CN100503654C

CN100503654C - Modified block copolymer

Info

Publication number: CN100503654C
Application number: CNB2007100021239A
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: 2009-06-24
Anticipated expiration: 2022-07-18
Also published as: CN100500760C; CN1978520A; ES2366577T3; CN1974610A; CN100503719C; CN1974656A

Abstract

A second-order modified block copolymer which can be obtained by reacting a first-order modified block copolymer with a second-order modifier, wherein the first-order modified block copolymer comprises a base block copolymer and a functional group-containing first-order modifier group bonded to the base block copolymer, wherein the base block copolymer comprises at least one polymer block comprised mainly of vinyl aromatic hydrocarbon monomer units and at least one polymer block comprised mainly of conjugated diene monomer units, and wherein the second-order modifier has a specific functional group which is reactive to the functional group of the first-order modifier group of the first-order modified block copolymer. A second-order modified block copolymer-containing polymer composition comprising the second-order modified block copolymer as well as a thermoplastic resin and/or a rubbery polymer.

Description

Modified block copolymer

The application is application number 02813151.7, July 18 2002 applying date, the dividing an application of denomination of invention " modified block copolymer ".

Technical field

The present invention relates to be suitable for to prepare the modified block copolymer of the outstanding polymer composition in the balance aspect of rigidity and shock-resistance.More specifically, the present invention relates to modified block copolymer (following usually be called " second-order modified block copolymer "), it is by comprising basic segmented copolymer and containing half modified block copolymer (following usually be called " modified block copolymer ") with a properties-correcting agent group of the functional group of this basis segmented copolymer bonding, form with twice-modified dose of reaction with other particular functional group, wherein basic segmented copolymer comprises at least one polymer blocks that mainly contains unitary at least one polymer blocks of vinyl aromatic hydrocarbon monomer and mainly contain conjugated diene monomeric unit.In addition, the present invention relates to by in thermoplastic resin and/or rubbery polymer, adding the polymer composition that contains second-order modified block copolymer that this second-order modified block copolymer (below be sometimes referred to as " modified block copolymer ") obtains.The polymer composition that contains above-mentioned second-order modified block copolymer has demonstrated the outstanding rigidity and the balance of shock-resistance.The above-mentioned polymeric composition that contains second-order modified block copolymer of the present invention can be processed into the molding of different shape by injection molding, extrusion molding etc., can be advantageously used in various uses such as various containers, electrical home appliances, medical machinery parts, industrial part, toy such as trolley part (automobile inside material, automobile exterior material), food container.

The invention still further relates to and comprise an above-mentioned modified block copolymer and thermoplastic resin and/or rubbery polymer and above-mentioned twice-modified dose polymer composition.By above-mentioned polymer composition fusing is mediated, can also obtain to contain the polymer composition of above-mentioned second-order modified block copolymer.

Background technology

All the time, often the trial of carrying out be polymer substance as purposes such as the thin plate of material, film, molding in, use the composition and the laminate that are grouped into by a plurality of one-tenth, make it have enough intensity, perhaps improve its processing characteristics, perhaps reduce the cost of product.But, different types of polymer substance is mixed with each other and when forming composition, the combination that intermiscibility is good is also few.And the composition of the polymer substance of intermiscibility difference is owing to resulting from the ununiformity of Combination difference, the splitting of different sorts polymer substance, so there is the inadequate situation of modified effect that produces by mixing.

As everyone knows, as for by mixing the composition that polymer substance obtains the outstanding composition of character, can use styrene-butadiene block copolymer or its hydride and styrene-isoprene block copolymer or its hydride etc.But because these segmented copolymers and the polymkeric substance with polar functional group, for example the intermiscibility of polymeric amide, polyester, urethane etc. is poor, so can not give full play to the modified effect that produces by mixing, can not obtain useful blend compositions.

As improving styrene-butadiene block copolymer or its hydride and styrene-isoprene block copolymer or its hydride method with the intermiscibility of polymkeric substance with polar functional group, the composition of terminal-modified segmented copolymer and thermoplastic resin for example, is disclosed in the special fair 4-39495 communique of Japan (corresponding U.S. Patent number 5332784).In Japanese kokai publication hei 7-173390 communique, disclose polyamide resin, polymeric amide and in hydrogenated block copolymer, carried out grafted graft copolymer and unsaturated carboxylic acid or its derivative carry out the hydrogenated block copolymer of bonding with specified amount composition in addition.In addition, in TOHKEMY 2000-219800 communique, disclose the composition of vibrin and polyamide resin and epoxidized block copolymer, in TOHKEMY 2001-55492 communique, disclose the composition of vibrin, epoxidized block copolymer, multi-functional compounds and polyester elastomer.

On the other hand, the method that has the segmented copolymer of functional group as acquisition, in Japanese kokai publication sho 59-98106 communique (corresponding U.S. Patent number 4465809), put down in writing by polymkeric substance-alkali metal compositions is contacted with epoxy compounds, and the resultant of acquisition is directly contacted with the cyclic acid anhydrides, prepare the method for the polymkeric substance that contains carboxyl.But this polymkeric substance (be in the reaction of polymer ends and epoxy compounds residue cyclic acid anhydride carry out bonding) that contains carboxyl is poor with the avidity of thermoplastic resin and/or rubbery polymer, mineral filler etc.

In addition, in Japanese kokai publication sho 63-238107 communique (corresponding U.S. Patent number 4972023), polymkeric substance, its method for making and the purposes of also carrying out modification by amide group have been put down in writing with terminal acidic group or its salt at the end of the chain.But this polymer-modified being actually by attempt with 1,5-diaza-dicyclo [3.1.0] cyclohexane and derivative thereof and carry out from the Schiff's base (Schiff base) of fatty amine or aromatic amine and aldehyde that the method for modification obtains, and the polymkeric substance that obtains (being to carry out modification by amide group with terminal acidic group or its salt) is poor with the avidity of thermoplastic resin and/or rubbery polymer, mineral filler etc.

Like this, in the prior art,, not equilibrated composition with outstanding rigidity and shock-resistance as the composition that the segmented copolymer of being made up of vinyl aromatic hydrocarbon and conjugated diolefine and thermoplastic resin and/or rubbery copolymer are formed.

Summary of the invention

Under these circumstances, the inventor etc. are in order to solve above-mentioned prior art problem, and just comprise that the characteristic improvement of the composition of segmented copolymer that vinyl aromatic hydrocarbon and conjugated diolefine are formed and thermoplastic resin and/or rubbery copolymer carried out wholwe-hearted research.Its result, be surprised to find that by making twice-modified dose can obtain second-order modified block copolymer with the reaction of modified block copolymer, wherein modified block copolymer comprises basic segmented copolymer and contains a properties-correcting agent group with the functional group of this basis segmented copolymer bonding, the basis segmented copolymer comprises at least one polymer blocks that mainly contains unitary at least one polymer blocks of vinyl aromatic hydrocarbon monomer and mainly contain conjugated diene monomeric unit, twice-modified dose have can with the particular functional group of this functional group reactions of this properties-correcting agent base of this modified block copolymer, by comprising the outstanding polymer composition that contains second-order modified block copolymer of balance that the combination of this second-order modified block copolymer and thermoplastic resin and/or rubbery polymer can obtain rigidity and shock-resistance.In addition, discovery is mediated by the polymer composition fusing that will comprise an above-mentioned modified block copolymer and thermoplastic resin and/or rubbery polymer and above-mentioned twice-modified dose of composition, can also obtain the outstanding polymer composition that contains second-order modified block copolymer of balance of rigidity and shock-resistance.In addition, if find with above-mentioned second-order modified block copolymer and the composition combination that is selected from various compositions such as mineral filler, tackifier, pitch, the polymer composition that can have the outstanding characteristic that is suitable for various uses according to this combination acquisition then.Based on these discoveries, finished the present invention.

Therefore, an object of the present invention is to provide above-mentioned second-order modified block copolymer,, can be used in the outstanding polymer composition in balance aspect of making rigidity and shock-resistance by it is mixed with thermoplastic resin and/or rubbery polymer.

