbon monomer unit has resin properties when the content is 60 wt% or more, preferably 65 wt% or more, and has elastic properties when the content is less than 60 wt%, preferably 55 wt% or less. The amount of the conjugated diene monomer unit in the base block copolymer is 95 to 5% by weight based on the total amount of the vinyl aromatic hydrocarbon monomer unit and the conjugated diene monomer unit.

The base block copolymer of the present invention can be prepared by living anionic polymerization using an organolithium compound as a catalyst in a solvent.

Examples of the method for producing the base block copolymer include methods such as Japanese patent publication No. 36-19286 (corresponding U.S. Pat. No. 2975160), Japanese patent publication No. 43-17979, Japanese patent publication No. 46-32415, Japanese patent publication No. 49-36957 (corresponding U.S. Pat. No. 3281383), Japanese patent publication No. 48-2423, Japanese patent publication No. 48-4106 (corresponding U.S. Pat. No. 3639517), Japanese patent publication No. 51-49567, and Japanese patent publication No. 59-166518 (corresponding U.S. Pat. No. 4603155). The primary modified block copolymer having a primary modifier group having a functional group, which has, for example, a structure represented by the following general formula, can be obtained by addition-bonding the following primary modifier having a functional group to the living end of the base block copolymer obtained by these methods.

(A-B)_n-z，A-(B-A)_n-z，B-(A-B)_n-z，z-(A-B)_n，z-(A-B)_n-z，

Z-A-(B-A)_n-Z，Z-B-(A-B)_n-Z，[(B-A)_n]_m-Z，[(A-B)_n]_m-z，

[(B-A)_n-B]_m-z，and[(A-B)_n-A]_m-z.

In the above formula, A is a polymer block mainly comprising vinyl aromatic hydrocarbon monomer units, and B is a polymer block mainly comprising conjugated diene monomer units. The boundaries of the a and B cells need not be significantly different. N is an integer of 1 or more, preferably 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. Z represents a residue of a primary modifier in which the atomic groups having the following functional groups are bonded. When Z is added according to the metallation reaction described below, Z is bonded to the side chain of the a unit and/or the B unit. When a plurality of a units and B units are present in the block copolymer, the structures of these units may be the same or different. The structures of the polymer chains bonded to Z may be the same or different.

In the present invention, the polymer block a mainly containing vinyl aromatic hydrocarbon monomer units is a copolymer unit of a vinyl aromatic hydrocarbon and a conjugated diene containing a vinyl aromatic monomer unit preferably in an amount of 50 wt% or more, more preferably 70 wt% or more, or a vinyl aromatic hydrocarbon homopolymer unit, and the polymer block B mainly containing a conjugated diene monomer unit is a copolymer unit of a conjugated diene and a vinyl aromatic hydrocarbon containing a conjugated diene preferably in an amount of more than 50 wt%, more preferably 60 wt% or more, or a conjugated diene homopolymer unit. The vinyl aromatic hydrocarbon in the copolymer block may be uniformly distributed or may be distributed in a tapered shape. In the copolymer block portion, at least one of a portion in which the vinyl aromatic hydrocarbon monomer units are uniformly distributed and a portion in which the vinyl aromatic hydrocarbon monomer units are distributed in a tapered shape may be present in combination. In the copolymer block portion, a plurality of portions having different contents of the vinyl aromatic hydrocarbon monomer unit may be present at the same time. The base block copolymer used in the present invention may also be any mixture of a plurality of different base block copolymers.

In the present invention, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene portion in the block copolymer can be arbitrarily changed by using a polar compound or the like, and when 1, 3-butadiene (which is addition polymerized by cis-1, 4 bonds, trans-1, 4 bonds or 1, 2-vinyl bonds) is used as the conjugated diene, the amount of 1, 2-vinyl bonds is preferably 5 to 90%, more preferably 10 to 80%, based on the total molar amount of cis-1, 4 bonds, trans-1, 4 bonds and 1, 2-vinyl bonds, and when isoprene is used as the conjugated diene or when 1, 3-butadiene and isoprene are used together, the amount of 1, 4 bonds, trans-1, 4 bonds, 1, 2-vinyl bonds and 3, the total molar amount of 4-vinyl bonds, and the total amount of 1, 2-vinyl bonds and 3, 4-vinyl bonds is preferably 3 to 80%, more preferably 5 to 70%. However, in the case of using a hydrogenated block copolymer as the base block copolymer, it is recommended that the amount of 1, 2-vinyl bonds is preferably 10 to 80%, more preferably 25 to 75%, based on the total molar amount of cis-1, 4 bonds, trans-1, 4 bonds and 1, 2-alkenyl bonds when 1, 3-butadiene is used as the conjugated diene, and that the total amount of 1, 2-vinyl bonds and 3, 4-vinyl bonds is preferably 5 to 70%, based on the total molar amount of cis-1, 4 bonds, trans-1, 4 bonds, 1, 2-vinyl bonds and 3, 4-vinyl bonds when isoprene is used as the conjugated diene or when 1, 3-butadiene and isoprene are used together. Hereinafter, the total amount of 1, 2-vinyl bonds and 3, 4-vinyl bonds (however, 1, 2-vinyl bonds when 1, 3-butadiene is used as the conjugated diene) is referred to as "vinyl bonds". "

In the present invention, the conjugated diene is a diene having a pair of conjugated double bonds, and examples thereof include 1, 3-butadiene, 2-methyl-1, 3-butadiene (isoprene), 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, and 1, 3-hexadiene. Among them, 1, 3-butadiene and isoprene are particularly preferable. These conjugated dienes may be used alone or in combination of two or more.

The vinyl aromatic hydrocarbon includes styrene, o-methylstyrene, p-tert-butylstyrene, 1, 3-dimethylstyrene, α -methylstyrene, vinylnaphthalene, vinylanthracene, etc., and among them, styrene is particularly preferably included. These vinyl aromatic hydrocarbons may be used alone or in combination of two or more.

In the present invention, when isoprene and 1, 3-butadiene are used together as a conjugated diene in the preparation of the base block copolymer, the weight ratio of isoprene to 1, 3-butadiene is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, and still more preferably 85/15 to 15/85. In particular, from the viewpoint of obtaining a polymer composition excellent in low-temperature impact resistance, it is recommended that the weight ratio of isoprene to 1, 3-butadiene is preferably 49/51 to 5/95, more preferably 45/55 to 10/90, and further preferably 40/60 to 15/85. When isoprene and 1, 3-butadiene are used together, a polymer composition which is a molded article having an excellent balance between appearance and mechanical properties can be obtained even when molding is carried out at a high temperature.

In the present invention, in either case of producing a polymer composition excellent in flexibility comprising the secondary modified block copolymer and the rubbery polymer or producing a polymer composition excellent in impact resistance comprising the secondary modified block copolymer and the thermoplastic resin, it is also recommended that the proportion of the vinyl aromatic hydrocarbon polymer block to be embedded in the base block copolymer (hereinafter referred to as "block ratio of vinyl aromatic hydrocarbon") is preferably 50% by weight or more, more preferably 50 to 97% by weight, even more preferably 60 to 95% by weight, most preferably 70 to 92% by weight, from the viewpoint of maintaining the rigidity of the molded article. The block ratio of the vinyl aromatic hydrocarbon polymer incorporated into the base block copolymer can be measured by the method described in the following (i.m. kolthoff et al, j.polym. sci.1, 429 (1946)): the block component of a vinyl aromatic hydrocarbon polymer obtained by a method of oxidatively decomposing a block copolymer with t-butyl hydroperoxide using osmium tetroxide as a catalyst (except for a vinyl aromatic hydrocarbon polymer component having an average polymerization degree of about 30 or less) was used and was determined by the following formula.

Block ratio (wt%) of the vinyl aromatic hydrocarbon polymer ═ 100 (weight of the vinyl aromatic hydrocarbon polymer block in the base block copolymer/weight of all the vinyl aromatic hydrocarbons in the base block copolymer) ×

In the present invention, as the solvent used for the production of the base block copolymer, an aliphatic hydrocarbon such as butane, pentane, hexane, isopentane, heptane, survivan, or isohexadecane, an alicyclic hydrocarbon such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, or ethylcyclohexane, or a hydrocarbon solvent such as an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, or xylene can be used. These solvents may be used alone or in combination of two or more.

The organolithium compound used for the preparation of the block copolymer is an organic compound having 1 or more lithium atoms bonded to the molecule, and examples thereof include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium and isoprenedilithium. These organic lithium compounds may be used alone or in combination of two or more. In addition, the organolithium compound may be added all at once or may be added in two or more portions in the preparation of the block copolymer.

In the present invention, a polar compound and a randomizer may be used for the purpose of adjusting the polymerization rate in the production of the base block copolymer, changing the microstructure of the conjugated diene portion to be polymerized, adjusting the reactivity ratio of the conjugated diene and the vinyl aromatic hydrocarbon, and the like. Examples of the polar compound and randomizer include ethers, amines, thioethers, phosphoramides, potassium salts or sodium salts of alkylbenzenesulfonic acids, and potassium or sodium alkoxides. Examples of preferred ethers are dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether. Examples of the amines include tertiary amines, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines. Examples of phosphoramides include hexamethylphosphoramide.

In the present invention, the polymerization temperature for preparing the block copolymer is preferably-10 to 150 ℃ and more preferably 30 to 120 ℃. The time required for the polymerization varies depending on the conditions, but is preferably within 48 hours, and particularly preferably 0.5 to 10 hours. The atmosphere of the polymerization reaction system is preferably an inert gas atmosphere such as nitrogen. The polymerization pressure is not particularly limited as long as the monomer and the solvent can be sufficiently maintained in a liquid phase within the above polymerization temperature range. Further, it is preferable that impurities such as water, oxygen, carbon dioxide and the like which deactivate the catalyst and the active polymer are not mixed in the polymerization reaction system.

The once-modified block copolymer used in the present invention is prepared by the following method: for example, a method in which a base block copolymer having a living end is produced by living anionic polymerization, and a primary modified block copolymer is obtained by addition reaction of a primary modifier having a functional group with the living end of the base block copolymer, and the primary modified block copolymer is partially or completely hydrogenated as required.

The primary modified block copolymer (hereinafter, also referred to as "component (I-1)") of the present invention is a modified block copolymer comprising the above-mentioned base block copolymer and a functional group-containing primary modifier group bonded to the base block copolymer, and has a structure represented by a formula selected from the above-mentioned formulae (6) to (10).

The primary modified block copolymer having the functional group-containing primary modifier group can be obtained by a method in which the following functional group-containing primary modifier is subjected to an addition reaction with the living end of the base block copolymer. Furthermore, the functional group of the primary modifier may also be protected using known methods. Other methods for obtaining the primary modified block copolymer include a method in which an organic alkali metal compound such as an organolithium compound is reacted (metalation reaction) with a base block copolymer having no active end, and further an organic alkali metal is added to the base block copolymer, and then the primary modifier is subjected to addition reaction. In the case of the latter method, the above-mentioned primary modifier may be reacted by obtaining a hydrogenated product of the base block copolymer and then subjecting it to a metalation reaction.

In the step of reacting the primary modifier with the base block copolymer, the hydroxyl group, amino group, etc. of the primary modifier group in the obtained primary modified block copolymer may be usually converted into an alkali metal salt depending on the kind of the primary modifier, but in this case, it may be converted into a functional group, etc. of the hydroxyl group and amino group again by reacting with a compound having active hydrogen, such as water, alcohol, inorganic acid, etc. In this case, when the primary modified block copolymer is optionally hydrogenated, the reaction with the active hydrogen-containing compound may be carried out before or simultaneously with the hydrogenation.

In the present invention, the block copolymer which is not modified after the primary modifier is reacted with the living end of the block copolymer may be mixed with the primary modified block copolymer of the component (A). It is recommended that the proportion of the unmodified block copolymer in the primary modified block copolymer as the component is preferably 70% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less, based on the weight of the primary modified block copolymer.

In the present invention, the primary modifier used for obtaining the primary modified block copolymer includes the following.

For example, the primary modifier used for obtaining the primary modified block copolymer represented by the above formula (6) or the above formula (7) (which corresponds to the secondary modified block copolymer represented by the above formula (1) or the above formula (2), respectively) may be a polyepoxy compound such as tetraglycidyl m-xylylenediamine, tetraglycidyl-1, 3-diaminomethylcyclohexane, tetraglycidyl p-xylylenediamine, tetraglycidyl diaminodiphenylmethane, diglycidylaniline, diglycido-toluidine, 4 '-diglycidyldiphenylmethylamine, 4' -diglycidyldimethylbenzylamine, diglycidylaminomethylcyclohexane, or the like.

The primary modifier used for obtaining the primary modified block copolymer represented by the above formula (10) (corresponding to the secondary modified block copolymer represented by the above formula (5)) may be gamma-glycidoxyethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxybutyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltripropoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropylethyldiethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropylethyldiethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropylmethyldipropoxysilane, gamma-glycidoxypropylmethyldibutoxysilane, gamma-glycidoxypropylmethyldiphenoxysilane, gamma-glycidoxypropyldimethylmethoxysilane, gamma-glycidoxypropyldiethylethoxysilane, gamma-glycidoxypropyldimethylethoxysilane, gamma-glycidoxypropyldimethylphenoxysilane, gamma-glycidoxypropyldiethylmethoxysilane, gamma-glycidoxypropylmethyldisisopropenoxysilane, di (gamma-glycidoxypropyl) dimethoxysilane and di (gamma-glycidoxypropyl) diethoxysilane.

Further, it may be bis (gamma-glycidoxypropyl) dipropoxysilane, bis (gamma-glycidoxypropyl) dibutoxysilane, bis (gamma-glycidoxypropyl) diphenoxysilane, bis (gamma-glycidoxypropyl) methylmethoxysilane, bis (gamma-glycidoxypropyl) methylethoxysilane, bis (gamma-glycidoxypropyl) methylpropoxysilane, bis (gamma-glycidoxypropyl) methylbutoxysilane, bis (gamma-glycidoxypropyl) methylphenoxysilane, tris (gamma-glycidoxypropyl) methoxysilane, gamma-methylpropanoxypropyltrimethoxysilane, gamma-methylpropanoxypropyltriethoxysilane, gamma-methylpropanoxymethyltrimethoxysilane, di (gamma-glycidoxypropyl) methylethoxysilane, di (gamma-glycidoxypropyl) methyl, Gamma-methacryloyloxyethyltriethoxysilane, bis (gamma-methacryloyloxypropyl) dimethoxysilane and tris (gamma-methacryloyloxypropyl) methoxysilane.