Another object of the present invention provides by comprising above-mentioned second-order modified block copolymer and makes up the polymer composition with good characteristic that obtains with the composition that is selected from various compositions such as mineral filler, tackifier, pitch.

Above-mentioned and other various purposes, various feature and various advantage of the present invention can be become apparent by following detailed description.

According to the present invention, modified block copolymer then is provided, it comprises:

The basis segmented copolymer, it comprises at least one polymer blocks (B) that mainly contains unitary at least one polymer blocks of vinyl aromatic hydrocarbon monomer (A) and mainly contain conjugated diene monomeric unit, this vinyl aromatic hydrocarbon monomer unit in this basis segmented copolymer and the amount of this conjugated diene monomeric unit, with respect to the total amount of vinyl aromatic hydrocarbon monomer unit and conjugated diene monomeric unit be respectively 5～95 weight % and 95～5 weight % and

With the properties-correcting agent group that contains functional group of this basis segmented copolymer bonding,

Wherein, this basis segmented copolymer is not hydrogenated or is hydrogenated to small part,

This modified block copolymer is represented with the formula that is selected from following formula (1)～formula (5):

(3)C ¹—NR ³—D ₁

(4)C ¹—D ¹

(5)E ¹—F ¹

In above-mentioned formula, A ¹Represent unit with any one expression of following formula (a) and formula (b),

B ¹Represent unit with any one expression of following formula (c)～formula (e),

(d)—R ⁴—CHR ⁵—CR ⁶R ⁷—O—X ¹

C ¹Represent unit with any one expression of following formula (f)～formula (h),

D ¹The unit that representative is represented with following formula (i),

(i)—R ⁸—NR ³—X ¹

E ¹The unit that representative is represented with following formula (j),

(j)—R ⁹—P ¹

F ¹Represent unit with any one expression of following formula (k)～formula (m),

Wherein, X ¹Be selected from unit with any one expression of following formula (n)～formula (s),

(q)—Si(OR ¹¹) ₂—R ¹⁹—Si(OR ¹¹) ₃、

In above-mentioned formula (1)～formula (3) and formula (a)～formula (s),

N represents nitrogen-atoms, and Si represents Siliciumatom, and O represents Sauerstoffatom, and C represents carbon atom, and H represents hydrogen atom,

P ¹Represent basic segmented copolymer,

R ^1aExpression C _1-48The trivalent aliphatic alkyl,

R ^1b, R ⁴, R ⁸～R ¹⁰And R ¹³～R ²⁰Represent C respectively independently _1-48Alkylidene group,

R ², R ³And R ¹¹Represent C independently of one another _1-48Alkyl, C _6-48Aryl, by C _1-48Moieties and C _6-48The alkaryl formed of aryl moiety, by C _1-48Moieties and C _6-48The aralkyl formed of aryl moiety, perhaps C _3-48Cycloalkyl,

Wherein, R ^1a, R ^1b, R ³, R ⁴, R ⁸～R ¹⁰, R ¹³～R ¹⁵And R ¹⁷～R ²⁰Not necessarily have the hydroxyl of being selected from, epoxy group(ing), amino, silanol, C independently of one another _1-24At least a functional group of alkoxysilane groups,

R ⁵～R ⁷And Rg ¹²Represent hydrogen atom independently of one another, C _1-48Alkyl, C _6-48Aryl, by C _1-48Moieties and C _6-48The alkaryl formed of aryl moiety, by C _1- ₄₈Moieties and C _6-48The aralkyl formed of aryl moiety, perhaps C _3-48Cycloalkyl,

Wherein, R ^1a, R ^1b, R ²～R ⁴And R ⁸～R ²⁰Not necessarily has at least a atom that is selected from Sauerstoffatom, nitrogen-atoms, sulphur atom, Siliciumatom that is bonded on it independently of one another, described at least a atom is to be different from the mode bonding of hydroxyl, epoxy group(ing), amino, silanol and alkoxysilane groups

T, u, v, x are 0 or above integer independently of one another, but t and u are not 0 simultaneously, and w, y, z, α are 1 or above integer independently of one another.

1. modified block copolymer comprises:

(3)C ¹—NR ³—D ¹

(4)C ¹—D ¹

(5)E ¹—F ¹

(d)—R ⁴—CHR ⁵—CR ⁶R ⁷—O—X ¹

D ¹The unit that representative is represented with following formula (i),

(i)—R ⁸—NR ³—X ¹

E ¹The unit that representative is represented with following formula (j),

(j)—R ⁹—P ¹

(q)—Si(OR ¹¹) ₂—R ¹⁹—Si(OR ¹¹) ₃

In above-mentioned formula (1)～formula (3) and formula (a)～formula (s),

P ¹Represent basic segmented copolymer,

R ^1aExpression C _1-48The trivalent aliphatic alkyl,

R ⁵～R ⁷And R ¹²Represent hydrogen atom independently of one another, C _1-48Alkyl, C _6-48Aryl, by C _1-48Moieties and C _6-48The alkaryl formed of aryl moiety, by C _1- ₄₈Moieties and C _6-48The aralkyl formed of aryl moiety, perhaps C _3-48Cycloalkyl,

2. above-mentioned 1 modified block copolymer, it is represented with formula (1).

3. above-mentioned 1 modified block copolymer, it is represented with formula (2).

4. above-mentioned 1 modified block copolymer, it is represented with formula (3).

5. above-mentioned 1 modified block copolymer, it is represented with formula (4).

6. above-mentioned 1 modified block copolymer, it is represented with formula (5).

7. polymer composition, comprise: be above-mentioned 1～6 any one modified block copolymer composition (I) of 1～99 weight % and be at least a component of polymer (II) that is selected from thermoplastic resin and rubbery polymer of 99～1 weight % with respect to the total amount of composition (I) and composition (II) with respect to the total amount of composition (I) and composition (II).

8. above-mentioned 7 polymer composition, wherein the thermoplastic resin in the composition (II) is the thermoplastic resin that contains functional group, the rubbery polymer in the composition (II) is the rubbery polymer that contains functional group.

9. above-mentioned 8 polymer composition, wherein this thermoplastic resin that contains functional group comprises and is selected from least a in polyester resin, polyamide-based resin, polycarbonate resin, polyurethanes resin, polyhenylene ether resin and the polyformaldehyde resin,

This rubbery polymer that contains functional group comprises and is selected from olefin type elastomer and the elastomeric at least a composition of styrenic, and wherein said elastomerics contains separately and is selected from anhydride group, carboxyl, hydroxyl, epoxy group(ing) and amino at least a functional group.

10. polymer composition comprises:

Total amount with respect to composition (I-1) and composition (II) is the half modified block copolymer composition (I-1) of 1～99 weight %, and this half modified block copolymer comprises:

The basic segmented copolymer that comprises at least one polymer blocks (B) that mainly contains unitary at least one polymer blocks of vinyl aromatic hydrocarbon monomer (A) and mainly contain conjugated diene monomeric unit, this vinyl aromatic hydrocarbon monomer unit in this basis segmented copolymer and the amount of this conjugated diene monomeric unit, with respect to the total amount of vinyl aromatic hydrocarbon monomer unit and conjugated diene monomeric unit be respectively 5～95 weight % and 95～5 weight % and

Wherein should the basis segmented copolymer be hydrogenated or be hydrogenated to small part,

Represent this half modified block copolymer with the formula that is selected from following formula (6)～formula (10); With

Total amount with respect to composition (I-1) and composition (II) is at least a component of polymer (II) that is selected from thermoplastic resin and rubbery polymer of 99～1 weight %; With

With respect to composition (I-1) that amounts to 100 weight parts and twice-modified dose (III) that composition (II) is 0.01～20 weight part, this twice-modified dose (III) have can with the functional group of the functional group reactions of a properties-correcting agent base of this half modified block copolymer (I-1);

(8)C ²—NR ³—D ²

(9)C ²—D ²

(10)E ²—F ²

In above-mentioned formula,

A ²Represent unit with any one expression of following formula (a-1) and formula (b-1),

B ²The unit that representative is represented with following formula (c-1),

C ²Represent unit with any one expression of following formula (d-1) and formula (e-1),

D ²The unit that representative is represented with following formula (f-1),

(f—1)—R ⁸—NHR ³

E ²The unit that representative is represented with following formula (g-1),

(g—1)—R ⁹—P ¹

F ²Represent unit with any one expression of following formula (h-1)～formula (j-1),

(h—1)—NH—R ¹⁰—Si(OR ¹¹) ₃

In above-mentioned formula (6)～formula (8) and formula (a-1)～formula (j-1),

P ¹Represent basic segmented copolymer,

R ^1aExpression C _1-48The trivalent aliphatic alkyl,

Wherein, R ^1a, R ^1b, R ³, R ⁴, R ⁸～R ¹⁰And R ¹³～R ¹⁵Not necessarily have the hydroxyl of being selected from, epoxy group(ing), amino, silanol, C independently of one another _1-24At least a functional group of alkoxysilane groups,

Wherein, R ^1a, R ^1b, R ²～R ⁴And R ⁸～R ¹⁵Have at least one atom that is selected from Sauerstoffatom, nitrogen-atoms, sulphur atom and Siliciumatom that is bonded on it independently of one another, described at least a atom to be being different from the mode bonding of hydroxyl, epoxy group(ing), amino, silanol and alkoxysilane groups,

T, u, v, x are 0 or above integer independently of one another, but t and u are not 0 simultaneously, and w is 1 or above integer.

11. above-mentioned 10 polymer composition, wherein the thermoplastic resin in the composition (II) is the thermoplastic resin that contains functional group, and the rubbery polymer in the composition (II) is the rubbery polymer that contains functional group.

12. above-mentioned 11 polymer composition, wherein this thermoplastic resin that contains functional group comprises at least a composition that is selected from polyester resin, polyamide-based resin, polycarbonate resin, polyurethanes resin, polyhenylene ether resin and the polyformaldehyde resin,

13. above-mentioned 11 or 12 polymer composition, wherein the functional group of this twice-modified dose (III) can with the functional group of a properties-correcting agent base of this half modified block copolymer (I-1) and the two reaction of functional group of composition (II).

14. the polymer composition of any one of above-mentioned 10～13, wherein the functional group of this twice-modified dose (III) comprises and is selected from least a of carboxyl, anhydride group, isocyanate group, epoxy group(ing) and alkoxysilane group.

15. flame-retardant polymer composition, it comprises

Above-mentioned 1～6 any one modified block copolymer (I) of 100 weight parts,

The mineral filler of 10～2000 weight parts (VI), and

The olefin polymer of 0～1000 weight part.

16. flame-retardant polymer composition, it comprises above-mentioned 7 polymer composition of 100 weight parts, and the mineral filler of 10～2000 weight parts (VI).

17. flame-retardant polymer composition, it comprises above-mentioned 10 polymer composition of 100 weight parts, and the mineral filler of 10～2000 weight parts (VI).

18. crosslinked, it is by mediating acquisition with the bridging property material melts in the presence of vulcanizing agent, wherein the bridging property material comprises:

With respect to the total amount of composition (I) and composition (II) is above-mentioned 1～6 any one the modified block copolymer composition (I) of 10～100 weight %, and

Total amount with respect to composition (I) and composition (II) is at least a component of polymer (II) that is selected from thermoplastic resin and rubbery polymer of 90～0 weight %.

19. in the presence of vulcanizing agent, obtain crosslinked mediated in above-mentioned 10 polymer composition fusing.

20. binder composition comprises:

Above-mentioned 1～6 any one modified block copolymer (I) of 100 weight parts, and the tackifier of 20～400 weight parts (VIII).

21. binder composition comprises

Half modified block copolymer (I-1) of 100 weight parts, this half modified block copolymer comprises:

With a properties-correcting agent group that contains functional group of this basis segmented copolymer bonding,

This half modified block copolymer (I-1) is represented with the formula that is selected from following formula (6)～formula (10);

The tackifier of 20～400 weight parts (VIII); And

0.01 twice-modified dose (III) of～20 weight parts, this twice-modified dose (III) have can with the functional group of the functional group reactions of a properties-correcting agent base of this half modified block copolymer (I-1);

(8) C ²—NR ³—D ²

(9) C ²—D ²

(10)?E ²—F ²

In above-mentioned formula,

B ²The unit that representative is represented with following formula (c-1),

D ²The unit that representative is represented with following formula (f-1),

(f—1)?—R ⁸—NHR ³

E ²The bonding unit that representative is represented with following formula (g-1),

(g—1)?—R ⁹—P ¹

(h—1)?—NH—R ¹⁰—Si(OR ¹¹) ₃

In above-mentioned formula (6)～formula (8) and formula (a-1)～formula (j-1),

P ¹Represent basic segmented copolymer,

R ^1aExpression C _1-48The trivalent aliphatic alkyl,

Wherein, R ^1a, R ^1b, R ³, R ⁴, R ⁸～R ¹⁰And R ¹³～R ¹⁵Not necessarily have the hydroxyl of being selected from, epoxy group(ing), amino, silanol and C independently of one another _1-24At least a functional group of alkoxysilane groups,

R wherein ^1a, R ^1b, R ²～R ⁴And R ⁸～R ¹⁵Not necessarily has at least a atom that is selected from Sauerstoffatom, nitrogen-atoms, sulphur atom and Siliciumatom that is bonded on it independently of one another, described at least a atom is to be different from the mode bonding of hydroxyl, epoxy group(ing), amino, silanol and alkoxysilane groups

22. above-mentioned 21 binder composition, wherein the functional group of this twice-modified dose (III) comprises and is selected from least a of carboxyl, anhydride group, isocyanate group, epoxy group(ing) and alkoxysilane group.

23. the surface protection binder film, it obtains by form binder layer on resin molding, and wherein binder layer comprises binder composition, and described binder composition comprises:

Above-mentioned 1～6 any one modified block copolymer (I) of 100 weight parts, and the tackifier of 3～200 weight parts (VIII).

24. the surface protection binder film, it obtains by form binder layer on resin molding, and wherein binder layer comprises binder composition, and described binder composition comprises:

The tackifier of 3～200 weight parts (VIII); And

0.01 twice-modified dose (III) of～20 weight parts, wherein this twice-modified dose (III) have can with the functional group of the functional group reactions of a properties-correcting agent base of this half modified block copolymer (I-1);

(8)?C ²—NR ³—D ²

(9)?C ²—D ²

(10)?E ²—F ²

In above-mentioned formula,

B ²The unit that representative is represented with following formula (c-1),

D ²The unit that representative is represented with following formula (f-1),

(f—1)?—R ⁸—NHR ³

E ²The unit that representative is represented with following formula (g-1),

(g—1)?—R ⁹—P ¹

(h—1)?—NH—R ¹⁰—Si(OR ¹¹) ₃

In above-mentioned formula (6)～formula (8) and formula (a-1)～formula (j-1),

P ¹Represent basic segmented copolymer,

R ^1aExpression C _1-48The trivalent aliphatic alkyl,

Wherein, R ^1a, R ^1b, R ²～R ⁴And R ⁸～R ¹⁵Not necessarily has at least a atom that is selected from Sauerstoffatom, nitrogen-atoms, sulphur atom and Siliciumatom that is bonded on it independently of one another, described at least a atom is to be different from the mode bonding of hydroxyl, epoxy group(ing), amino, silanol and alkoxysilane groups

25. bituminous composition, it comprises:

0.5 above-mentioned 1～6 any one modified block copolymer (I) of～50 weight parts, and the pitch of 100 weight parts (IX).