Also possible are beta- (3, 4-epoxycyclohexyl) ethyl-trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-ethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-tripropoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-tributoxysilane and beta- (3, 4-epoxycyclohexyl) ethyl-triphenoxysilane.

Further, 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, beta- (3, 4-epoxycyclohexyl) ethyl-methyldibutoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, beta-bis (ethoxysilyl) silane, beta- (3, 4-epoxycyclohexyl) ethyl, 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 and beta- (3, 4-epoxycyclohexyl) ethyl-dimethylphenoxysilane.

Also useful are beta- (3, 4-epoxycyclohexyl) ethyl-diethylmethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-methyldiisoprenoxysilane and N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine.

Examples of the primary modifier used for obtaining the primary modified block copolymer represented by the above formula (8) (corresponding to the secondary modified block copolymer represented by the above formula (3)) include 1, 3-dimethyl-2-imidazolidinone, 1, 3-diethyl-2-imidazolidinone, N' -dimethylpropyleneurea, 1, 3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone, 1-methyl-3- (2-methoxyethyl) -2-imidazolidinone, 1-methyl-3- (2-ethoxyethyl) -2-imidazolidinone Ketones, 1, 3-bis (2-ethoxyethyl) -2-imidazolidinone, 1, 3-dimethylethylenethiourea, N '-diethylpropyleneurea and N-methyl-N' -ethylpropyleneurea.

Examples of the primary modifier used for obtaining the primary modified block copolymer represented by the above formula (9) (corresponding to the secondary modified block copolymer represented by the above formula (4)) include 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1, 5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone, 1-methyl-2-piperidone, 1, 4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-tert-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1, 5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-piperidone, and the like, 1-isopropyl-2-piperidone and 1-isopropyl-5, 5-dimethyl-2-piperidone.

By reacting the above-mentioned primary modifier with the base block copolymer, a primary modified block copolymer having a primary modifier residue having a functional group defined in the present invention bonded thereto can be obtained. When the primary modifier having a functional group is subjected to addition reaction with the living end of the base block copolymer, the living end of the base block copolymer may be either one of the polymer block a and the polymer block B, but in order to obtain a composition excellent in balance of rigidity and impact resistance, it is preferable to add with the living end of the polymer block a (to which the primary modifier having a functional group is added).

The amount of the primary modifier having the functional group is preferably more than 0.5 equivalent to 10 equivalents, more preferably more than 0.7 equivalent to 5 equivalents, and still more preferably more than 1 equivalent to 4 equivalents, based on 1 equivalent of the living end of the base block copolymer. In the present invention, the amount of the active end of the base block copolymer can be calculated from the amount of the organolithium compound used in the polymerization.

In the present invention, the hydrogenated product of the primary modified block copolymer can be obtained by partially or completely hydrogenating the above-mentioned primary modified block copolymer as required. Hydrogenation is carried out after the first modification and before the second modification. The hydrogenation catalyst is not particularly limited, and conventionally known catalysts can be used. Exemplary hydrogenation catalysts include:

(1) a supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd or Ru is supported on carbon, silicon, aluminum, diatomaceous earth or the like;

(2) a Ziegler catalyst which uses a bond between an organic acid salt such as Ni, Co, Fe or Cr, or a transition metal salt such as an acetylacetonate, and a reducing agent such as organoaluminum;

(3) and a homogeneous hydrogenation catalyst such as a so-called organometallic complex containing an organometallic compound such as Ti, Ru, Rh or Zr.

As specific hydrogenation catalysts, there can be used those described in Japanese patent publication No. 42-8704 (corresponding U.S. Pat. No. 3706814), Japanese patent publication No. 43-6636 (corresponding U.S. Pat. No. 3333024), Japanese patent publication No. 63-4841 (corresponding U.S. Pat. No. 4501857), Japanese patent publication No. 1-37970 (corresponding U.S. Pat. No. 4673714), Japanese patent publication No. 1-53851 and Japanese patent publication No. 2-9041. As preferred hydrogenation catalysts, titanocene compounds and/or mixtures with reducing organometallic compounds may be mentioned.

As the titanocene compound, a compound disclosed in Japanese patent application laid-open No. 8-109219 can be used, but specific examples thereof include compounds having at least one ligand having a (substituted) cyclopentadienyl skeleton, an indenyl skeleton or a fluorenyl skeleton, such as dicyclopentadienyl titanium dichloride and monocyclopentadienyl titanium trichloride. Examples of the reducing organometallic compound include an organic alkali metal compound such as organolithium, an organomagnesium compound, an organoaluminum compound, an organoboron compound, an organozinc compound, and the like.

The hydrogenation reaction is preferably carried out at a temperature of 0 to 200 ℃ and more preferably 30 to 150 ℃. It is recommended that the hydrogen pressure used in the hydrogenation reaction is preferably 0.1 to 15MPa, more preferably 0.2 to 10MPa, and still more preferably 0.3 to 5 MPa. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction may be carried out in any of a batch reaction, a continuous reaction, or a combination of these.

In the hydrogenation of the first-modified block copolymer in the present invention, the total hydrogenation rate of the unsaturated double bonds based on the conjugated diene compound may be arbitrarily selected depending on the purpose, and is not particularly limited.

In the present invention, it is recommended that the hydrogenation rate of the vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more, in the hydrogenated primary-modified block copolymer, from the viewpoint of obtaining a resin composition excellent in thermal stability. The hydrogenation ratio of vinyl bonds here means the proportion of hydrogenated vinyl bonds in the vinyl bonds based on the conjugated diene incorporated into the base block copolymer (before hydrogenation).

The hydrogenation rate of the aromatic double bonds of the vinyl aromatic hydrocarbon monomer units in the first-modified block copolymer is not particularly limited, but it is recommended that the hydrogenation rate is preferably 50% or less, more preferably 30% or less, and still more preferably 20% or less.

The hydrogenation rate can be measured by a nuclear magnetic resonance apparatus (NMR).

The second-order modified block copolymer of the present invention is a second-order modified block copolymer (hereinafter, often referred to as component (I)) obtained by reacting a second-order modifier (hereinafter, often referred to as component (III)) having a functional group reactive with the functional group of the first-order modifier group of the first-order modified block copolymer with the first-order modified block copolymer (I-1) (half-modified block copolymer), and is a second-order modified block copolymer having a structure represented by any one of the above-described formulas (1) to (5).

As described above, the method for producing the secondary modified block copolymer of the present invention includes a method in which a basic block copolymer having a living end is produced by living anionic polymerization using an organolithium compound as a catalyst, and then a primary modifier is reacted therewith to produce a primary modified block copolymer, and a secondary modifier is reacted therewith to obtain a secondary modified block copolymer. Incidentally, if the examples of the "base block copolymer having an active end", "first-modified block copolymer" and "second-modified block copolymer" are represented by schematic diagrams, they are as follows (i) to (iii), respectively.

Wherein,represents a base block copolymer, Li represents lithium ions, M represents a primary modifier group, and D represents a secondary modifier group.

In another embodiment of the present invention, there is provided a method for preparing the secondarily modified block copolymer of the present invention, which comprises

(1) Providing a once-modified block copolymer comprising:

a base block copolymer comprising at least one polymer block (A) mainly comprising vinyl aromatic hydrocarbon monomer units and at least one polymer block (B) mainly comprising conjugated diene monomer units, the amounts of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units in the base block copolymer being 5 to 95% by weight and 95 to 5% by weight, respectively, relative to the total amount of the vinyl aromatic hydrocarbon monomer units and the conjugated diene monomer units, and

the first-order modified block copolymer is prepared by the following method: producing a base block copolymer having a living end by living anionic polymerization, and obtaining a first-order modified block copolymer by addition-bonding a first-order modifier having a functional group to the living end of the base block copolymer, optionally followed by partial or complete hydrogenation of the first-order modified block copolymer, wherein the first-order modified block copolymer is represented by a formula selected from the group consisting of the above-mentioned formulae (6) to (10), and

thereby obtaining a second-modified block copolymer.

In the secondary-modified block copolymer of the present invention, the functional group contained in the functional group-containing atomic group X1 (as the secondary modifier group) is reactive with the functional group-containing thermoplastic resin and/or the functional group-containing rubbery polymer, or the inorganic filler, and the primary modifier group and the secondary modifier group each contain a nitrogen atom, an oxygen atom, or a carbonyl group. The interaction of physical affinity such as hydrogen bond between these atoms and groups and polar groups such as thermoplastic resin and/or rubbery polymer, inorganic filler and the like can be remarkably generated, thereby achieving the objective effect of the present invention.

The secondary modifier used in the present invention is a secondary modifier having a functional group reactive with the functional group of the primary-modified block copolymer component (I-1). Examples of preferred secondary modifiers are as follows. Preferred examples of the secondary modifier for obtaining a secondary modified block copolymer having a functional group represented by the above formula (n) are secondary modifiers having a carboxyl group or an acid anhydride group; preferred examples of the secondary modifier for obtaining a secondary modified block copolymer having a functional group represented by the above formula (o) are secondary modifiers having an isocyanate group; preferred examples of the secondary modifier for obtaining a secondary modified block copolymer having a functional group represented by the above formula (p) are secondary modifiers having an epoxy group; a preferable example of the secondary modifier for obtaining the secondary modified block copolymer having the functional group represented by the above formula (q) is a secondary modifier having a silanol group or an alkoxysilane group. The secondary modifier component (III) is a secondary modifier having at least two functional groups selected from these functional groups. However, when the functional group is an acid anhydride group, the secondary modifier component (III) may be a secondary modifier having only one acid anhydride group. When the secondary modifier component (III) is reacted with the primary modified block copolymer component (I-1), it is recommended that the component (III) is 0.3 to 10 mol, preferably 0.4 to 5 mol, more preferably 0.5 to 4 mol, based on 1 equivalent of the functional group bonded to the component (I-1). The method for reacting the component (I-1) with the component (III) is not particularly limited, and a known method can be used. Examples thereof include the following melt kneading method and a method of dissolving or dispersing and mixing the components in a solvent or the like to cause the reaction. In the method of reacting the components by dissolving or dispersing and mixing the components in a solvent or the like, the solvent is not particularly limited as long as the components can be dissolved or dispersed, and a hydrocarbon solvent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a halogen-containing solvent, an ester solvent, an ether solvent, or the like can be used. The temperature for reacting the components in this method is usually-10 to 150 ℃ and preferably 30 to 120 ℃. The time required for the reaction varies depending on the conditions, but is generally within 3 hours, preferably several seconds to 1 hour. Particularly preferred is a method in which the component (III) is added to a solution of the reaction mixture containing the prepared first-modified block copolymer (I-1) to react the mixture, thereby obtaining a second-modified block copolymer. In this case, from the viewpoint of obtaining a secondary modified block copolymer excellent in color tone, it is recommended to react the primary modifier having a functional group with the active end of the base block copolymer and then treat it with an active hydrogen-containing compound. Alcohols such as water, methanol, ethanol, propanol, and isopropanol; treating with a compound having active hydrogen such as inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and carbonic acid. In this treatment, it is recommended that the solution of the primary modified block copolymer (I-1) after the treatment is brought to a pH of 10 or less, preferably 9 or less, more preferably 8 or less, and then reacted with the secondary modifier, from the viewpoint of stability of the secondary modifier residue bonded to the secondary modified block copolymer.

Specific examples of the secondary modifier component (III) 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; aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid.

Examples of the secondary 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-dioxotetrahydroxyfuryl) -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.

The secondary modifier having an epoxy group includes the above-mentioned epoxy compound used as a primary modifier for obtaining the primary modified block copolymer of the component (I-1) in addition to tetraglycidyl-1, 3-diaminomethylcyclohexane, tetraglycidyl metaxylenediamine, diglycidylaniline, diglycidylethylene glycol, diglycidylpropylene glycol, and diglycidyl terephthalate acrylate.

The secondary modifier having a silanol group includes a hydrolysate of the above alkoxysilane compound used as a primary modifier to obtain the primary modified block copolymer of the component (I-1), and the like. Examples of the secondary modifier having an alkoxysilyl group include the above silane compounds used as the primary modifier to obtain the primary modified block copolymer of the component (I-1) and the like, in addition to bis- (3-triethoxysilylpropyl) -tetrasulfane, bis- (3-triethoxysilylpropyl) -disulfane, ethoxysiloxane oligomer and the like.

Particularly preferred secondary modifiers in the present invention are carboxylic acids having two or more carboxyl groups or anhydrides thereof, or secondary modifiers having two or more anhydride groups, isocyanate groups, epoxy groups, silanol groups, or alkoxysilane groups, for example, maleic anhydride, pyromellitic anhydride, 1, 2, 4, 5-benzenetetracarboxylic dianhydride, tolylene diisocyanate, tetraglycidyl-1, 3-diaminomethylcyclohexane, bis- (3-triethoxysilylpropyl) -tetrasulfane, and the like.

The weight average molecular weight of the first-order modified block copolymer and the second-order modified block copolymer obtained by reacting the first-order modifier with the first-order modifier is preferably 3 ten thousand or more from the viewpoint of mechanical strength and impact resistance of the polymer composition, and is preferably 100 ten thousand or less, more preferably 4 to 80 ten thousand, and further preferably 5 to 60 ten thousand from the viewpoint of processability and compatibility with the thermoplastic resin and/or the rubbery polymer.

In the present invention, the amount of vinyl groups in the bonded monomer units of the conjugated diene of the block copolymer can be measured using a nuclear magnetic resonance apparatus (NMR). Alternatively, the hydrogenation rate can be measured by NMR using the same apparatus. The weight average molecular weights of the first-order modified block copolymer and the second-order modified block copolymer can be measured by Gel Permeation Chromatography (GPC), and are determined by using a calibration curve obtained from a commercially available standard styrene sample, that is, a calibration curve prepared by using the peak molecular weight of standard polystyrene.

By the solution of the first-modified block copolymer and the solution of the second-modified block copolymer obtained as described above, the copolymers can be separated from the solutions as needed. If necessary, the catalyst residue may be removed first, and the polymer may be separated from the solution. Examples of the method for separating the polymer from the solvent include a method of precipitating the polymer by adding a polar solvent such as acetone or alcohol (which is a solvent hardly soluble in the polymer) to the solution after polymerization or hydrogenation to recover the polymer, a method of adding the solution of the polymer to hot water under stirring to remove the solvent by stripping to recover the polymer, and a method of removing the catalyst by directly heating the polymer solution. Further, various stabilizers such as phenol stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers may be added to the first-modified block copolymer and the second-modified block copolymer of the present invention.

In the present invention, a polymer composition suitable for various molding materials can be obtained by combining the secondary modified block copolymer (component (I)) with at least one polymer component selected from a thermoplastic resin and a rubbery polymer (hereinafter, this is often referred to as component (II)). The ratio of the component (I) to the component (II) can be arbitrarily controlled so as to maximize the effects of the respective components. The mixing ratio of the component (I) and the component (II) is generally 1/99 to 99/1, preferably 2/98 to 90/10, more preferably 5/95 to 70/30 in terms of the mixing weight ratio of the component (I)/the component (II). When the component (II) is a thermoplastic resin, it is recommended that the component (I)/component (II) be mixed in a weight ratio of 2/98 to 90/10, preferably 5/95 to 60/40, more preferably 10/90 to 40/60. In the polymer composition comprising the component (I) and the component (II), the component (III) may be mixed in an amount of 0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, based on 100 parts by weight of the total amount of the component (I) and the component (II).

When the secondary modified block copolymer of the present invention and a thermoplastic resin are mixed, a polymer composition excellent in impact resistance and molding processability can be obtained.

As the thermoplastic resin, a block copolymer resin including the above-mentioned conjugated diene compound and vinyl aromatic compound in connection with the preparation of the base block copolymer; a polymer of the vinyl aromatic compound; the vinyl aromatic compound and at least one other vinyl monomer (but different from the vinyl aromatic monomer), such as copolymer resins of ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, etc.; rubber-modified styrene-based resin (HIPS); acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene-styrene copolymer resins (MBS); an olefin-based polymer; cyclic olefin resins such as ethylene-norbornene resins; polybutylene resin; polyvinyl chloride resin; polyvinyl acetate resin; polymers of acrylic acid and its esters and amides; a polyacrylate resin; polymers of acrylonitrile and/or methacrylonitrile; a copolymer of these acrylonitrile-based monomers and monomers copolymerizable therewith, and a nitrile resin containing 50% by weight or more of acrylonitrile-based monomer units; a polyamide-based resin; a polyester resin; thermoplastic polyurethane resin; a polycarbonate-series polymer; thermoplastic polysulfones such as polyether sulfone and polyallyl sulfone; a polyoxymethylene resin; polyphenylene ether resin; polyphenylene sulfide resins such as polyphenylene sulfide and poly-4, 4' -diphenylene sulfide; a polyallyl ester resin; polyetherketone polymers or copolymers; a polyketone resin; a fluororesin; a polyoxybenzoyl polymer; a polyimide resin; a polymer having a structure in which hydrogen of a chain hydrocarbon polymer compound is partially or entirely substituted with fluorine, specifically a fluororesin such as polytetrafluoroethylene or a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer; polybutadiene resins such as 1, 2-polybutadiene and trans-polybutadiene. These thermoplastic resins may also be modified with the above-mentioned secondary modifier component (III). The number average molecular weight of these thermoplastic resins is usually 1000 or more, preferably 5000 to 500 ten thousand, and more preferably 1 to 100 ten thousand.

Among the above thermoplastic resins, polyester resins, polyamide resins, polycarbonate resins, polyurethane resins, polyphenylene ether resins, and polyacetal resins are preferable. These thermoplastic resins all contain functional groups. The thermoplastic resins may be used singly or in combination. The compatibility of the composition can be significantly improved by reacting the functional group-containing thermoplastic resin with the secondary modified block copolymer (component (I)) or with the primary modified block copolymer (component (I-1)) and the secondary modifier (component (III)).

Further, when the second-order modified block copolymer of the present invention and the rubbery polymer are mixed, a polymer composition excellent in tensile strength, tensile elongation and molding processability can be obtained.

The rubbery polymer used as the component (II) includes butadiene rubber and its hydride; styrene-butadiene rubber and its hydride (but unlike the secondary modified block copolymer of the present invention); isoprene rubber; acrylonitrile-butadiene rubber and its hydride; olefin elastomers such as chloroprene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, and ethylene-octene rubber; butyl rubber; acrylic rubber; a fluororubber; a silicone rubber; chlorinated polyethylene rubber; propylene oxide rubber; an α, β -unsaturated nitrile-acrylate-conjugated diene copolymer rubber; a urethane rubber; a polysulfide rubber; styrene-butadiene block copolymers and hydrogenated products thereof; styrene-based elastomers such as styrene-isoprene block copolymers and hydrogenated products thereof; natural rubber, and the like. These rubbery polymers may also be modified rubbers having functional groups introduced thereto, for example, rubbers obtained by modifying these rubbery polymers with the component (III). Preferable modified rubbers include olefin elastomers such as ethylene-propylene rubbers and ethylene-propylene-diene rubbers into which a functional group selected from a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, an amino group and an alkoxysilane group is introduced; styrene-butadiene copolymers and their hydrides (but unlike the modified block copolymers of the present invention); styrene-based elastomers such as styrene-isoprene copolymers and hydrogenated products thereof; butadiene rubber; isoprene rubber, and the like. The number average molecular weight of these rubbery polymers is preferably 1 ten thousand or more, more preferably 2 to 100 ten thousand, and further preferably 3 to 80 ten thousand.

Two or more of these thermoplastic resins and rubbery polymers may be mixed and used as necessary. The mixing of different polymers such as the component (II) is not particularly limited. For example, the component (II) may be used either between thermoplastic resin components or between rubber-like polymer components. Further, a mixture of the thermoplastic resin and the rubbery polymer may be used.

In the present invention, there is also provided a polymer composition comprising:

1 to 99% by weight, preferably 2 to 90% by weight, more preferably 5 to 70% by weight of the above-mentioned primary modified block copolymer component (I-1) based on the total amount of the component (I-1) and the component (II), and

99 to 1% by weight, preferably 98 to 10% by weight, more preferably 95 to 30% by weight, relative to the total amount of the component (I-1) and the component (II), of at least one polymer selected from the group consisting of thermoplastic resins and rubbery polymers, and

a secondary modifier component (III) having a functional group reactive with the functional group of the primary modifier group of the modified block copolymer (I-1) in an amount of 0.1 to 20 parts by weight, preferably 0.02 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, based on 100 parts by weight of the total of the component (I-1) and the component (II).

When the component (II) is a thermoplastic resin, it is recommended that the component (I-1)/the component (II) be mixed in a weight ratio of 2/98 to 90/10, preferably 5/95 to 60/40, more preferably 10/90 to 40/60.

In the above polymer composition, it is preferable that the thermoplastic resin in the component (II) is a functional group-containing thermoplastic resin, and the rubbery polymer in the component (II) is a functional group-containing rubbery polymer. When the component (II) has a functional group, it is advisable to use a secondary modifier (III) having a functional group reactive with both the functional group of the component (I) and the functional group of the component (II), or a secondary modifier (III) having a functional group reactive with both the functional group of the primary modifier group of the component (I-1) and the functional group of the component (II).

As the thermoplastic resin having a functional group, polyester resins are included; a polyamide-based resin; a polycarbonate-series resin; a polyurethane resin; a polymer having an imide bond in the main chain, for example, a polyimide-based resin such as polyimide, polyaminobismaleimide (polydimaleimide), bismaleimidotriazine resin, and polyimide resin (imide or polyetherimide); polymers of formaldehyde or trioxane, and polyacetal resins such as copolymers of formaldehyde or trioxane with other aldehydes, cyclic ethers, epoxides, isocyanates, vinyl compounds, etc.; polysulfone-based resins such as polyethersulfone and polyallylsulfone; 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 poly (allyl ester) resin which is a condensation polymer composed of bisphenol a and phthalic acid; polyketone resins.

In addition, examples of the thermoplastic resin having a functional group include copolymer resins of a vinyl aromatic compound and at least one vinyl monomer (other than the vinyl aromatic compound), such as vinyl acetate, acrylic acid or acrylic acid ester (e.g., methyl acrylate), acrylic nitrile, methacrylonitrile, and the like; acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene-styrene copolymer resins (MBS); resins containing 50% by weight or more of ethylene units as copolymers of ethylene and other copolymerizable monomers (e.g., ethylene-vinyl acetate copolymers and hydrolysates thereof); and like polyethylene-based resins (e.g., ethylene-acrylic acid ionomers); resins containing 50% by weight or more of propylene units as copolymers of propylene and other copolymerizable monomers, for example, polypropylene resins such as propylene-ethyl acrylate copolymers; polyvinyl acetate resin containing 50 wt% or more of vinyl acetate unit as a copolymer of vinyl acetate and other copolymerizable monomer, and a hydrolysate thereof.

In addition, examples of the thermoplastic resin having a functional group include polymers of acrylic acid and esters and amides thereof; polymers of methacrylic acid and its esters and amides; a polyacrylate monomer having an acrylic monomer content of 50 wt% or more as a copolymer of the (meth) acrylic monomer and another copolymerizable monomer; polymers of acrylonitrile and/or methacrylonitrile; nitrile monomers having a nitrile monomer content of 50 wt% or more, which are copolymers of these (meth) acrylonitrile monomers and other copolymerizable monomers; and polyoxybenzoyl polymers such as polymers or copolymers prepared by polycondensation using p-hydroxybenzoic acid, terephthalic acid, isophthalic acid, 4' -dihydroxybiphenyl or derivatives thereof.

The polyester-based resin used in the present invention contains an ester bond in the molecule, and the representative polyester-based resin has a structure in which dicarboxylic acid and ethylene glycol are polycondensed, and is obtained by polycondensing dicarboxylic acid, its lower ester, its acid halide or acid anhydride and ethylene glycol. Examples of the aromatic or aliphatic dicarboxylic acid which is a raw material of the polyester-based resin include oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, adipic acid, sebacic acid, azelaic acid, 1, 9-nonanedicarboxylic acid, 1, 10-decanedicarboxylic acid, 1, 16-hexadecanedicarboxylic acid, terephthalic acid, isophthalic acid, p' -dicarboxybiphenyl, p-carboxyphenoxyacetic acid, and 2, 6-naphthalenedicarboxylic acid, and these may be used alone or in any combination. Among them, terephthalic acid and isophthalic acid are preferable. These may be used in any combination. The ethylene glycol (or diol) as another raw material of the polyester-based resin is aromatic or aliphatic, and includes, for example, ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 10-decanediol, neopentyl glycol, p-xylene glycol, and the like, and these may be used alone or in any combination. Of these, ethylene glycol, 1, 3-propanediol and 1, 4-butanediol are preferred.

In addition, as other useful polyester resins, there are included polylactones obtained by ring-opening polymerization of cyclic lactones such as pivalolactone, β -propiolactone, and ∈ -caprolactone. These polyester-based resins may be used alone or in combination of two or more.

The polyamide-based resin used in the present invention is a polycondensate of a dicarboxylic acid and a diamine, a polycondensate of an α -aminocarboxylic acid, a ring-opening polymer of a cyclic lactam, or the like. Specifically, nylon-4, 6, nylon-6, 10, nylon-11, nylon-12, and the like and copolymers of these (for example, nylon-6-nylon-6, 6 copolymer, nylon-6-nylon-12 copolymer) are included. These polyamide resins preferably have a melting point of 150 to 270 ℃ and, when further excellent processability is required, polyamide resins having a melting point of 260 ℃ or lower are more preferred. The polyamide-based resins may be used singly or in combination.

The polycarbonate-series resin used in the present invention is specifically a polymer obtained by reacting a phenol compound having a valence of 2 or more with a carbonate precursor. Examples of the 2-valent phenol compound include 2, 2-bis (4-hydroxyphenyl) propane (commonly referred to as "bisphenol A"), bis (4-hydroxyphenyl) methane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfone, 1-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) cyclohexane, and 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane.

Preferred 2-valent phenols include bis (4-hydroxyphenyl) alkanes, especially bisphenol A. The above-mentioned 2-valent phenols may be used alone or in combination of two or more. Also included as carbonate precursors are carbonyl halides, carbonyl esters, or haloformates. More particularly, it may be selected from phosgene, diphenyl carbonate, dihaloformates of 2-valent phenols and mixtures thereof.

The viscosity average molecular weight of the polycarbonate-series resin used in the present invention is preferably 1 ten thousand or more from the viewpoint of the strength and heat resistance of the obtained composition, and is preferably 6 ten thousand or less from the viewpoint of processability, more preferably 12000 to 45000, and further preferably 13000 to 35000. The viscosity average molecular weight (M) in the present invention is calculated from the specific viscosity obtained by dissolving 0.7g of the polycarbonate-based resin in 100ml of methylene chloride at 20 ℃.

The polyurethane-based resin used in the present invention can be obtained by subjecting a diisocyanate and a diol to polyaddition, for example, a polymer block comprising a polyol (polyester or polyether) as a soft segment and a polymer block comprising a diisocyanate and an ethylene glycol as a hard segment. The polyester diol used as a raw material of the polyurethane resin includes poly (1, 4-butene adipate), poly (1, 6-hexane adipate), polycaprolactone, and the like. Examples of the polyether glycol include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and the like.

Examples of the diol include ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, and 1, 6-hexanediol, and examples of the diisocyanate include aromatic, alicyclic, and aliphatic diisocyanates, such as toluene diisocyanate, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

The weight average molecular weight of the polyurethane resin used in the present invention is preferably 5000 to 50 ten thousand, and more preferably 1 to 30 ten thousand, from the viewpoint of mechanical properties of the obtained composition.

The polyphenylene ether resin is not particularly limited and known resins can be used. Specific examples thereof include poly (2, 6-dimethyl-1, 4-phenylene ether), poly (2-methyl-6-ethyl-1, 4-phenylene ether), poly (2, 6-diphenyl-1, 4-phenylene ether), poly (2-methyl-6-phenyl-1, 4-phenylene ether), poly (2, 6-dichloro-1, 4-phenylene ether), and modified products thereof (for example, maleic anhydride modified products), and copolymers of 2, 6-dimethylphenol and other phenols (for example, 2, 3, 6-trimethylphenol or 2-methyl-6-butylphenol). Among them, poly (2, 6-dimethyl-1, 4-phenylene ether), a copolymer of 2, 6-dimethylphenol and 2, 3, 6-trimethylphenol, and a modified product thereof are preferable. It is recommended that the polyphenylene ether resin has a reduced viscosity (measured at 30 ℃ in a 0.5g/dI chloroform solution) of preferably 0.05 to 0.70, more preferably 0.10 to 0.60, and still more preferably 0.15 to 0.60. When obtaining polymer compositions having excellent mechanical strength, polyphenylene ethers having reduced viscosity of 0.30 to 0.60 are recommended.