26. bituminous composition, it comprises:

0.5 half modified block copolymer (I-1) of～50 weight parts, this half modified block copolymer comprises:

The pitch of 100 weight parts (IX); And

0.01 twice-modified dose (III) of～5 weight parts, wherein this twice-modified dose (III) has the functional group with the functional group reactions of a properties-correcting agent base of this half modified block copolymer (I-1);

(8)?C ²—NR ³—D ²

(9)?C ²—D ²

(10)?E ²—F ²

In above-mentioned formula,

B ²The unit that representative is represented with following formula (c-1),

D ²The unit that representative is represented with following formula (f-1),

(f—1)?—R ⁸—NHR ³

E ²The unit that representative is represented with following formula (g-1),

(g—1)?—R ⁹—P ¹

(h—1)?—NH—R ¹⁰—Si(OR ¹¹) ₃

In above-mentioned formula (6)～formula (8) and formula (a-1)～formula (j-1),

P ¹Represent basic segmented copolymer,

R ^1aExpression C _1-48The trivalent aliphatic alkyl,

Wherein, R ^1a, R ^1b, R ²～R ⁴And R ⁸～R ¹⁵And necessarily has at least a atom that is selected from Sauerstoffatom, nitrogen-atoms, sulphur atom and Siliciumatom that is bonded on it independently of one another, described at least a atom is to be different from the mode bonding of hydroxyl, epoxy group(ing), amino, silanol, alkoxysilane groups

27. drainage road, it comprises the drainage road layer that hole is used in a plurality of drainings that has of road and formation thereon, and this drainage road layer comprises multiple gathering materials and binding agent, and this binding agent comprises above-mentioned 25 bituminous composition.

28. above-mentioned 27 drainage road, wherein the porosity of this drainage road layer is 5～35%.

29. drainage road, it comprises the drainage road layer that hole is used in a plurality of drainings that has of road and formation thereon, and this drainage road layer is by comprising multiple gathering materials and binding agent, and this binding agent comprises above-mentioned 26 bituminous composition.

30. above-mentioned 29 drainage road, wherein the porosity of this drainage road layer is 5～35%.

31. prepare the method for above-mentioned 1 modified block copolymer, it comprises

(1) provide modified block copolymer one time, it comprises:

The basis segmented copolymer, it comprises and mainly contains unitary at least one polymer blocks of vinyl aromatic hydrocarbon monomer (A) and mainly contain basic segmented copolymer with at least one polymer blocks (B) of conjugated diene monomeric unit, this vinyl aromatic hydrocarbon monomer unit in this basis segmented copolymer and the amount of this conjugated diene monomeric unit, with respect to the total amount of vinyl aromatic hydrocarbon monomer unit and conjugated diene monomeric unit be respectively 5～95 weight % and 95～5 weight % and

This modified block copolymer prepares by following method: prepare the basic segmented copolymer with active end by active anionic polymerization, with by making the properties-correcting agent containing functional group and the activity end addition bonding of this basis segmented copolymer, obtain one time modified block copolymer, not necessarily, subsequently with this partly or completely hydrogenation of modified block copolymer, wherein this modified block copolymer represent with the formula that is selected from following formula (6)～formula (10) and

(2) make a modified block copolymer and twice-modified dose of reaction, wherein this twice-modified dose have can with the functional group of the functional group reactions of a properties-correcting agent base of this modified block copolymer, wherein this usage quantity of twice-modified dose is 0.3～10 mole with respect to the functional group of a properties-correcting agent base of 1 normal this modified block copolymer

Thereby obtained second-order modified block copolymer,

(8)?C ²—NR ³—D ²

(9)?C ²—D ²

(10)?E ²—F ²

In above-mentioned formula,

B ²The unit that representative is represented with following formula (c-1),

D ²The unit that representative is represented with following formula (f-1),

(f—1)?—R ⁸—NHR ³

E ²The unit that representative is represented with following formula (g-1),

(g—1)?—R ⁹—P ¹

(h—1)?—NH—R ¹⁰—Si(OR ¹¹) ₃

In above-mentioned formula (6)～formula (8) and formula (a-1)～formula (j-1),

P ¹Represent basic segmented copolymer,

R ^1aExpression C _1-48The trivalent aliphatic alkyl,

Wherein, R ^1a, R ^1b, R ³, R ⁴, R ⁸～R ¹⁰And R ¹³～R ¹⁵Not necessarily have the group, the C that are selected from hydroxyl, epoxy group(ing), amino, silane independently of one another ₁- ₂₄At least a functional group of alkoxysilane groups,

32. above-mentioned 31 method wherein, in (1), after a properties-correcting agent addition that contains functional group is bonded to the activity end of basic segmented copolymer, also can makes modified block copolymer obtaining and contain compound bearing active hydrogen and react,

Wherein, when carrying out the nonessential hydrogenation of this modified block copolymer, can before hydrogenation or with hydrogenation, carry out simultaneously with this reaction that contains compound bearing active hydrogen.

At this moment, when carrying out any hydrogenation of this modified block copolymer, can before hydrogenation or with hydrogenation, carry out simultaneously with this reaction that contains compound bearing active hydrogen.

Below, describe the present invention in detail.

A modified block copolymer of the present invention is a modified block copolymer, and it comprises:

The basis segmented copolymer, it comprises the basic segmented copolymer of at least one polymer blocks (B) that mainly contains unitary at least one polymer blocks of vinyl aromatic hydrocarbon monomer (A) and mainly contain conjugated diene monomeric unit, with with the properties-correcting agent group that contains functional group of this basis segmented copolymer bonding, wherein this this basis segmented copolymer is not to be hydrogenated or to be hydrogenated to small part, and this modified block copolymer is represented with the formula that is selected from above-mentioned formula (6)～formula (10).On the other hand, second-order modified block copolymer of the present invention is a modified block copolymer, it obtains by making this modified block copolymer and twice-modified dose of reaction, wherein twice-modified dose have can with the functional group of the functional group reactions of a properties-correcting agent base of this modified block copolymer, and second-order modified block copolymer is represented with the formula that is selected from above-mentioned formula (1)～formula (5).

The unitary amount of vinyl aromatic hydrocarbon monomer in the basic segmented copolymer of the present invention, total amount with respect to vinyl aromatic hydrocarbon monomer unit and conjugated diene monomeric unit, from the inflexible viewpoint is more than the 5 weight %, from the effect of improving of shock-resistance is below the 95 weight %, more preferably 10～90 weight %, further 15～85 weight % preferably.The unitary amount of this vinyl aromatic hydrocarbon monomer is more than the 60 weight %, when preferred 65 weight % are above, have the characteristic of resin, and have elastic properties when following less than 60 weight %, preferred 55 weight %.Also have, the amount of the conjugated diene monomeric unit in the basic segmented copolymer is 95～5 weight % with respect to the total amount of vinyl aromatic hydrocarbon monomer unit and conjugated diene monomeric unit.

Basic segmented copolymer of the present invention can be by preparing organolithium compound in solvent as the active anionic polymerization that catalyzer uses.

As the manufacture method of basic segmented copolymer, can exemplify as Japanese Patent Publication 36-19286 communique (corresponding U.S. Patent number 2975160), Japanese Patent Publication 43-17979 communique, Japanese Patent Publication 46-32415 communique, Japanese Patent Publication 49-36957 communique (corresponding U.S. Patent number 3281383), Japanese Patent Publication 48-2423 communique, Japanese Patent Publication 48-4106 communique (corresponding U.S. Patent number 3639517), Japanese Patent Publication 51-49567 communique, the method of Japanese kokai publication sho 59-166518 communique (corresponding U.S. Patent number 4603155) etc.By activity end at the basic segmented copolymer that obtains with these methods, make a following properties-correcting agent addition bonding that contains functional group, can obtain to have a modified block copolymer of a properties-correcting agent base that contains functional group, it has, for example the structure of representing with following general formula.

(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 following formula, A mainly contains the unitary polymer blocks of vinyl aromatic hydrocarbon monomer, and B is the polymer blocks that mainly contains conjugated diene monomeric unit.The unitary boundary of A unit and B need not have tangible difference.In addition, n is the integer more than 1, preferably 1～5 integer.M is the integer more than 2, preferably 2～11 integer.The atomic group that Z represents to have following functional group carries out the residue of a properties-correcting agent of bonding.When making Z carry out addition according to following metallization reaction, the unitary side chain bonding of Z and A unit and/or B.A unit and B unit exist respectively when a plurality of in the segmented copolymer, and these structure both can be identical, also can be different.In addition, both can be identical with the structure of the polymer chain of Z bonding, also can be different.