The polyoxymethylene resin used in the present invention includes homopolymers prepared by polymerization of formaldehyde or trioxane, and copolymers containing the above monomers as main components. Homopolymers such as polyoxymethylene resins are generally used in a modified form in which the terminal groups of the polymer are converted into ester or ether groups, thereby improving the heat resistance and chemical resistance of the polymer. The copolymer of the polyoxymethylene resin includes a copolymer of formaldehyde or trioxane and at least one member selected from the group consisting of other aldehydes, cyclic ethers, cyclic carbonates, epoxides, isocyanates, and vinyl compounds.

In the present invention, any additive may be mixed as required. The kind of the additive is not particularly limited as long as it can be used by being mixed with the thermoplastic resin and the rubbery polymer in general.

The optional additives include, for example, inorganic fillers such as metal hydroxides, silica-based inorganic fillers, and metal oxides, and organic fillers. From the viewpoint of the balance between the action and effect of these fillers and the processability, the amount of the inorganic filler and the organic filler is 0.5 to 2000 parts by weight, preferably 1 to 1000 parts by weight, and more preferably 3 to 500 parts by weight, based on 100 parts by weight of the component (I) or the component (I-1).

The metal hydroxide for the inorganic filler is a hydrated inorganic filler, and examples thereof include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, hydrates of tin oxide, and hydrates of inorganic metal compounds such as borax. Mixtures of two or more kinds of metal oxides and mixtures of metal hydroxides and inorganic fillers other than metal hydroxides may also be used.

As the silica-based inorganic filler, a filler represented by the chemical formula Si. O₂Or Si₃Examples of the silica-based inorganic filler include inorganic fibrous materials such as silica, clay, talc, kaolin, mica, wollastonite, bentonite, montmorillonite, zeolite, diatomaceous earth, synthetic silica, glass beads, glass spheres, glass flakes, and glass fibers. A mixture of silica-based inorganic filler having a surface hydrophobized and two or more silica-based inorganic fillers, or a mixture of silica-based inorganic filler and inorganic filler other than silica-based inorganic filler may be used. As the silica, dry white carbon ink, wet white carbon ink, synthetic silicate white carbon ink, so-called colloidal silica, and the like can be used.

As metal oxides, use may be made of compounds of the formula M_x·O_y(M is a metal atom, and x and y are each an integer of 1 to 6) as a main component of the structural unit, for example, alumina, titanium oxide, magnesium oxide, zinc oxide, iron oxide, etc. Mixtures of two or more kinds of metal oxides, and mixtures of metal oxides and inorganic fillers other than metal oxides may also be used.

These inorganic fillers may be used singly or in combination. Other inorganic fillers include inorganic fillers such as calcium carbonate, magnesium carbonate, barium carbonate, calcium silicate, calcium sulfate, calcium sulfite, titanium oxide, potassium titanate, barium sulfate, barium titanate, zinc oxide, asbestos, and slag wool.

The organic filler includes carbon black, acetylene black, furnace black, and the like. The carbon black may include various grades of carbon black such as FT, SRF, FEF, HAF, ISAF, and SAF, and carbon black having a nitrogen adsorption specific surface area of 50mg/g or more is preferable.

In the present invention, fatty acids such as stearic acid, oleic acid, palmitic acid, etc. or metal salts thereof; paraffin, wax, polyethylene wax, or a modified product of these; organic metal compounds such as organoboranes and organotitanates; the surface of the inorganic filler is treated with a silane coupling agent or the like.

As the silane coupling agent, inorganic fillers such as silane to be used for filling may be used, and examples thereof include 3-mercaptopropyltrimethoxysilane, 3-mercaptomethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Particularly preferred silane coupling agents in the present invention are compounds having silanol groups or alkoxysilane groups, and also having mercapto groups or/and two or more sulfur-bonded polysulfide bonds. Examples of such silane coupling agents include 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis [3- (triethoxysilyl) propyl ] tetrasulfide, bis [3- (triethoxysilyl) propyl ] disulfide, bis [3- (triethoxysilyl) propyl ] trisulfide, bis [3- (triethoxysilyl) ethyl ] tetrasulfide, 3-triethoxysilylpropyl-N, N' -dimethylaminothiocarbonyl-tetrasulfide, 3-trimethoxysilylpropyl-N, n' -dimethylaminothiocarbonyl-tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, and the like.

The amount of the silane coupling agent to be blended is 0.1 to 20% by weight, preferably 0.5 to 18% by weight, and more preferably 1 to 15% by weight based on the filler in order to sufficiently exhibit the reinforcing effect by the filler such as an inorganic filler in the polymer composition. When a silane coupling agent is used, sulfur and an organic peroxide may be used together.

In the present invention, a rubber softener (VII) (hereinafter, also often referred to as "component (VII)") may be blended for improving processability. As the softening agent (VII) for rubber, mineral oil or a liquid or low molecular weight synthetic softening agent is suitably used, and a softening agent for rubber of mineral oil type called "process oil" or "extender oil" which is generally used for softening, compatibilization, and improvement of processability of rubber, and a softening agent such as polybutene, low molecular weight polybutadiene, liquid paraffin, mineral oil, organopolysiloxane, castor oil, linseed oil, and the like can be used. These softeners may also be added to the modified block copolymer of the present invention after the block copolymer of the present invention is prepared. As the softening agent for rubber used in the present invention, a cycloalkane-based softening agent and/or a paraffin-based softening agent is preferable from the viewpoint of color. The amount of these softeners to be mixed is 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of component (I) or component (I-1).

In the present invention, as other Additives, antioxidants such as "Gomu Purasuchikukuhou Yakuhin (Additives for Rubber and plastics)" (published byRubber Digest Co., Ltd., Japan (1968)); an ultraviolet absorber; a light stabilizer; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, or ethylene distearamide; a mold release agent; paraffin wax; a plasticizer; a flame retardant; an antistatic agent; reinforcing agents such as organic fibers, carbon fibers, metal whiskers and the like; a pigment; colorants, and the like.

The method for producing the polymer composition of the present invention is not particularly limited, and a known method can be used. For example, a melt kneading method using a general mixer, such as an internal mixer, a single screw extruder, a twin screw extruder, a combination kneader, or a multi screw extruder; and a method of dissolving or dispersing and mixing the respective components, and then heating to remove the solvent. In the present invention, a melt kneading method using an extruder is preferred from the viewpoint of productivity and uniform mixing. The shape of the obtained polymer composition is not particularly limited, but includes pellets, flakes, strands, chips and the like. Alternatively, the melt-kneaded product may be directly formed into a molded article.

In addition, when the polymer composition of the present invention is prepared, the order of addition of the components is not limited, and for example, a method of mixing all the components at once, or a mixing method of mixing optional components in advance and then adding the remaining components and the like may be employed. Particularly preferred is a method of melt-kneading the component (I) and the component (II), or a method of melt-kneading the component (I-1), the component (II) and the component (III).

In the present invention, the melt kneading temperature may be selected depending on the softening temperature, melting point, etc. of the thermoplastic resin and the rubbery polymer to be used, but from the viewpoint of the melt viscosity of the thermoplastic resin and the heat aging of the rubbery polymer and the secondary modified block copolymer component (I), the primary modified block copolymer component (I-1) or the hydrogenated product thereof, it is usually preferably 50 to 350 ℃, more preferably 100 to 330 ℃, and still more preferably 130 to 300 ℃. The melt-kneading time (or the average residence time in the melt-kneading step) is preferably 0.2 to 60 minutes, more preferably 0.5 to 30 minutes, and still more preferably 1 to 20 minutes, from the viewpoints of the degree of mixing (dispersibility), productivity, aging of the mixed components, and the like.

The secondary modified block copolymer and the polymer composition of the present invention can be processed into particularly useful molded articles by a conventionally known method, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, blow molding, compression molding, vacuum molding, rotational molding, powder slush molding, foam molding, laminate molding, calender molding, as they are or in combination with various additives. Further, if necessary, processing such as foaming, pulverizing, stretching, sticking, printing, coloring, and plating may be performed. By this molding method, various molded articles such as sheets, films, injection molded articles of various shapes, blow molded articles, pressure molded articles, vacuum molded articles, extrusion molded articles, foam molded articles, nonwoven fabrics, fibrous molded articles, and synthetic leathers can be formed. These molded articles can be used for food packaging materials, medical devices, home electric appliances and parts thereof, electronic devices and parts thereof, automobile parts, industrial parts, household goods, materials for toys and the like, footwear materials, adhesive materials, asphalt modifiers and the like.

The present invention will be described specifically with respect to a secondary modified block copolymer, a composition obtained by mixing a polymer composition with other additives, and various applications using these.

[ flame retardant Polymer composition ]

The flame-retardant polymer composition of the present invention is obtained by using any one of the following processes (i) to (iii):

(i) a method of mixing the secondary modified block copolymer (I) of the present invention with an inorganic filler (VI) and an olefin polymer;

(ii) a method of mixing the polymer composition of the present invention comprising the component (I) and the component (II) with the inorganic filler (VI); and

(iii) a method of mixing the polymer composition of the present invention comprising the component (I-1), the component (II) and the component (III) with the inorganic filler (VI).

In the flame retardant polymer composition of the present invention, the functional group-containing atomic group X in the secondary modified block copolymer¹The functional group (B) is reactive with the thermoplastic resin and/or the rubbery polymer and the inorganic filler (VI) having a functional group, and since the secondary modified block copolymer contains a nitrogen atom, an oxygen atom or a carbonyl group, an interaction due to physical affinity, such as a hydrogen bond, is effectively generated between these atoms and groups and the polar groups of the thermoplastic resin and/or the rubbery polymer and the inorganic filler (VI), and a composition having excellent flame retardancy and high toughness is obtained.

In the flame-retardant polymer composition of the present invention, the amount of the inorganic filler (VI) is usually 10 to 2000 parts by weight, preferably 20 to 1000 parts by weight, and more preferably 25 to 500 parts by weight, based on 100 parts by weight of the component (I), based on 100 parts by weight of the polymer composition of the present invention comprising the component (I) and the component (II), or based on 100 parts by weight of the polymer composition of the present invention comprising the component (I-1), the component (II), and the component (III), from the viewpoint of the balance between the flame-retardant effect of the composition and the tensile strength and tensile elongation at break.

As the inorganic filler (VI), the above-mentioned inorganic filler can be used.

In the flame-retardant polymer composition of the present invention, in order to improve flame retardancy, as the inorganic filler (VI), among the above inorganic fillers, hydrated inorganic fillers 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 hydrates of inorganic metal compounds such as borax are preferably used, and magnesium hydroxide and aluminum hydroxide are more preferably used. These inorganic fillers may be used singly or in combination.

In the flame-retardant polymer composition of the present invention, an ammonium polyphosphate flame retardant, a phosphorus flame retardant such as phosphate, a silicone compound, quartz glass, or the like may be used as necessary to improve the flame-retardant effect, and liquid glass, glass frit, or the like may be used as a flame retardant, and silicon nitride short fibers or the like may be used to prevent dripping.

Examples of the olefin polymer used in the flame retardant polymer composition of the present invention include linear α -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-hexene; polymers and copolymers of branched alpha-olefins such as 4-methyl-1-pentene, 2-methyl-1-propene, 3-methyl-1-pentene, 5-methyl-1-hexene, 4' -dimethyl-1-pentene and the like. When the above-mentioned olefin is copolymerized, the structure of the copolymer is not particularly limited, and may be arbitrarily selected from, for example, a random copolymer, a block copolymer, a graft copolymer, and a mixed configuration of these. As specific examples of the olefin-based polymer, polyethylene; copolymers containing ethylene in an amount of 50% by weight or more and a monomer copolymerizable therewith, such as ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers; polyethylene resins such as chlorinated polyethylene; polypropylene; copolymers containing propylene in an amount of 50% by weight or more and a monomer copolymerizable therewith, such as propylene-ethylene copolymers, propylene-ethyl acrylate copolymers; polypropylene resins such as chlorinated polypropylene; poly-1-butene, and the like.

Particularly preferred olefin polymers include polyethylene, polypropylene, poly-1-butene, propylene-ethylene copolymers, propylene-1-butene copolymers, 1-but-vinyl-ene copolymers, propylene-ethylene-1-butene copolymers, and the like.

These olefin-based polymers may be used singly or in combination of two or more.

The amount of the olefin-based polymer to be blended in the flame-retardant polymer composition of the present invention is usually 0 to 1000 parts by weight, preferably 2 to 1000 parts by weight, more preferably 5 to 800 parts by weight, and still more preferably 10 to 500 parts by weight, based on 100 parts by weight of the secondary modified block copolymer (I), from the viewpoint of the balance between the tensile strength and the tensile elongation of the composition.

The flame-retardant polymer composition of the present invention has excellent flame retardancy, does not generate toxic gases such as halogen gas even when burned, and exhibits well-balanced mechanical properties, and thus can be used as materials suitable for applications such as wire coating materials for wiring in devices and automobile harnesses, and industrial materials such as insulating tapes.

[ CROSS-LINKED PRODUCT ]

The crosslinked product of the present invention is the polymer composition of the present invention comprising the following (i) or (ii), which is obtained by melt-kneading in the presence of a vulcanizing agent.

(i) A crosslinkable material comprising a component (I) (the secondary modified block copolymer of the present invention) and a polymer component (II) selected from at least one of a thermoplastic resin and a rubbery polymer; or

(ii) The polymer composition of the present invention comprises a component (I-1), a component (II) and a component (III).

In the crosslinked product of the invention, the functional group-containing atomic group X in the second-order modified block copolymer (I)¹The functional group (b) can be reacted with a thermoplastic resin and/or a rubbery polymer, etc., which contain a functional group. The second-order modified block copolymer contains a nitrogen atom and an oxygen atom, or a carbonyl group. In the presence of these atoms and groups and in the thermoplasticThe polar groups of the resin and/or the rubbery polymer are effective for the interaction of physical affinity, for example, hydrogen bond, and the like, and thus the composition has good mechanical strength, oil resistance, and the like.

In the crosslinkable material, the weight ratio of the component (I) to the component (II) is usually 10/90 to 100/0, preferably 20/80 to 90/10, and more preferably 30/70 to 80/20. The crosslinkable material may contain 0.01 to 20 parts by weight of the component (III) per 100 parts by weight of the component (I).

When the crosslinked product of the present invention is obtained from the polymer composition of the present invention comprising the component (I-1), the component (II) and the component (III), the weight ratio of the component (I-1) to the component (II) is usually 10/90 to 100/0, preferably 20/80 to 90/10, and more preferably 30/70 to 80/20. The amount of the component (III) is usually 0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, based on 100 parts by weight of the total of the component (I-1) and the component (II).

The melt-kneading in the presence of the vulcanizing agent is carried out under temperature conditions at which the vulcanizing agent reacts in a molten state, whereby dispersion and crosslinking can be simultaneously caused. For melt kneading in the presence of a vulcanizing agent, it is described in detail in the document Rub.chem.Andtechnol.vol.53, 141(1980) of A.Y.Coran et al. The kneader used for melt kneading in the presence of a vulcanizing agent is generally carried out using a closed kneader such as a Banbury mixer or a pressure kneader, a single-screw or twin-screw extruder, or the like. The melt kneading temperature is usually 130 to 300 ℃ and preferably 150 to 250 ℃. The melt kneading time is usually 1 to 30 minutes. Typically, organic peroxide and phenol resin crosslinking agents are used as vulcanizing agents.

As the organic peroxide used as the vulcanizing agent, known substances such as "Gomu Purasuchikukuhou Yakuhin (Additives for Rubber and plastics)" (published byRubber Digest Co., Ltd., Japan (1968)) and the like can be used. Of these, cumene peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne, 1, 3-di (t-butylperoxyisopropyl) benzene, 1, 1-di (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, n-butyl-4, 4-di (t-butylperoxy) valerate, di-t-butyl peroxide and the like are preferable.

When the desired crosslinked product is obtained by crosslinking using the above organic peroxide, it is preferable to use the organic peroxide in combination with a crosslinking assistant, for example, a peroxy crosslinking assistant such as sulfur, P-benzoquinone dioxime, P '-dibenzoylbenzoquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, and trimethylolpropane-N, N' -m-phenyleneimaleimide; divinylbenzene; triallyl cyanurate; multifunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate; and polyfunctional vinyl monomers such as butylated ethylene and vinyl stearate.

When the melt kneading is carried out in the presence of a vulcanizing agent, the amount of the vulcanizing agent to be used is usually 0.01 to 15 parts by weight, preferably 0.04 to 10 parts by weight, based on 100 parts by weight of the component (I) when the component (II) is not contained or 100 parts by weight of the polymer composition when the component (II) is contained.

In the crosslinked product of the present invention, additives may be previously mixed before crosslinking as necessary within a range not impairing the characteristics thereof. The additives include softening agent, heat-resistant stabilizer, antistatic agent, weathering agent, aging inhibitor, filler, colorant, lubricant, etc.

The above-mentioned component (VII) can be used as a softener to be mixed as required for adjusting hardness and fluidity of the product. The amount of the component (I) is usually 0 to 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the component (I) or the component (I-1).

Examples of the filler include calcium carbonate, talc, clay, calcium silicate, magnesium carbonate, and magnesium hydroxide. The amount of these fillers added is usually 0 to 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the component (I) or the component (I-1).

The gel content in the crosslinked product of the present invention (however, the gel content does not contain an incompatible component such as an inorganic filler) is preferably 5 to 80 wt%, more preferably 10 to 70 wt%, and still more preferably 20 to 60 wt%. Here, the gel content is measured by the following method. A sample (1g) of the crosslinked product was refluxed for 10 hours in a Soxhlet extractor using boiling xylene, the residue was filtered through an 80-mesh wire net, the dry weight (g) of insoluble matter remaining on the mesh was measured, and the ratio (wt%) of the resulting dry weight to the sample weight was calculated. The obtained ratio was defined as the gel content of the crosslinked product.

The crosslinked product of the present invention is a composition excellent in mechanical strength, oil resistance, and the like, and can be used for the above-mentioned various applications.

[ Binder composition ]

The adhesive composition of the present invention can be obtained by mixing a tackifier (VIII) (hereinafter often referred to as component (VIII)) to component (I) (the second-order modified block copolymer) or to a mixture of component (I-1) (the first-order modified block copolymer or a hydride thereof) and the second-order modifier component (III).

In the adhesive composition of the invention, the functional group-containing atomic group X in the secondary modified block copolymer¹The functional group or the secondary modifier (III) can react with the adhesive containing a functional group, and since a nitrogen atom and an oxygen atom, or a carbonyl group is contained in the secondary modified block copolymer or the reaction product of the primary modified block copolymer (component (I-1)) and the secondary modifier (component (III)), an interaction due to physical affinity, such as a hydrogen bond, can be effectively generated between these atoms and groups and the polar group of the adhesive (VIII), and the composition is excellent in balance of adhesive properties such as adhesion and holding power.

In the adhesive composition of the present invention, the above-mentioned component (I) or component (I-1) can be used, and particularly preferred is a base block copolymer of component (I) or component (I-1) comprising:

(a)20 to 90% by weight, preferably 25 to 80% by weight of a block copolymer having as the basic skeleton a copolymer of one polymer block A mainly comprising a vinyl aromatic hydrocarbon and one polymer block B mainly comprising a conjugated diene, and

(b)80 to 10 wt%, preferably 75 to 20 wt%, of a block copolymer having as a basic skeleton a copolymer of at least two polymer blocks A mainly comprising a vinyl aromatic hydrocarbon and at least one polymer block B mainly comprising a conjugated diene,

if a base block copolymer comprising the above-mentioned base block copolymer components (a) and (b) is used, an adhesive composition having a particularly excellent balance of holding power, tackiness and melt viscosity can be obtained. These molecular weights (peak molecular weight in terms of standard polystyrene in GPC measurement) are preferably 3 to 15 ten thousand, more preferably 4 to 14 ten thousand, and still more preferably 5 to 13 ten thousand for the component (a) and 10 to 30 ten thousand, preferably 12 to 28 ten thousand, and still more preferably 14 to 26 ten thousand for the component (b), and are also used from the viewpoint of balance between holding power and tackiness and melt viscosity.

The component (VIII) (tackifier) used in the present invention is not particularly limited in kind, and any tackifier resin may be used, for example, known tackifier resins such as rosin-type terpene resin, hydrogenated rosin-type terpene resin, coumarone resin, phenol resin, terpene-phenol resin, aromatic hydrocarbon resin, and aliphatic hydrocarbon resin. These tackifiers may be mixed in two or more kinds. As a specific example of the tackifier, the above-mentioned one of "Gomu PurasuchikukuHaigou Yakuhin" (Additives for Rubber and Plastic) "(published byRubber Digest Co., Ltd., Japan (1968)) can be used. The tackifier is used in an amount of 20 to 400 parts by weight, preferably 50 to 350 parts by weight, based on 100 parts by weight of the component (I) or the component (I-1), from the viewpoint of the balance between the tackiness and the holding force of the adhesive composition.

In addition, the above-mentioned component (VII) (rubber softener) may be added as a softener to the adhesive composition of the present invention, and since the viscosity of the adhesive composition can be reduced by adding the softener, the workability can be improved and the tackiness can be improved. The softener is used in an amount of 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the component (I) or the component (I-1), from the viewpoint of the balance between the tackiness and the holding force of the adhesive composition.

In addition, stabilizers such as antioxidants, light stabilizers, ultraviolet absorbers and the like, specifically, those described in "Gomu … (1968)" may be added to the adhesive composition of the present invention as needed. In the adhesive composition of the present invention, waxes such as paraffin wax, microcrystalline wax, and low-molecular-weight polyethylene wax; polyolefin-based or low-molecular-weight vinyl aromatic thermoplastic resins such as amorphous polyolefins and ethylene-ethyl acrylate copolymers; natural rubber; synthetic rubbers such as polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, polytenanenamer rubber, styrene-butadiene-based or styrene-isoprene-based block copolymers other than the half-modified block copolymer or the modified block copolymer of the present invention, and the like.

The adhesive composition of the present invention can be prepared by uniformly mixing the components under heating using a known mixer, kneader, or the like. The heating temperature is usually 150 to 210 ℃.

The adhesive composition of the present invention has an improved softening temperature and exhibits excellent balance of adhesive properties such as adhesion and holding power, and thus can be used as a raw material for various tapes and labels, pressure-sensitive adhesive sheets, back adhesives for fixing various lightweight plastic moldings, back adhesives for fixing carpets, back adhesives for fixing tiles, and the like, and is particularly advantageously used as a tape and label.

[ adhesive film for surface protection ]

The adhesive film for surface protection of the present invention can be obtained by forming an adhesive layer containing the above-mentioned component (I) and component (VIII) or an adhesive layer containing the component (I-1), component (III) and component (VIII) on a resin film. In the adhesive film for surface protection of the present invention, the functional group-containing atomic group X in the secondary modified block copolymer¹The functional group (b) is reactive with a tackifier (component (VIII)) having a functional group, and since a nitrogen atom and an oxygen atom, or a carbonyl group is contained in the secondary modified block copolymer, an interaction due to physical affinity, such as a hydrogen bond, can be effectively generated between these atoms and groups and a polar group of the adhesive, thereby obtaining an adhesive film for surface protection excellent in anchor strength.

In the surface-protecting adhesive film of the present invention, the thickness of the adhesive layer is usually 200 μm or less, preferably 5 to 50 μm. The thickness of the resin film is usually 300 μm or less, preferably 10 to 100 μm.

In the surface-protecting adhesive film of the present invention, the amount of the tackifier component (VIII) (tackifier) which is one of the components constituting the adhesive layer is 3 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 10 to 120 parts by weight, based on 100 parts by weight of the component (I) or the component (I-1), in consideration of the adhesive strength of the surface-protecting adhesive film, the adhesive strength after long-term attachment, and the adhesive residue during peeling. The amount of the component (VIII) is 0.01 to 20 parts by weight based on 100 parts by weight of the component (I-1).

In the surface-protecting adhesive film of the present invention, a nonpolar resin or a polar resin is used as the resin film. The nonpolar resin includes polystyrene resin, polyolefin resin, and the like. The polystyrene-based resin includes polystyrene, block copolymer resins of styrene and a conjugated diene compound, polymers of the above-mentioned vinyl aromatic compounds, copolymer resins of the above-mentioned vinyl aromatic compounds and other vinyl monomers, for example, ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, etc., rubber-modified styrene-based resin (HIPS), acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylate-butadiene-styrene copolymer resin (MBS), etc. The polyolefin-based resin, which is a nonpolar resin used as a resin, may contain an olefin-based thermoplastic elastomer such as a copolymer rubber of two or more kinds of α -olefins or a copolymer of an α -olefin and another monomer. As these copolymer rubbers, ethylene-propylene copolymer rubbers (EPR), ethylene-butene copolymer rubbers (EBR), ethylene-octene copolymer rubbers, ethylene-propylene-diene copolymer rubbers (EPDM), and the like are included.

On the other hand, in the adhesive film for surface protection of the present invention, the polar resin used as the resin film is the above-mentioned thermoplastic resin having a functional group.

In the surface-protecting adhesive film of the present invention, as the resin used in the resin film, a resin capable of producing a resin film by melt extrusion molding is preferable even among these nonpolar resins or polar resins, and from the viewpoint of performance, price, and the like, a homopolymer or a block copolymer of polyethylene, propylene; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; a polyamide-based resin; ethylene-vinyl acetate copolymers and their hydrolysates, and the like.

The surface-protecting adhesive film of the present invention can be produced as in the following example.

That is, the surface-protecting adhesive film is manufactured by dividing the adhesive component and the thermoplastic resin component into two fluids by using a melt-co-extruder, that is, by forming a single fluid by adding the adhesive layer-forming fluid and the resin film-forming fluid in port ダィス and extruding, and compounding the adhesive layer and the resin film layer. It is also possible to easily manufacture the adhesive layer composition by coating the resin film with the adhesive layer composition.

The surface-protecting adhesive film obtained by the method of the present invention has a good tieback (adhesion between the adhesive layer and the resin film), and therefore, when the surface-protecting adhesive film is formed into sheet metal, for example, on a metal plate, or the metal plate is left for a long period of time, the adhesive film does not cause excess glue.

[ ASPHALT COMPOSITION ]

The asphalt composition of the present invention can be obtained by adding an asphalt (hereinafter often referred to as component (IX)) to component (I) (the second-order modified block copolymer) or by mixing component (I-1), component (III) and component (IX). In the asphalt composition of the present invention, the functional group-containing atomic group X in the secondary modified block copolymer¹The functional group or the secondary modifier (III) is reactive with the functional group in the asphalt (component (IX)), and since the modified block copolymer or the reaction product of the half-modified block copolymer (component (I-1)) and the secondary modifier (component (III)) contains a nitrogen atom, an oxygen atom, or a carbonyl group, an interaction due to physical affinity, for example, a hydrogen bond, is effectively generated between these atoms and groups and the polar group of the asphalt, and an asphalt composition excellent in softening point, elongation, flexibility, polymer grip and high-temperature storage stability is obtained.

In the surface asphalt composition of the present invention, component (I) or component (I-1) may be used, and particularly preferred is a base block copolymer of component (I) or component (I-1) comprising:

if the base block copolymer comprising the above-mentioned base block copolymer components (a) and (b) is used, an asphalt composition excellent in the balance of softening point and phase separation stability can be obtained. These molecular weights (peak molecular weight in terms of standard polystyrene in GPC measurement) are preferably 3 to 15 ten thousand, more preferably 4 to 14 ten thousand, and still more preferably 5 to 13 ten thousand for the component (a) and 10 to 30 ten thousand, preferably 12 to 28 ten thousand, and still more preferably 14 to 26 ten thousand for the component (b), and are also used from the viewpoint of the balance between the softening point and the phase separation stability of the asphalt composition.