Also have, in the present invention, the polymer blocks A that vinyl aromatic hydrocarbon monomer unit mainly contains contains the vinyl aromatic monomers unit to be preferably more than the 50 weight %, the more preferably above vinyl aromatic hydrocarbon of 70 weight % and the copolymer unit of conjugated diolefine, or vinyl aromatic hydrocarbon homopolymer unit, and the polymer blocks B that mainly contains conjugated diene monomeric unit contains the amount that conjugated diolefine preferably surpasses 50 weight %, the more preferably above conjugated diolefine of 60 weight % and the copolymer unit of vinyl aromatic hydrocarbon, or conjugated diene homopolymers unit.Vinyl aromatic hydrocarbon in the copolymer block both can uniform distribution, distribution of shapes that can also taper.In addition, in this copolymer block part, at least a form of equally distributed part in vinyl aromatic hydrocarbon monomer unit and the part that distributes with conical in shape also can a plurality ofly exist simultaneously.In addition, in this copolymer block part, vinyl aromatic hydrocarbon monomer unit amount distinct portions also can a plurality ofly exist simultaneously.The basic segmented copolymer that uses among the present invention also can be any mixture of a plurality of different basic segmented copolymers.

In the present invention, the microtexture (cis of conjugated diolefine part in the segmented copolymer, trans, the ratio of vinyl) can change arbitrarily by using following polar compound etc., use 1, (it is by cis-1 to the 3-divinyl, 4 keys, anti-form-1,4 keys or 1, the addition polymerization of 2-vinyl bonds) during as conjugated diolefine, based on cis-1,4 keys, anti-form-1,4 keys and 1, the integral molar quantity of 2-vinyl bonds, 1,2-vinyl bonds resultant is preferably 5～90%, and more preferably 10～80%, when using isoprene or use 1 simultaneously as conjugated diolefine, when 3-divinyl and isoprene, based on cis-1,4 chain, anti-form-1, the 4-key, 1,2-vinyl bonds and 3, the integral molar quantity of 4-vinyl bonds, 1,2-vinyl bonds and 3, the total amount of 4-vinyl bonds preferably 3～80% is more preferably 5～70%.But the microtexture when using the hydrogenant segmented copolymer as basic segmented copolymer is using 1, the 3-divinyl is during as conjugated diolefine, based on cis-1,4 key, anti-form-1,4 keys and 1, the integral molar quantity of 2-thiazolinyl key, suggestion 1,2-vinyl bonds resultant is preferably 10～80%, more preferably 25-75%, when using isoprene or use 1 simultaneously as conjugated diolefine, when 3-divinyl and isoprene, based on cis-1,4 key, anti-form-1,4 keys, 1,2-vinyl bonds and 3, the integral molar quantity of 4-vinyl bonds, suggestion 1,2-vinyl bonds and 3, the total amount of 4-vinyl bonds preferably 5～70%.Also have, below, 1,2-vinyl bonds and 3, the total amount of 4-vinyl bonds (still, when using 1,3-butadiene as conjugated diolefine, being 1,2-vinyl bonds resultant) is called " vinyl bonds resultant.”

In the present invention, so-called conjugated diolefine is the diolefine with a pair of conjugated double bond, for example 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene etc.Wherein, as particularly preferred 1,3-butadiene, the isoprene of comprising.These conjugated diolefines both can only have been used a kind of, also can make up more than two kinds and use.

In addition, as the vinyl aromatic hydrocarbon, comprise vinylbenzene, o-methyl styrene, p-methylstyrene, to t-butyl styrene, 1,3-dimethyl styrene, alpha-methyl styrene, vinyl naphthalene, vinyl anthracene etc., wherein, as the particularly preferred vinylbenzene that comprises.These vinyl aromatic hydrocarbon can only use a kind of, also can make up more than two kinds and use.

Among the present invention, when in the basic segmented copolymer of preparation, using isoprene and 1,3-butadiene simultaneously as conjugated diolefine, isoprene and 1, the weight ratio of 3-divinyl preferably 95/5～5/95, more preferably 90/10～10/90, further preferred 85/15～15/85.Especially, from obtaining the viewpoint of the outstanding polymer composition of low temperature shock-resistance, the weight ratio of suggestion isoprene and 1,3-butadiene preferably 49/51～5/95, more preferably 45/55～10/90, further preferred 40/60～15/85.If use isoprene and 1,3-butadiene simultaneously, add man-hour even then at high temperature form, also can obtain the polymer composition of the good molding of the balance quality of appearance characteristics and mechanical characteristics.

Among the present invention, comprise in preparation under any one situation of situation of the outstanding polymer composition of the situation of the outstanding polymer composition of the flexibility of this second-order modified block copolymer and rubbery polymer and shock-resistance that preparation comprises this second-order modified block copolymer and thermoplastic resin, from keeping the inflexible viewpoint of molding, the ratio (hereinafter referred to as " the block rate of vinyl aromatic hydrocarbon ") that also can advise the vinyl aromatic hydrocarbon polymer block that will embed in the basic segmented copolymer is preferably more than the 50 weight %, more preferably 50～97 weight %, further preferred 60～95 weight %, most preferably 70～92 weight %.The block rate of the vinyl aromatic hydrocarbon polymer that embeds in the segmented copolymer of basis can be by following method (I.M.KOLTHOFF etc., J.Polym.Sci.1,429 (1946)) method of record is measured: use by with perosmic anhydride as catalyzer, with the vinyl aromatic hydrocarbon polymer block composition of the method acquisition of tert-butyl hydroperoxide oxygenolysis segmented copolymer (but mean polymerisation degree be about vinyl aromatic hydrocarbon polymer composition below 30 except), obtain by following formula.

The block rate (weight %) of vinyl aromatic hydrocarbon polymer=(in the basic segmented copolymer in the weight/foundation segmented copolymer of vinyl aromatic hydrocarbon polymer block the weight of all vinyl aromatic hydrocarbon) * 100

Among the present invention, the solvent that uses in the preparation as basic segmented copolymer, can use aliphatic hydrocarbons such as butane, pentane, hexane, iso-pentane, heptane, good fortune alkane, different good fortune alkane, alicyclic hydrocarbon such as pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane, perhaps varsols such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene, dimethylbenzene.These solvents can separately or mix use more than two kinds.

In addition, the organolithium compound that uses in the preparation of segmented copolymer be in the molecule bonding organic compound of the lithium atom more than 1, can exemplify as lithium ethide, n-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexa-methylene two lithiums, butadienyl two lithiums, prenyl two lithiums etc.These organolithium compounds can separately or mix use more than two kinds.In addition, organolithium compound both can once all add in the preparation of segmented copolymer, also can be divided into the above adding of secondary.

Among the present invention, the reactivity ratio of the polymerization velocity when preparing in order to regulate basic segmented copolymer, the microtexture that changes polymeric conjugated diolefine part, adjusting conjugated diolefine and vinyl aromatic hydrocarbon etc. can use polar compound and randomization agent.As polar compound and randomization agent, can exemplify as the sylvite of ethers, amine, thioether class, phosphamide, alkyl benzene sulphonate (ABS) or the alkoxide of sodium salt, potassium or sodium etc.The example of preferred ethers is dme, diethyl ether, diphenyl ether, tetrahydrofuran (THF), diethylene glycol dimethyl ether, Diethylene Glycol dibutyl ether.Can also use tertiary amine, Trimethylamine 99, triethylamine, Tetramethyl Ethylene Diamine, other cyclic tertiary amine etc. as the example of amine.Example as phosphamide comprises hexamethylphosphoramide.

Among the present invention, the polymerization temperature during the preparation segmented copolymer is preferably-10～150 ℃, more preferably 30～120 ℃.The time that needs during polymerization is different along with condition, but preferably in 48 hours, especially preferably 0.5～10 hour.In addition, the atmosphere of polymerization reaction system is preferably inert gas atmospheres such as nitrogen.Polymerization pressure limits especially, as long as it is just passable monomer and solvent fully can be maintained the pressure of liquid phase in above-mentioned polymerization temperature scope.In addition, do not sneak into the impurity that makes catalyzer and reactive polymer inerting in the preferred polymeric reaction system, for example water, oxygen, carbonic acid gas etc.

A modified block copolymer that uses among the present invention prepares by following method: for example, the basic segmented copolymer that has active end by active anionic polymerization manufacturing, with by making the properties-correcting agent containing functional group and the activity end of this basis segmented copolymer carry out addition reaction, can obtain modified block copolymer one time, as required, with this modified block copolymer hydrogenant method partly or completely.