The asphalt (component (IX)) used in the asphalt composition includes petroleum asphalt (a by-product in petroleum refining), or natural asphalt, or a mixture of these with petroleum, and the main component thereof may be asphalt (bitumen). Specifically, straight asphalt, semi-blown asphalt, tar, pitch, cutback asphalt with petroleum added, asphalt emulsion, and the like can be included. These bitumens may be used individually or in admixture. Preferred asphalt in the present invention is straight-chain asphalt having a penetration (measured according to JIS-K2207) of 30 to 300, preferably 40 to 200, and more preferably 45 to 150. In the asphalt composition of the present invention, the mixing ratio of the component (I) or the component (I-1) is 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 3 to 20 parts by weight, based on 100 parts by weight of the component (IX) (asphalt).

When the asphalt composition of the present invention comprises the component (I-1), the component (IX) and the component (III), the component (III) is blended in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.2 to 3 parts by weight, and further preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the asphalt component (IX). Further, the asphalt composition comprising the component (I) and the component (IX) may further comprise 0.1 to 5 parts by weight of the component (III) per 100 parts by weight of the component (IX).

The asphalt composition of the present invention may be mixed with a sulfur-containing component (hereinafter, often referred to as "component (X)") as required. The component (X) may be powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, inert sulfur, or the like, and sulfur-containing compounds such as sulfur chloride, sulfur dioxide, morpholine disulfide, alkylphenol disulfide, and high-molecular polysulfide may be used. Further, the component (X) may be used in combination with an appropriate amount of a crosslinking accelerator. As the crosslinking accelerator, a sulfonamide accelerator, a guanidine accelerator, a thiuram accelerator, an aldehyde amine accelerator, an aldehyde ammonia accelerator, a thiazole accelerator, a thiourea accelerator, a dithiocarbamate accelerator, a xanthate accelerator, and the like can be used. Specific examples of the crosslinking agent include diphenylguanidine, N-butylaldehyde-aniline condensate, hexamethylenetetramine, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazylsulfenamide, diphenylthiourea, tetramethylthiuram monosulfide, sodium dimethyldithiocarbamate and zinc isopropylsulfonate. The amount of sulfur in the component (X) is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the component (IX). When a crosslinking accelerator is used, the amount thereof is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the component (IX).

In addition, in the asphalt composition of the present invention, a silane coupling agent may be added. The silane coupling agent may be used in an amount of usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the component (IX).

In the asphalt composition of the present invention, a surfactant such as an anionic surfactant, a cationic surfactant, and a nonionic surfactant may be mixed as necessary from the viewpoint of grip performance. Specific examples of the surfactant include higher fatty acids, metal salts of higher fatty acids, monoamine compounds, diamine compounds, polyamine compounds, copolymerized oligomers of polyethylene oxide and polypropylene oxide, and the like. Further, an acidic organic phosphorus compound, a mixture of an acidic organic phosphorus compound and an inorganic phosphorus compound, a higher alcohol phosphate such as a polycarboxylic acid and an anhydride thereof, an aliphatic phosphate, a stearyl phosphate, a mixture of a higher alcohol and a phosphated alcohol, gallic acid or a derivative thereof, tall oil acid or a derivative thereof, a condensate of polyalkylene polyamine and a fatty acid, a liquid epoxy resin, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified SBS (styrene-butadiene block copolymer), maleic anhydride graft-modified SEBS (styrene-ethylene/butylene block copolymer), maleic anhydride graft-modified SEPS (styrene-ethylene/propylene block copolymer), and the like can be used.

In the asphalt composition of the present invention, any additives may be mixed as needed. The type of the additive is not particularly limited as long as it is generally used for mixing the thermoplastic resin and the rubber-like polymer. For example, the inorganic filler component (VI) and other inorganic fillers, organic fillers, silane coupling agents, rubber softener component (VII), tackifier component (VIII), stabilizers such as antioxidants, vulcanizing agents such as organic peroxides and phenolic resin crosslinking agents, auxiliaries for peroxide crosslinking, polyfunctional vinyl monomers, and other various additives described above can be added. Component (II) may also be added as required.

The asphalt composition of the present invention has excellent softening point, elongation, flexibility, and holding properties, and has excellent high-temperature storage stability, and can be widely used for paving, waterproof sheets, sound-insulating sheets, roofing materials, and the like.

The asphalt composition of the present invention is suitable for use as a binder for drainage road surfaces such as roads which are likely to be encountered by overweight vehicles such as high-traffic roads, highways, intersections, and turning spots, because of its high-temperature storage stability, elongation, low-temperature flexibility, and good handleability.

The water-draining pavement road of the present invention is a water-draining pavement road comprising a road and a water-draining pavement layer having a plurality of drainage pores formed thereon, the water-draining pavement layer being composed of a plurality of aggregates and a binder composed of the asphalt composition of the present invention.

The water-draining road surface using the asphalt composition of the present invention as a binder has excellent low-temperature characteristics such as rut resistance, water permeability, reduced traffic noise, and resistance to cracking at low temperatures.

Generally, an asphalt pavement road is formed by the following method. A binder is added to a mixture of coarse aggregates (crushed stones), fine aggregates (sand, crushed sand, stone powder), etc. having an appropriate particle size distribution in a heated state (temperature is usually 150 to 210 ℃) to obtain an asphalt mixture (binder amount is 5.3 to 6.5%, preferably 5.5 to 6%). The resulting asphalt mixture is coated on a road surface, and an asphalt mixture layer on the road surface is rolled flat with a roller or the like, thereby obtaining an asphalt road.

The water-draining road surface of the present invention is formed by the following method. The asphalt composition of the present invention as a binder is added in a heated state (temperature is usually 150 to 210 ℃) to a mixture of coarse aggregates (crushed stones), fine aggregates (sand, crushed sand, stone powder) and the like having an appropriate particle size distribution to obtain an asphalt mixture (binder amount is 4.5 to 5.5%, preferably 4.7 to 5.3%). The obtained asphalt mixture (containing the asphalt composition of the present invention) is coated on a road surface, and the asphalt mixture layer on the road surface is rolled flat with a roller or the like, thereby obtaining the water-permeable road surface of the present invention. The water-drainage pavement layer of the water-drainage pavement road of the present invention has a very large number of continuous pores for water drainage, compared to many pores on the pavement layer of a general pavement road formed using a general asphalt mixture. Due to this characteristic, the water-draining road surface of the present invention exhibits excellent properties such as water drainage for preventing the generation of rain puddles, the ability to ensure safety of walking by preventing rain on the road surface from forming a continuous water film, and the ability to reduce traffic noise (e.g., exhaust noise or noise generated by contact of tires with the road surface). Also, the porosity can be obtained by controlling the size (particle diameter) of the aggregate and the mixing ratio of the aggregate and the asphalt to obtain a desired value. The drainage pavement layer formed by using the asphalt composition has a porosity of 5 to 35%, more preferably 10 to 30%, and still more preferably 12 to 28%.

The porosity of the bitumen composition is defined by the following formula.

Asphalt porosity (%)

In the formula, ρ_mRepresents the density (g/cm) of the bituminous mixture³) And V represents the volume (cm) of the asphalt mixture³)，V_VRepresents the pore volume (cm) of the bituminous mixture³) And D represents the theoretical maximum density (g/cm) of the bituminous mixture³)。

Best mode for carrying out the invention

The present invention is specifically illustrated by the following examples, but the present invention is not limited to these examples.

1. Characteristics of Block copolymer and hydrogenated product thereof

(1) Styrene content

The absorption intensity of the block copolymer was measured at 262nm using an ultraviolet spectrophotometer (UV 200, manufactured by Hitachi, Japan) to calculate the styrene content.

(2) Styrene Block Rate

A predetermined amount (30 to 50mg) of the block copolymer was precisely weighed, about 10ml of chloroform was added thereto, osmium tetroxide (catalyst) and tert-butyl hydroxyperoxide (oxidant) were added thereto, and the mixture was boiled at 100 ℃ for 20 minutes to oxidatively decompose the block copolymer. To the resulting reaction mixture was added 200ml of methanol, thereby precipitating polystyrene. The precipitate was filtered using 11G4 (manufactured by japan diesel field scientific instruments industry ltd.) to obtain a filtered residue composed of polystyrene, and the weight of the obtained polystyrene was measured. The styrene Block ratio (% by weight) was calculated from the following formula

Styrene block ratio (% by weight) × 100 (weight of filtration residue/total weight of styrene monomer units in the predetermined amount of block copolymer) × 100

(3) Vinyl bond content and hydrogenation rate

Measured using a nuclear magnetic resonance apparatus (DPX-400, manufactured by BRUKER, Germany).

(4) Weight average molecular weight

Measured by GPC (apparatus: LC10 manufactured by Shimpan, Japan; column: Shimpac GPC805+ GPC804+ GPC804+ GPC803 manufactured by Shimadzu, Japan). The measurement was performed at a temperature of 35 ℃ using tetrahydrofuran as a solvent. The weight average molecular weight was determined by GPC chromatography showing peak molecular weights using a calibration curve obtained from commercially available monodisperse standard polystyrene samples.

(5) Proportion of unmodified Block copolymer

The ratio (a) of the modified block copolymer to the standard polystyrene was determined from the chromatogram obtained by GPC measurement by the same method as (4) above with respect to a sample solution containing 10mg of the modified block copolymer and 10mg of low-molecular-weight internal standard polystyrene having a weight-average molecular weight of 8000 in 20ml of tetrahydrofuran. The sample solution was subjected to GPC measurement using the same method as in (4) except that a Zorbax apparatus manufactured by DuPont, U.S.A., and a column using silica gel as a filler were used, to determine the ratio (b) of the unmodified block copolymer to the standard polystyrene. Since (a) is the sum of the modified block copolymer portion and the unmodified block copolymer portion and (b) is only the unmodified block copolymer portion, the ratio of the unmodified block copolymer in the modified block copolymer can be obtained by these two ratios (a) and (b).

2. Preparation of hydrogenation catalyst

The hydrogenation catalyst used in the hydrogenation reaction was prepared by the following method.

(1) Hydrogenation catalyst I

A nitrogen-substituted reactor was charged with 1 liter of dried, purified cyclohexane, and then 100 mmol of bis (. eta.) (eta.)⁵Cyclopentadienyl) titanium dichloride, a solution of n-hexane containing 200 mmol of trimethylammonium was added with stirring thoroughly, and reacted at room temperature for 3 days to obtain hydrogenation catalyst I.

(2) Hydrogenation catalyst II

A nitrogen-substituted reactor was charged with dried, purified 2L cyclohexane, and then 40 mmol of bis (. eta.) (eta.)⁵After dissolving cyclopentadienyl-di- (p-tolyl) titanium and 150g of 1, 2-polybutadiene having a molecular weight of about 1000 (1, 2-vinyl bond content: about 85%), a cyclohexane solution containing 60 mmol of n-butyllithium was added and allowed to react at room temperature for 5 minutes, and then 40 mmol of n-butanol was immediately added thereto with stirring, thereby obtaining hydrogenation catalyst II, which was stored at room temperature.

3. Preparation of living polymers of Block copolymers

Preparation of Polymer 1 (hereinafter often referred to as P-1):

an autoclave equipped with a stirrer and a jacket was washed, dried, and replaced with nitrogen, and then a cyclohexane solution (styrene concentration 20 wt%) containing 10 parts by weight of previously purified styrene was added. Then, n-butyllithium and tetramethylethylenediamine (used as a vinylating agent and a randomizing agent) were added in amounts shown in Table 1, respectively, and after 1 hour of polymerization at 70 ℃, a cyclohexane solution containing 80 parts by weight of butadiene purified in advance (butadiene concentration: 20% by weight) was added and polymerized at 70 ℃ for 1 hour, and further a cyclohexane solution containing 10 parts by weight of styrene was added and polymerized at 70 ℃ for 1 hour, thereby obtaining Polymer 1(P-1), which is a living polymer of a block copolymer. The properties of polymer 1 are shown in table 1.

Preparation of polymers 2 to 23 (hereinafter often referred to as P-2 to P-23, respectively):

polymers 2 to 23 (hereinafter, often referred to as P-2 to P-23, respectively) which are living polymers of block copolymers having the characteristics shown in Table 1 were obtained in the same manner as the polymer 1 except that the amount of the added monomer was changed.

4. Preparation of once-modified block copolymer and hydride thereof

The first-order modified block copolymer was prepared as follows. To the solutions of the living polymers 1 to 23 each containing the block copolymer, a predetermined amount of the primary modifier shown in tables 2, 5, 8, 13, 15, 21 and 23 was added, and the mixture was reacted at 70 ℃ for 20 minutes to obtain a primary modified block copolymer.

The hydrogenated product of the once-modified block copolymer was prepared as follows. A hydrogenation catalyst I or II was added to the solution of the primary modified block copolymer in an amount of 100ppm in terms of Ti, and hydrogenation was carried out at a hydrogen pressure of 0.7MPa and a temperature of 65 ℃ for 1 hour to obtain a hydrogenated product of the primary modified block copolymer.

Each of the solutions of the once-modified block copolymer and the hydrogenated product thereof was added with methanol in an amount of 10 mol per n-butyllithium used for the polymerization, and then with soda water to adjust the pH to 8 or less.

The properties of the obtained primary modified block copolymer or the hydrogenated product thereof are shown in tables 2, 5, 8, 13, 15, 21 and 23.

5. Preparation of Secondary modified Block copolymer

The second-order modified block copolymer was prepared as follows. The primary modified block copolymer or the hydrogenated product thereof obtained above is reacted with a secondary modifier by a melt kneading method or a solution method, respectively, to obtain a secondary modified block copolymer.

In the case of the melt-kneading method, 0.3 part by weight of octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer in each of the above-obtained first-order modified block copolymers or hydrogenated product solutions thereof, and then the solvent was removed by heating. A predetermined amount of the secondary modifier shown in tables 2, 5, 8, 13, 15, 21 and 23 was mixed with the obtained primary modified block copolymer or the hydrogenated product thereof, and the mixture was melt-kneaded at 220 ℃ with a 30mm φ twin-screw extruder at a screw revolution number of 100rpm to react.

In the case of the solution method, methanol is added to a solution of the first-order modified block copolymer or the hydrogenated product thereof in an amount of 10 times the mole of n-butyllithium used for the polymerization, soda water is then added to adjust the pH to 8 or less, and then the second-order modifier in the amounts shown in tables 2, 5, 8, 13, 15, 21 and 23 is added to the solution and reacted at about 60 ℃ for 30 minutes. 0.3 part by weight of octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer, and the solvent was removed by heating to obtain a secondary modified block copolymer.

The properties of the obtained secondary modified block copolymer are shown in tables 2, 5, 8, 13, 15, 21 and 23.

6. The relationship between the primary modifiers (M1 to M5) and the secondary modifiers (D1, D2) used in the examples, the structures of the obtained primary modified block copolymers, and the structures of the secondary modified block copolymers was as follows.

Relationship between primary modifiers (M1-M5) and Structure:

m1: when M1 is used as the primary modifier, the resulting primary modified block copolymer has a structure represented by the formula (8) wherein C²Represents any of a unit of the formula (D-1) and a unit of the formula (e-1), D²Represents a unit of the formula (f-1).

M2: when M2 is used as the primary modifier, the resulting primary modified block copolymer has a structure represented by the formula (6) or (7) wherein A²Represents any of a unit of the formula (a-1) and a unit of the formula (B-1), B²Represents a unit of the formula (c-1).

M3: when M3 is used as the primary modifier, the resulting primary modified block copolymer has a structure represented by the formula (10) wherein E is²Represents a unit of the formula (g-1), F²Represents any of the units of formulae (h-1), (I-1) and (j-1).

M4: when M4 is used as the primary modifier, the resulting primary modified block copolymer has a structure represented by the formula (9) wherein C²Represents any of a unit of the formula (D-1) and a unit of the formula (e-1), D²Represents a unit of the formula (f-1).

M5: when M5 is used as the primary modifier, the resulting primary modified block copolymer has a structure represented by the formula (10) wherein E is²Represents a unit of the formula (g-1), F²Represents a unit of the formula (h-1).

Relationship of secondary modifier (D1, D2) and structure:

d1: when the primary modification is carried out using any of the above-mentioned primary modifiers (M1 to M5) and then the secondary modification is carried out using D1, a compound having X¹Is a secondary modified block copolymer with a unit structure of a formula (n).

D2: if a secondary modification is carried out using D2 after a primary modification is carried out using any of the above-mentioned primary modifiers (M1-M5), a compound having X can be obtained¹Is a secondary modified block copolymer with a unit structure of a formula (p).

Thermoplastic polymersExamples and comparative examples of resin compositions

(1) Modified block copolymer

The modified block copolymers used are shown in table 2.

(2) Thermoplastic resin

PET: chemical three-well ペット SA135 of Japan three-well

Polyamide: nylon 6 (east Li system of Japan アミラン CM1017)

(3) Measurement of physical Properties

Flexibility ratio (MPa): ASTM-D790 is used as a standard.

Notched Izod impact strength (J/m): JIS K-7110 was used as a standard.

Examples 1 to 8 and comparative examples 1 to 6

Examples 1 to 8 and comparative examples 1 to 6 were prepared by dry-mixing predetermined amounts of a thermoplastic resin, a first modified block copolymer or an unmodified block copolymer, and a second modifier according to the mixing formulation shown in Table 3, adding 0.3 part by weight of 2-tert-amyl-6- [1- (3, 5-di-tert-amyl-2-hydroxyphenyl) ethyl ] -4-tert-aminophenyl acrylate as a stabilizer to 100 parts by weight of the mixture, and melt-kneading at 250 ℃ in the case where the thermoplastic resin was PET and at 260 ℃ with a screw revolution number of 250rpm in the case where the thermoplastic resin was polyamide using a 30mm phi twin-screw extruder. The physical properties of the obtained composition are shown in table 3.

Examples 9 to 13 and comparative examples 7 and 8

In examples 9 to 13 and comparative examples 7 and 8, resin compositions were obtained in the same manner as in examples 1 to 8 using the twice-modified block copolymer or the unmodified block copolymer according to the mixing formulation shown in Table 4. The composition and physical properties of the composition are shown in Table 4. Further, "P-2/D2 (1.2 mol/Li)" of comparative example 7 and comparative example 8 in Table 4 means "a mixture of polymer P-2 and a secondary modifier, the concentration of D2 in preparing polymer P-2 was 1.2 mol/mol of added butyl lithium".

From the results of examples 1 to 13 and comparative examples 1 to 8, it is understood that the functional group-containing block copolymer of the present invention is effective in improving the impact strength of a thermoplastic resin.

Examples and comparative examples of flame retardant Polymer compositions

(1) Modified block copolymer

The modified block copolymers used are shown in table 5.

(2) Inorganic flame retardant

X-1: magnesium hydroxide surface-treated with higher fatty acid (KISUMA 5A, manufactured by KISUMA CO CHEMICAL CO., LTD.)

X-2: untreated magnesium hydroxide (KISUMA 5A manufactured by Kyowa chemical Co., Ltd., Japan)

(3) Olefin polymer

PM801A manufactured by polypropylene Moutell SDK

(4) Measurement of physical Properties

Tensile strength: the breaking strength (MPa) and the elongation at break (%) were measured in accordance with JIS K7210.

Oxygen index (O.I.): measured according to JIS K7210. The oxygen index means that the polymer sample, N, is added to the cylindrical vessel₂And O₂After sealing the mixture, and burning the sample, the sample continuously burns for more than 3 minutes to determine the N₂/O₂The oxygen concentration in the mixture. The higher the oxygen index, the higher the flame retardancy. The oxygen index was measured and evaluated at three levels of |,. o, and ×, according to the following criteria.

Very good: over 28 percent

O: more than 24 percent and less than 28 percent

X: less than 24 percent

Examples 14 to 21 and comparative examples 9 to 11

Examples 14 to 21 and comparative examples 9 to 11 were flame retardant polymer compositions blended according to the blending formulation shown in Table 6, wherein 100 parts by weight of the hydrogenated product of the primary modified block copolymer was added with predetermined amounts of an inorganic flame retardant, a secondary modifier, and polypropylene, and 0.03 part by weight of 2-tert-amyl-6- [1- (3, 5-di-tert-amyl-2-hydroxyphenyl) ethyl ] -4-tert-aminophenyl acrylate as a stabilizer, and the mixture was melt-kneaded at 220 ℃ using a 30mm phi twin-screw extruder to obtain flame retardant polymer composition pellets. The obtained pellets were subjected to injection press molding to prepare samples for evaluation of physical properties. The physical properties of the composition are shown in Table 6.

Examples 22 to 24 and comparative example 12

In examples 22 to 24 and comparative example 12, flame retardant polymer compositions were obtained according to the mixing formulations shown in Table 7 in the same manner as in examples 14 to 21. The composition and physical properties of the composition are shown in table 7. Further, "1P-10/D1 (2.1 mol/Li)" in comparative example 12 of Table 7 means "a mixture of polymer 1P-10 and secondary modifier D1, and the concentration of D1 in the preparation of polymer 1P-10 was 2.1 mol/mol of added butyl lithium. "

From the results of examples 14 to 24 and comparative examples 9 to 12, it was found that the flame retardant polymer composition of the present invention is excellent in flame retardancy, does not generate toxic gas (halogen gas or the like) even when burned, and is suitable for applications such as wire coating materials for wiring in equipment and automobile harnesses, industrial materials such as insulating tapes, and the like because of its excellent balance of mechanical properties.

Examples of adhesive films for surface protection and comparative examples

(1) Block copolymer

The modified block copolymers used are shown in table 8.

(2) Measurement of physical Properties

The physical properties of the surface-protecting adhesive film were measured as follows. The adhesive composition obtained by the following method was taken out in a molten state, and applied on a resin film having a thickness of 100 μm to form a coating layer having a thickness of 15 μm, to prepare an adhesive film, and the anchorage force, the adhesive force, and the residual adhesive after the attachment were measured by the following methods.

Tieback (g/20 mm): after a film having a width of 20mm was firmly adhered between the surfaces to which the adhesive was applied, a 180-degree peel test was performed at a peel rate of 200mm/min at 20 ℃ C.. times.65% Relative Humidity (RH).

Adhesion (g/25 mm): an adhesive film was attached to a SUS304 steel plate 25mm in width, and a 180-degree peel test was performed at a peel speed of 200mm/min at 20 ℃ C.. times.65% Relative Humidity (RH).

The glue remaining after attachment: an adhesive film was attached to an SUS304 steel plate, and after standing at 40 ℃ for 6 months, the presence or absence of the remaining adhesive was observed at 20 ℃ C.. times.65% Relative Humidity (RH).

Examples 25 to 29 and comparative examples 13 and 14

In examples 25 to 29 and comparative examples 13 and 14, adhesive compositions were prepared by mixing adhesive compositions according to the mixing formulation shown in Table 9, mixing predetermined amounts of a tackifier and a secondary modifier with 100 parts by weight of a primary modified block copolymer or a hydrogenated product thereof, and further 0.3 part by weight of 2-tert-amyl-6- [1- (3, 5-di-tert-amyl-2-hydroxyphenyl) ethyl ] -4-tert-aminophenyl acrylate as a stabilizer, and melt-mixing the mixture at 180 ℃ for 2 hours in a vessel equipped with a stirrer. An adhesive film was produced using the obtained adhesive composition and a polyethylene film, and physical properties were measured. The composition and physical properties of the mixture are shown in table 9.

Examples 30 to 34 and comparative examples 15 and 16

Adhesive compositions were prepared in examples 30 to 34 and comparative examples 15 and 16 by mixing adhesive compositions according to the mixing formulation shown in table 10 and using the same method as in examples 25 to 29. An adhesive film was produced using the obtained adhesive composition and PET film, and physical properties were measured. The composition and physical properties of the mixture are shown in table 10.

Examples 35 to 38 and comparative example 17

Adhesive compositions were obtained in examples 35 to 38 and comparative example 17 according to the mixing formulation shown in Table 11, using the second-order modified block copolymer, and by the same method as in examples 25 to 29. An adhesive film was produced using the obtained adhesive composition and a polyolefin film, and physical properties were measured. The composition and physical properties of the mixture are shown in table 11. Further, "1P-16/D1 (2.1 mol/Li)" in comparative example 17 in Table 11 means "a mixture of polymer 1P-16 and secondary modifier D1, the concentration of D1 in the preparation of polymer 1P-16 was 2.1 mol/mol of added butyl lithium. "

Examples 39 to 41 and comparative example 18

Adhesive compositions were obtained in examples 39 to 41 and comparative example 18 according to the mixing formulations shown in Table 12 in the same manner as in examples 30 to 34. An adhesive film was produced using the obtained adhesive composition and PET film, and physical properties were measured. The blend composition and physical properties are shown in table 12. Further, "1P-16/D1 (2.1 mol/Li)" in comparative example 18 in Table 12 means "a mixture of polymer 1P-16 and secondary modifier D1, the concentration of D1 in the preparation of polymer 1P-16 was 2.1 mol/mol of added butyl lithium. "

It is understood from examples 25 to 41 and comparative examples 13 to 18 that the protective adhesive film of the present invention is excellent in anchor strength and adhesive force and does not generate excess adhesive even after long-term storage.

Adhesive composition examples and comparative examples

(1) Block copolymer

The modified block copolymers used are shown in table 13.

(2) Measurement of physical Properties of adhesive composition

a. Softening point

The softening point was measured according to JIS-K2207 (ring pulling method and ball printing method).

Further, the adhesive composition obtained in a molten state immediately after the preparation was coated on a resin film so as to have a thickness of 50 μm using an applicator to prepare an adhesive tape, and the physical properties were measured by the following method.

b. Adhesion (g/10 mm): a sample having a width of 25mm was attached to styrene, and a 180-degree peel test was performed at a peel rate of 300mm/min at 20 ℃ C.. times.65% Relative Humidity (RH), and the width was converted to 10 mm.

c. Shear adhesion (min): the shear adhesion was measured according to JIS Z-1524. A tape sample having an adhesive composition layer with an area of 25mm × 25mm was provided and adhered to a stainless steel plate, a load of 1kg was given at 60 ℃ and the time for which the tape was peeled off was measured.

d. Peel strength: after preheating a sample having a thickness of about 100 μm at 150 ℃ on a support plate, it was pressurized at the same temperature (load of 1 kg/cm)²) The adhesion was carried out for 5 minutes, and the peel strength was measured by the method according to the peel test of JISK 6854. The measurement was carried out at a peeling speed of 200 mm/min.

Examples 42 to 45 and comparative example 19

In examples 42 to 45 and comparative example 19, an adhesive composition was obtained by mixing a tackifier, Diana process oil PW90 (manufactured by sunrise of japan) as a softening agent, and a secondary modifier with 100 parts by weight of the primary modified block copolymer or the secondary modified block copolymer, and 1 part by weight of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate as a stabilizer in accordance with the mixing formulation shown in table 14, and melt-mixing the mixture at 180 ℃ for 2 hours in a container equipped with a stirrer. The composition and physical properties of the mixture are shown in table 14.

Example 46

In example 46 according to the mixing formulation shown in Table 14, a secondary modified block was used

(2) Measurement of physical Properties of asphalt composition

a. Softening point

Measured according to JIS-K2207 (Ring pulling method and ball printing method).

b. Melt viscosity

Measured at 180 ℃ with a Brookfield viscometer.

c. Penetration rate

The penetration rate is a length of penetration of a probe into a sample of the asphalt composition kept at 25 ℃ in a constant temperature water bath for 5 seconds, as specified in JIS-K2207.

d. Elongation percentage

The elongation is measured as the distance to be elongated until the specimen is broken when the specimen is pulled at a speed of 5cm/min after the specimen of the asphalt composition is poured into a mold and is transformed into a predetermined shape in accordance with JIS-K2207 and is kept at 4 ℃ in a constant temperature water bath.

e. Adhesive strength

The asphalt composition dissolved in toluene was applied to canvas by a coater, dried at room temperature for 1 hour, and dried in an oven at 70 ℃ for 7 minutes to completely evaporate toluene. Then, the canvas coated with the asphalt composition was put into an oven at 70 ℃ for 1 hour together with granite having a smooth surface as an adherend, and was taken out and then pressed twice with a roller bearing a load of 1 kg. The 180 degree peel test of canvas and granite was then performed in a thermostatic chamber at 23 ℃ x 65% Relative Humidity (RH).

f. Low temperature bending characteristics

The asphalt composition was poured into a 20mm × 20mm × 120mm mold, the excess asphalt composition was cut off, and the asphalt composition was quickly taken out after 4 hours of maintenance in a-10 ℃ cold box, and the bending stress and the bending strain (displacement up to the yield point) were measured at a distance of 80mm, a load speed of 100mm/min, and a two-point supported central load.

g. High temperature storage stability

Immediately after the production of the asphalt composition, the asphalt composition was poured into an aluminum pot having an inner diameter of 50mm and a height of 130mm up to the upper limit, and then placed in an oven at 180 ℃ and taken out after 24 hours to allow it to be naturally cooled. Then, the softening points of the upper layer part and the lower layer part were measured using the asphalt composition of 4cm from the lower end and 4cm from the upper end, and the difference in the softening points was used as a measure of the high-temperature storage stability.