A modified block copolymer of the present invention (following usually be also referred to as " composition (I-1) ") be comprise above-mentioned basic segmented copolymer and with the modified block copolymer of the properties-correcting agent base that contains functional group of this basis segmented copolymer bonding, and have the structure of representing with the formula that is selected from above-mentioned formula (6)～formula (10).

As the method for a modified block copolymer that obtains to have this properties-correcting agent base that contains functional group, can carry out the method acquisition of addition reaction by making the following properties-correcting agent that contains functional group and the activity end of basic segmented copolymer.And this functional group of this properties-correcting agent also can use the known method protection.As other method that obtains a modified block copolymer, be included in organic alkali metal compound reactions (metallization reaction) such as making organolithium compound in the basic segmented copolymer with active end, and then organic alkali metal and basic segmented copolymer are carried out after the addition, the method that makes properties-correcting agent carry out addition reaction.Under the situation of latter's method, also can behind the hydride that obtains basic segmented copolymer, make it carry out metallization reaction, thereby make an above-mentioned properties-correcting agent reaction.

Kind according to a properties-correcting agent, in the stage that properties-correcting agent and basic segmented copolymer are reacted, the hydroxyl of a properties-correcting agent base in a modified block copolymer that obtains and amino etc. are converted into an alkali metal salt sometimes usually, but in such cases, by having the compound bearing active hydrogen reaction, can change the functional group of hydroxyl and amino etc. again into for example water, alcohol, mineral acid etc.At this moment, when this modified block copolymer carries out any hydrogenation, can before hydrogenation or with hydrogenation, carry out simultaneously with this reaction that contains compound bearing active hydrogen.

Also have, in the present invention, the activity end of properties-correcting agent and segmented copolymer is reacted after, do not have the segmented copolymer of modification can be mixed in the modified block copolymer of composition yet.Suggestion is mixed in the ratio of the segmented copolymer that does not have modification in the modified block copolymer of composition, based on the weight of a modified block copolymer, is preferably below the 70 weight %, more preferably below the 60 weight %, further below the preferred 50 weight %.

Among the present invention, a properties-correcting agent as using in order to obtain this modified block copolymer comprises following material.

For example, as a properties-correcting agent that uses in order to obtain a modified block copolymer (corresponding respectively to second-order modified block copolymer) with above-mentioned formula (1) or above-mentioned formula (2) expression with above-mentioned formula (6) or above-mentioned formula (7) expression, it can be the four glycidyl group m-xylene diamine, four glycidyl group-1,3-diamino methylcyclohexane, four glycidyl group is to the penylene diamines, the four glycidyl group diaminodiphenyl-methane, diglycidylaniline, the diglycidyl Ortho Toluidine, 4,4 '-diglycidyl-diphenyl methyl amine, 4,4 '-diglycidyl-dibenzyl methylamine, polyepoxy compounds such as diglycidyl amino methyl hexanaphthene.

In addition, as a properties-correcting agent that uses in order to obtain a modified block copolymer (corresponding to second-order modified block copolymer), can be γ-glycidoxy ethyl trimethoxy silane with above-mentioned formula (5) expression with above-mentioned formula (10) expression, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy butyl trimethoxy silane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group tripropoxy silane, γ-glycidoxy propyl group three butoxy silanes, γ-glycidoxy propyl group triple phenoxyl silane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-glycidoxy propyl group ethyl dimethoxy silane, γ-glycidoxy propyl group ethyl diethoxy silane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxy propyl group methyl dipropoxy silane, γ-glycidoxy propyl group methyl dibutoxy silane, γ-glycidoxy propyl group methyldiphenyl TMOS, γ-glycidoxy propyl-dimethyl methoxy silane, γ-glycidoxy propyl group diethyl Ethoxysilane, γ-glycidoxy propyl-dimethyl Ethoxysilane, γ-glycidoxy propyl-dimethyl phenoxy group silane, γ-glycidoxy propyl group diethyl methoxy silane, γ-glycidoxy propyl group methyl diisoamyl diene TMOS, two (γ-glycidoxy propyl group) dimethoxy silane and two (γ-glycidoxy propyl group) diethoxy silane.

In addition, can also be two (γ-glycidoxy propyl group) dipropoxy silane, two (γ-glycidoxy propyl group) dibutoxy silane, two (γ-glycidoxy propyl group) hexichol TMOS, two (γ-glycidoxy propyl group) methyl methoxy base silane, two (γ-glycidoxy propyl group) methyl ethoxy silane, two (γ-glycidoxy propyl group) methyl-prop TMOS, two (γ-glycidoxy propyl group) methyl butoxy silane, two (γ-glycidoxy propyl group) methylenedioxy phenoxy base silane, three (γ-glycidoxy propyl group) methoxy silane, the rare acyloxy propyl trimethoxy silicane of γ-methyl-prop, the rare acyloxy propyl-triethoxysilicane of γ-methyl-prop, the rare acyloxy methyltrimethoxy silane of γ-methyl-prop, the rare acyloxy ethyl triethoxysilane of γ-methyl-prop, two (the rare acyloxy propyl group of γ-methyl-prop) dimethoxy silane and three (the rare acyloxy propyl group of γ-methyl-prop) methoxy silane.

Can also be β-(3,4-epoxy group(ing) cyclohexyl) ethyl-Trimethoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-second methoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-tripropoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-three butoxy silane and β-(3,4-epoxy group(ing) cyclohexyl) ethyl-triple phenoxyl silane.

Can also be β-(3,4-epoxy group(ing) cyclohexyl) propyl group-Trimethoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-methyl dimethoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-ethyl dimethoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-ethyl diethoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-methyldiethoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-methyl dipropoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-methyl dibutoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-methyldiphenyl TMOS, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-dimethyl methyl TMOS, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-diethyl Ethoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-dimethylethoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-dimethyl propylene TMOS, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-dimethyl butyrate TMOS and β-(3,4-epoxy group(ing) cyclohexyl) ethyl-dimethyl phenoxy silane.

Can also be β-(3,4-epoxy group(ing) cyclohexyl) ethyl-diethyl methoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl-methyl diisoamyl diene TMOS and N-(1,3-dimethyl butylidene)-3-(triethoxysilyl)-1-propane amine.

As a properties-correcting agent that uses in order to obtain a modified block copolymer (corresponding to second-order modified block copolymer) with above-mentioned formula (3) expression with above-mentioned formula (8) expression, comprise 1,3-dimethyl-2-imidazolidone, 1,3-diethyl-2-imidazolidone, N, N '-dimethyl allene urea, 1,3-dipropyl-2-imidazolidone, 1-methyl-3-ethyl-2-imidazolidone, 1-methyl-3-propyl group-2-imidazolidone, 1-methyl-3-butyl-2-imidazolidone, 1-methyl-3-(2-methoxy ethyl)-2-imidazolidone, 1-methyl-3-(2-ethoxyethyl group)-2-imidazolidone, 1,3-two (2-ethoxyethyl group)-2-imidazolidone, 1,3-dimethyl ethylene thiourea, N, N '-diethyl propylene urea and N-methyl-N '-ethyl propylene urea.

As a properties-correcting agent that uses in order to obtain a modified block copolymer (corresponding to second-order modified block copolymer) with above-mentioned formula (4) expression with above-mentioned formula (9) expression, comprise 1-Methyl-2-Pyrrolidone, 1-cyclohexyl-2-Pyrrolidone, the 1-ethyl-2-pyrrolidone, 1-propyl group-2-Pyrrolidone, 1-butyl-2-Pyrrolidone, 1-sec.-propyl-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-sec.-propyl-2-piperidone and 1-sec.-propyl-5,5-dimethyl-2-piperidone.

By making above-mentioned properties-correcting agent and basic block copolymer reacting, can obtain to have a modified block copolymer of a properties-correcting agent residue bonding of the functional group that stipulates among the present invention.When the activity end that makes properties-correcting agent containing functional group and basic segmented copolymer carries out addition reaction, the activity end of basis segmented copolymer can be any one of polymer blocks A and polymer blocks B, but for the outstanding composition of the balance that obtains rigidity and shock-resistance, preferably with the activity end (carrying out addition) of polymer blocks A for a properties-correcting agent that contains functional group.