(3) Characteristics of water-draining pavement mixtures

A drainage pavement mixture having a porosity of about 20% was prepared by mixing aggregates designed for a porosity of about 20% with about 85% by weight of crushed stone No. 6 (S-13 crushed stone) (particle size range: 13mm to 5mm), about 10% by weight of crushed sand, and about 5% by weight of stone powder, heating to 170 ℃, adding 5% by weight of a heat-melted asphalt composition as a binder thereto, and mixing at 170 ℃, and the following characteristics were measured. The porosity is a value calculated from the volume and weight of the above mixture.

Cantabro mouth test

The Cantabro test is a test to evaluate aggregate dispersion resistance of asphalt mixtures. The measurement was performed according to the Cantabro test method of "pavement test method handbook (tentative test method)" (published by the society of Japan road Association (1988)). The maintenance temperature was 0 ℃ and the test temperature was 18 ℃.

b. Wheel Tracking Test (Wheel Tracking Test)

The wheel tracking test is a test for evaluating the flow resistance of the asphalt mixture in an indoor environment. The measurement was performed according to the wheel tracking test method of the "pavement test method accessibility book (tentative test method)" (published by the society of Japan road Association (1988)). Specifically, the Dynamic Stability (DS) is determined from the amount of change per unit time of a sample by repeatedly running a small rubber wheel having a predetermined load on the sample having a predetermined size. The test temperature was 60. + -. 0.5 ℃.

Examples 47 to 49 and comparative examples 20 to 21

In examples 47 to 49 and comparative examples 20 to 21, according to the mixing formulation shown in Table 16, 400g of straight-chain asphalt 60-80 (manufactured by Nippon Petroleum Co., Ltd.) was added to a 750ml metal can, and the metal can was sufficiently immersed in an oil bath at 180 ℃. Then, the block copolymer and the secondary modifier are added little by little in a predetermined amount to the asphalt which is in a molten state and stirred. After complete addition, the mixture was stirred at a rotation rate of 5000rpm for 90 minutes to prepare a pitch composition. The composition and physical properties of the mixture are shown in Table 16. Furthermore, 1, 2, 4, 5-benzenetetracarboxylic dianhydride is used as a secondary modifier. In example 49 and comparative example 21, the following examples were used

Asphalt compositions were prepared in the same manner as in example 47 according to the compounding formulations shown in Table 17 in example 50 and comparative examples 22 and 23. The composition and physical properties of the mixture are shown in Table 17.

TABLE 17

Example 51

An asphalt composition was obtained in the same manner as in example 47, except that 2 parts by weight of maleic anhydride was used as a secondary modifier. The physical properties thereof are shown in Table 18.

Example 52

A bituminous composition was obtained in the same manner as in example 47, except that 2P-13 was used as a block copolymer. The physical properties thereof are shown in Table 18.

Example 53

An asphalt composition was obtained in the same manner as in example 47, except that 1P-31 as a block copolymer, linear asphalt 80-100 and maleic anhydride as a secondary modifier were used. The physical properties thereof are shown in Table 18.

Example 54

A bituminous composition was obtained in the same manner as in example 53, except that 2P-14 was used as the block copolymer, respectively. The physical properties thereof are shown in Table 18.

Example 55

An asphalt composition was obtained in the same manner as in example 47, except that tolylene diisocyanate was used as the secondary modifier. The physical properties thereof are shown in Table 18.

Example 56

An asphalt composition comprising 100 parts by weight of a linear asphalt 60 to 80[ manufactured by Nippon Petroleum Co., Ltd ], 8 parts by weight of a solution-modified secondary modified block copolymer 2P-15 and 0.1 part by weight of sulfur (Jinhua printed micro powder sulfur, manufactured by Rigaku chemical industry Co., Ltd.) was obtained in the same manner as in example 47. The physical properties thereof are shown in Table 18.

Example 57

An asphalt composition consisting of 100 parts by weight of a linear asphalt 60 to 80[ manufactured by Nippon Petroleum Co., Ltd ], 8 parts by weight of a solution-modified secondary modified block copolymer 2P-16 was obtained in the same manner as in example 47. The characteristics of the obtained asphalt composition and the characteristics of the drainage pavement mixture obtained by mixing the asphalt composition are shown in Table 19.

Comparative example 24

An asphalt composition and a drainage pavement mixture were prepared in the same manner as in example 57, except that an unmodified block copolymer (P-20) which did not react the modifier was used in place of the second-modified block copolymer 2P-16. The physical properties thereof are shown in Table 19.

As can be seen from examples 47 to 57 and comparative examples 20 to 24, the asphalt composition of the present invention not only exhibited an excellent balance of asphalt properties, but also exhibited excellent high-temperature storage stability.

Examples of crosslinked products of modified Block copolymer compositions and comparative examples

(1) Modified block copolymer

The modified block copolymers used are shown in table 20.

Further, the second-order modified block copolymer (2P-17) used in example 58 was produced as follows. 1, 3-dimethyl-2-imidazolidinone (primary modifier M1) as a modifier was reacted with a living polymer P-21 (primary modification) in an amount equivalent to gram molecular weight with respect to n-butyllithium used in the polymerization, followed by hydrogenation, and 1 mole of a secondary modifier D1 (with respect to 1 equivalent of a functional group bonded to the polymer) was added to the polymer solution and reacted (secondary modification) to obtain a secondary modified block copolymer (2P-17).

The first-modified block copolymer (1P-34) used in comparative example 25 was prepared in the same manner as in 2P-17 above, except that the second modification was not conducted.

(2) Ingredients used in the preparation of crosslinked products

Silicon oxide: HDK-N200 of high-dispersibility silicon oxide prepared from Asahi-Kasei

Polypropylene resin: sun Allomer PC600S (manufactured by Montell SDK of Japan)

Paraffin oil: diana Process oil PW380 (the product of the light of China)

Organic peroxide: PERHEXA 25B (manufactured by Japanese fat and oil of Japan)

Vulcanization accelerator (b): divinylbenzene

(3) Measurement of physical Properties (tensile Strength (MPa), tensile elongation (%))

Tensile properties: the measurement was carried out at a tensile stress rate of 500mm/min using a No. 3 dumbbell in accordance with JIS K6251.

Example 58 and comparative example 25

In example 58 and comparative example 25, according to the mixing formulation shown in Table 20, 20 parts by weight of silica, 48 parts by weight of polypropylene and 72 parts by weight of paraffin oil were mixed by a Henschel mixer with respect to 100 parts by weight of the modified block copolymer, and the mixture before dynamic crosslinking was obtained by melt-kneading at 220 ℃ using a 30mm phi twin-screw extruder. To the mixture was added a vulcanizing agent, and melt-kneaded by a 30mm phi twin-screw extruder to obtain a vulcanized crosslinked product. The physical properties of the resulting crosslinked product are shown in Table 20.

Examples 59 to 64

In examples 59 to 69, resin compositions were obtained in the same manner as in examples 9 to 13 using the first-order modified block copolymer or the second-order modified block copolymer shown in Table 21 and according to the compounding formulation shown in Table 22. The composition and physical properties of the composition are shown in table 22.

Examples 65 to 66 and comparative example 26

The peel strength was measured for examples 65 to 66 and comparative example 26 using the second-order modified block copolymer shown in Table 23. The peel strength was measured by preheating a polymer having a thickness of about 100 μm on a support (aluminum plate, PET film, canvas) at a predetermined temperature shown in Table 24 for 5 minutes and then pressing for 5 minutes(load 1 kg/cm)²) Adhesion to the support, and a value measured at a peeling rate of 200 mm/min.

The results of measuring the peel strength are shown in table 24.

Example 67

A primary modified block copolymer was obtained in the same manner as in the preparation of 1P-12 (see Table 5) except that N- (1, 3-dimethylbutadiene) -3- (triethoxysilyl) -1-propylamine (modifier M5) as a modifier was reacted with a living polymer P-8 in an amount of equivalent molar weight with respect to N-butyllithium used in the polymerization; a flame-retardant polymer composition was obtained in the same manner as in example 20, except that the first-modified block copolymer was used in place of 1P-12. The resulting composition showed good properties (breaking strength, elongation at break, oxygen index) as in example 20.

Industrial applicability of the invention

The polymer composition containing a secondary-modified block copolymer of the present invention comprises a secondary-modified block copolymer and a thermoplastic resin and/or a rubbery polymer, and exhibits an excellent balance of rigidity and impact resistance. The polymer composition of the present invention can be processed into various shaped molded articles by injection molding, extrusion molding, etc., and can be advantageously used for various applications such as automobile parts (automobile interior materials, automobile exterior materials), various containers such as food packaging containers, household electric appliances, medical machine parts, industrial parts, toys, etc. Further, if the above-mentioned secondary modified block copolymer is combined with a component selected from various components such as an inorganic filler, a tackifier, and asphalt, a polymer composition having excellent characteristics suitable for various applications can be obtained by the combination.

Claims

1. A polymer composition comprising:

the semi-modified block copolymer is represented by the following formula (10); and

(10) E²—F²

in the above-mentioned formula, the compound of formula,

E²represents a unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the formulae (g-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

R⁹～R¹⁰and R¹³～R¹⁵Each independently represents C_1-48The alkylene group of (a) is,

R¹¹is represented by C_1-48Alkyl of (C)_6-48Aryl of (5) by C_1-48Alkyl moiety of (2) and C_6- ₄₈Alkylaryl of an aryl moiety consisting of C_1-48Alkyl moiety of (2) and C_6-48Aralkyl group consisting of an aryl moiety of, or C_3-48The cycloalkyl group of (a) is,

wherein R is⁹～R¹⁰And R¹³～R¹⁵Optionally each independently having a hydroxyl group, an epoxy group, an amino group, a silanol group, C_1-24At least one functional group of the alkoxysilane group of (a),

R¹²represents a hydrogen atom, C_1-48Alkyl of (C)_6-48Aryl of (5) by C_1-48Alkyl moiety of (2) and C_6-48Alkylaryl of an aryl moiety consisting of C_1-48Alkyl moiety of (2) and C_6-48Aralkyl group consisting of an aryl moiety of, or C_3-48The cycloalkyl group of (a) is,

wherein R is⁹～R¹⁵Each independently having bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, the at least one atom being bonded in a manner other than a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group.

2. The polymer composition according to claim 1, wherein the thermoplastic resin in the component (II) is a functional group-containing thermoplastic resin, and the rubbery polymer in the component (II) is a functional group-containing rubbery polymer.

3. The polymer composition according to claim 2, wherein the thermoplastic resin having a functional group comprises at least one member selected from the group consisting of polyester-based resins, polyamide-based resins, polycarbonate-based resins, polyurethane-based resins, polyphenylene ether-based resins and polyoxymethylene resins,

4. The polymer composition of claim 2 or 3, wherein the functional group of the secondary modifier (III) is reactive with both the functional group of the primary modifier group of the semi-modified block copolymer (I-1) and the functional group of component (II).

5. The polymer composition according to claim 1, wherein the functional group of the secondary modifier (III) comprises at least one selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group and an alkoxysilane group.

6. A flame retardant polymer composition comprising 100 parts by weight of the polymer composition of claim 1 and 10 to 2000 parts by weight of an inorganic filler (VI).

7. A crosslinked product obtained by melt-kneading the polymer composition of claim 1 in the presence of a vulcanizing agent.

8. An adhesive composition comprising

100 parts by weight of a half-modified block copolymer (I-1) comprising:

the semi-modified block copolymer (I-1) is represented by the following formula (10);

20 to 400 parts by weight of a tackifier (VIII); and

(10) E²—F²

in the above-mentioned formula, the compound of formula,

E²represents a bonding unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the formulae (g-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

wherein R is⁹～R¹⁰And R¹³～R¹⁵Optionally each independently having a group selected from hydroxyl, epoxy, amino, silanol and C_1-24At least one functional group of the alkoxysilane group of (a),

wherein R is⁹～R¹⁵Optionally each independently has bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, the at least one atom being bonded in a manner different from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group.

9. The adhesive composition according to claim 8, wherein the functional group of the secondary modifier (III) comprises at least one selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group and an alkoxysilane group.

10. An adhesive film for surface protection obtained by forming an adhesive layer on a resin film, wherein the adhesive layer comprises an adhesive composition comprising:

100 parts by weight of a half-modified block copolymer (I-1) comprising:

3 to 200 parts by weight of a tackifier (VIII); and

(10) E²a F²

In the above-mentioned formula, the compound of formula,

E²represents a unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the formulae (g-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

R²、R³and R¹¹Each independently represents C_1-48Alkyl of (C)_6-48Aryl of (5) by C_1-48Alkyl moiety of (2) and C_6-48Aryl moiety group ofTo alkylaryl radicals formed from C_1-48Alkyl moiety of (2) and C_6-48Aralkyl group consisting of an aryl moiety of, or C_3-48The cycloalkyl group of (a) is,

11. An asphalt composition comprising:

0.5 to 50 parts by weight of a half-modified block copolymer (I-1) comprising:

100 parts by weight of bitumen (IX); and

(10) E²—F²

in the above-mentioned formula, the compound of formula,

E²represents a unit represented by the following formula (g-1),

(g—1) —R⁹—P¹

(h—1) —NH—R¹⁰—Si(OR¹¹)₃

in the formulae (g-1) to (j-1),

P¹represents a basic block copolymer of a block copolymer of,

wherein R is⁹～R¹⁰And R¹³～R¹⁵Optionally independently of each other with a selectionFrom hydroxy, epoxy, amino, silanol and C_1-24At least one functional group of the alkoxysilane group of (a),

wherein R is⁹～R¹⁵And each necessarily independently has bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, the at least one atom being bonded in a manner different from a hydroxyl group, an epoxy group, an amino group, a silanol group, an alkoxysilane group.

12. A drainage pavement comprising a roadway and a drainage pavement layer having a plurality of drainage apertures formed thereon, the drainage pavement layer being formed from a composition comprising a plurality of aggregates and a binder, the binder comprising the asphalt composition of claim 11.

13. The water-draining pavement surface of claim 12, wherein the water-draining pavement layer has a porosity of 5 to 35%.