With respect to the activity end of 1 normal basic segmented copolymer, the usage quantity that suggestion contains a properties-correcting agent of above-mentioned functional group surpasses 0.5 equivalent, below 10 equivalents, preferably surpasses 0.7 equivalent, below 5 equivalents, more preferably surpasses 1 equivalent, below 4 equivalents.Also have, in the present invention, the amount of the activity end of basic segmented copolymer can be calculated by the amount of the organolithium compound that uses in the polymerization.

In the present invention, can be as required, by with an above-mentioned modified block copolymer partly or completely hydrogenation obtain the hydride of a modified block copolymer.Hydrogenation is after a modification, carries out before twice-modified.As hydrogenation catalyst, restriction especially can not used known all the time.Exemplify hydrogenation catalyst, comprising:

(1) on carbon, silicon, aluminium, diatomite etc., is loaded with the heterogeneous hydrogenation catalyst of carrier model of metals such as Ni, Pt, Pd or Ru;

(2) so-called Z-type catalyst, it uses the bonding of reductive agents such as transition metal salt such as organic acid salt such as Ni, Co, Fe or Cr or acetylacetonate and organoaluminum;

(3) contain homogeneous hydrogenation catalyzer such as so-called organometallic complex such as organometallic compound such as Ti, Ru, Rh or Zr.

As concrete hydrogenation catalyst, can use the hydrogenation catalyst of Japanese Patent Publication 42-8704 communique (corresponding U.S. Patent number 3706814), Japanese Patent Publication 43-6636 communique (corresponding U.S. Patent number 3333024), Japanese Patent Publication 63-4841 communique (corresponding U.S. Patent number 4501857), the special fair 1-37970 communique of Japan (corresponding U.S. Patent number 4673714), the special fair 1-53851 communique of Japan, the special fair 2-9041 communique of Japan.As preferred hydrogenation catalyst can give an example be two cyclopentadiene titanium compounds and/or with the mixture of reductibility organometallic compound.

As two cyclopentadiene titanium compounds, can use the compound of Japanese kokai publication hei 8-109219 communique, but as object lesson, what can give an example is the compound that dichloride dicyclopentadienyltitanium, tri-chlorination one penta methyl cyclopentadienyl titanium etc. have at least one and have the ligand of (replacement) cyclopentadienyi skeleton, indenyl skeleton or fluorenyl skeleton.In addition, as the reductibility organometallic compound, what can enumerate is organic alkali metal compound, organo-magnesium compound, organo-aluminium compound, organoboron compound or organic zinc compounds etc. such as organolithium.

Hydrogenation preferably 0～200 ℃, more preferably in 30～150 ℃ temperature range, carry out.The hydrogen pressure that uses in the suggestion hydrogenation is preferably 0.1～15MPa, more preferably 0.2～10MPa, further preferred 0.3～5MPa.In addition, the hydrogenation time is preferably 3 minutes～and 10 hours, more preferably 10 minutes～5 hours.Hydrogenation can rhythmic reaction, any one mode of successive reaction or these combination is carried out.

During in the present invention with a modified block copolymer hydrogenation, can select arbitrarily according to purpose, restriction especially based on total hydrogenation ratio of the unsaturated double-bond of conjugated diene compound.

In addition, for the present invention, in modified block copolymer of hydrogenation, from obtaining the viewpoint of the outstanding resin combination of thermostability, suggestion based on hydrogenation before the hydrogenation ratio of vinyl bonds of conjugated diolefine be preferably more than 85%, more preferably more than 90%, further preferred more than 95%.Here, the hydrogenation ratio of so-called vinyl bonds refers in based on the vinyl bonds that embeds (before the hydrogenation) conjugated diolefine in the basic segmented copolymer, hydrogenation the ratio of vinyl bonds.

Also have,, but advise that hydrogenation ratio is preferably below 50%, more preferably 30% below, further preferred below 20% for the restriction especially of hydrogenation ratio of the two keys of the unitary aromatic series of vinyl aromatic hydrocarbon monomer in the modified block copolymer.

Hydrogenation ratio can pass through nuclear magnetic resonance device (NMR) and measure.

Second-order modified block copolymer of the present invention is the second-order modified block copolymer (the following composition (I) that usually is called) that twice-modified dose (the following composition (III) that usually is called) and the reaction of an above-mentioned modified block copolymer (I-1) (half modified block copolymer) are obtained, and be the second-order modified block copolymer that has with the structure of above-mentioned formula (1)～any one expression of formula (5), wherein twice-modified dose of functional group that has with the functional group reactions of a properties-correcting agent base of this modified block copolymer.

As mentioned above, preparation method as second-order modified block copolymer of the present invention, comprise by the active anionic polymerization that organolithium compound is used as catalyzer and prepare basic segmented copolymer with active end, make properties-correcting agent and its reaction prepare modified block copolymer one time then, and then make twice-modified dose of method that obtains second-order modified block copolymer with its reaction.Also have, if above-mentioned " basic segmented copolymer ", " modified block copolymer " of diagramming, the example of " second-order modified block copolymer " with active end, then respectively as following (i)～(iii).

Wherein,

Represent basic segmented copolymer, Li represents lithium ion, and M represents the properties-correcting agent base one time, and D represents twice-modified dose of base.

In another mode of the present invention, a kind of method for preparing second-order modified block copolymer of the present invention is provided, it comprises

(1) provide modified block copolymer one time, it comprises:

The basis segmented copolymer, it comprises the basic segmented copolymer of at least one polymer blocks (B) that mainly contains unitary at least one polymer blocks of vinyl aromatic hydrocarbon monomer (A) and mainly contain conjugated diene monomeric unit, this vinyl aromatic hydrocarbon monomer unit in this basis segmented copolymer and the amount of this conjugated diene monomeric unit, with respect to the total amount of vinyl aromatic hydrocarbon monomer unit and conjugated diene monomeric unit be respectively 5～95 weight % and 95～5 weight % and

This modified block copolymer prepares by following method: the basic segmented copolymer that has active end by active anionic polymerization manufacturing, with by making the properties-correcting agent containing functional group and the activity end addition bonding of this basis segmented copolymer, can obtain modified block copolymer one time, not necessarily, subsequently with this partly or completely hydrogenation of modified block copolymer, wherein this modified block copolymer represent with the formula that is selected from above-mentioned formula (6)～formula (10) and

(2) modified block copolymer and twice-modified dose are reacted, this twice-modified dose functional group that has with the functional group reactions of a properties-correcting agent base of this modified block copolymer wherein, wherein this usage quantity of twice-modified dose is 0.3～10 mole with respect to the functional group of a properties-correcting agent base of 1 normal this modified block copolymer

Thereby obtained second-order modified block copolymer.

In second-order modified block copolymer of the present invention, containing the atomic group X of functional group ¹The rubbery polymer of functional group can and/or be contained or reaction such as mineral filler with the thermoplastic resin that contains functional group in the functional group of containing in (as twice-modified dose of base), and a properties-correcting agent base and twice-modified dose of base all contain nitrogen-atoms, Sauerstoffatom or carbonyl simultaneously.Can obviously produce the interaction of the physics avidity such as hydrogen bond between these atoms and group and polar group and thermoplastic resin and/or rubbery polymer, the mineral filler isopolarity group, thereby bring into play the purpose effect that the present invention will reach.

Use in the present invention twice-modified dose be have can with twice-modified dose of the functional group of the functional group reactions of a modified block copolymer composition (I-1).Preferred twice-modified dose example is as follows.Twice-modified dose the preferred example that is used for obtaining having the second-order modified block copolymer of the functional group that represents with above-mentioned formula (n) is to have carboxyl or anhydride group twice-modified dose; Twice-modified dose the preferred example that is used for obtaining having the second-order modified block copolymer of the functional group that represents with above-mentioned formula (o) is to have twice-modified dose of isocyanate group; Twice-modified dose the preferred example that is used for obtaining having the second-order modified block copolymer of the functional group that represents with above-mentioned formula (p) is to have twice-modified dose of epoxy group(ing); Twice-modified dose the preferred example that is used for obtaining having the second-order modified block copolymer of the functional group that represents with above-mentioned formula (q) is to have silanol base or alkoxysilane group twice-modified dose.Twice-modified dose of composition (III) is to have two twice-modified doses of being selected from these functional groups at least.But when functional group was anhydride group, twice-modified dose of composition (III) also can be only to have twice-modified dose an of anhydride group.When making twice-modified dose of composition (III) with a modified block copolymer composition (I-1) reaction, suggestion is with respect to the functional group of 1 equivalent and composition (I-1) bonding, and composition (III) is 0.3～10 mole, and preferred 0.4～5 mole, more preferably 0.5～4 mole.Make the not restriction especially of method of composition (I-1) and composition (III) reaction, can utilize known method.Can exemplify, for example, following fusing kneading method and make method of its reaction etc. by each composition being dissolved in solvent etc. or dispersing and mixing.Make in the method for its reaction by each composition being dissolved in solvent etc. or dispersing and mixing, as solvent, as long as can dissolve or disperse the just passable of each composition, restriction especially can not used varsols such as aliphatic hydrocarbon, ester ring type hydrocarbon, aromatic hydrocarbons, halogen-containing kind solvent, esters solvent, ether solvent etc.The temperature that makes the reaction of each composition in the method normally-10～150 ℃, preferred 30～120 ℃.React required time according to condition and difference, but generally be in 3 hours, preferably several seconds～1 hour.Particularly preferred method, recommendation be to make its reaction by in the solution of the reaction mixture of a modified block copolymer (I-1) that contains preparation, adding composition (III), and then obtain the method for second-order modified block copolymer.At this moment, from the viewpoint of the second-order modified block copolymer that obtains excellent color tone, suggestion is after the activity end reaction that makes properties-correcting agent containing functional group and basic segmented copolymer, with containing the compound bearing active hydrogen processing.Alcohol such as water, methyl alcohol, ethanol, propyl alcohol, Virahol for example; Mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid etc. have compound bearing active hydrogen to be handled.In addition, in this is handled, from with the viewpoint of the stability of twice-modified dose of residue of second-order modified block copolymer bonding, suggestion is after carrying out above-mentioned processing, the pH value of solution that makes a modified block copolymer (I-1) is below 10, preferred below 9, more preferably below 8 after, make itself and twice-modified dose of reaction.

Object lesson as twice-modified dose of composition (III), as twice-modified dose, comprise aliphatic carboxylic acids such as toxilic acid, oxalic acid, succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, Carbalic acid, cyclohexane dicarboxylic acid, pentamethylene dicarboxylic acid with carboxyl; Aromatic carboxylic acids such as terephthalic acid, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, diphenyl dicarboxylic acid, trimesic acid, trihemellitic acid, pyromellitic acid etc.

As twice-modified dose, comprise maleic anhydride, itaconic anhydride, PMA, suitable-4-hexanaphthene-1,2-dicarboxylic anhydride, 1 with anhydride group, 2,4,5-benzene tertacarbonic acid dianhydride, 5-(2,5-dioxy base tetrahydroxy furyl)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride etc.

As twice-modified dose, comprise tolylene diisocyanate, diphenylmethanediisocyanate, multi-functional aromatic isocyanate with isocyanate group.

As having twice-modified dose of epoxy group(ing), except four glycidyl group-1,3-diamino methylcyclohexane, four glycidyl group m-xylene diamine, diglycidylaniline, 2-glycidyl ethyl glycol, diglycidyl propylene glycol, terephthalic acid diglycidyl ester acrylate etc. also comprise the above-mentioned epoxy compounds of a properties-correcting agent of conduct that uses for a modified block copolymer that obtains composition (I-1) etc.

As twice-modified dose, comprise the hydrolysate etc. of the above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure of a properties-correcting agent of conduct that uses for a modified block copolymer that obtains composition (I-1) with silanol base.As twice-modified dose example with alkoxysilane group, except two-(3-triethoxysilylpropyltetrasulfide)-four sulfanes, two-(3-triethoxysilylpropyltetrasulfide)-disulphanes, oxyethyl group siloxane oligomer etc., also comprise the above-mentioned silane compound of a properties-correcting agent of conduct that uses for a modified block copolymer that obtains composition (I-1) etc.

Particularly preferred twice-modified dose is carboxylic acid or its acid anhydrides with two above carboxyls among the present invention, perhaps have two above anhydride group, isocyanate group, epoxy group(ing), silanol base, alkoxysilane group twice-modified dose, for example, maleic anhydride, PMA, 1,2,4,5-benzene tertacarbonic acid dianhydride, tolylene diisocyanate, four glycidyl group-1,3-diamino methylcyclohexane, two-(3-triethoxysilylpropyltetrasulfide)-four sulfanes etc.

Modified block copolymer among the present invention and by making the weight-average molecular weight of twice-modified dose of second-order modified block copolymer that obtains with its reaction, from the physical strength of polymer composition and the viewpoint of shock-resistance, be preferably more than 30,000, and from processibility and with the viewpoint of the intermiscibility of thermoplastic resin and/or rubbery polymer, be preferably below 1,000,000, more preferably 4～800,000, further preferred 5～600,000.

In the present invention, the amount of vinyl can use nuclear magnetic resonance device (NMR) to measure in the bonding monomeric unit of the conjugated diolefine of segmented copolymer.Hydrogenation ratio also can use identical device NMR to measure in addition.The weight-average molecular weight of modified block copolymer and second-order modified block copolymer can be measured by gel permeation chromatography (GPC), be the typical curve of obtaining by commercially available standard vinylbenzene sample by using, promptly use the typical curve that the peak molecular weight of polystyrene standard makes and the weight-average molecular weight of obtaining.

By the solution of a modified block copolymer obtaining as mentioned above and the solution of second-order modified block copolymer, can from solution, separate multipolymer as required.Can also remove catalyst residue earlier as required, and then from solution, isolate polymkeric substance.Method as isolating polymer from solvent, can give an example, the method that polymer precipitation is reclaimed by the polar solvent that adds acetone or alcohol etc. (with respect to awkward broad dose of polymkeric substance) in the solution after polymerization or after the hydrogenation for example, solution that under agitation will polymkeric substance adds in the hot water and with stripping and removes the method for desolvating and reclaiming, and perhaps removes the method etc. of catalyzer by the direct heating polymers soln.Also have, can in a modified block copolymer of the present invention and second-order modified block copolymer, add stablizers such as various phenol stabilizers, Phosphorus stablizer, sulphur class stablizer, amine stablizer.

Can be among the present invention by second-order modified block copolymer (composition (I)) and at least a component of polymer (following usually it is called composition (the II)) combination that is selected from thermoplastic resin and rubbery polymer being obtained to be suitable for the polymer composition of various shaped materials.The ratio of composition (I) and composition (II) can be controlled arbitrarily for maximum brings into play the effect of each composition.The blending ratio of composition (I) and composition (II) counts 1/99～99/1 with the mixed weight ratio of composition (I)/composition (II) generally speaking, and is preferred 2/98～90/10, and more preferably 5/95～70/30.When composition (II) when being thermoplastic resin, the mixed weight ratio of suggestion composition (I)/composition (II) is 2/98～90/10, and is preferred 5/95～60/40, more preferably 10/90～40/60.In the polymer composition of forming by composition (I) and composition (II), with respect to the total amount of the composition (I) and the composition (II) of 100 weight parts, can also mix 0.01～20 weight part, preferred 0.02～10 weight part, the more preferably composition of 0.05～7 weight part (III).

When with second-order modified block copolymer of the present invention and thermoplastic resin mixing, just can obtain the outstanding polymer composition of shock-resistance and shaping processability.

As thermoplastic resin, comprise the above-mentioned conjugated diene compound relevant and the block copolymer resin of vinyl aromatic compounds with the preparation of basic segmented copolymer; The polymkeric substance of this vinyl aromatic compounds; This vinyl aromatic compounds and other at least one vinyl monomer (but being different from vinyl aromatic monomers), for example copolymer resins such as ethene, propylene, butylene, vinylchlorid, vinylidene chloride; Rubber-modified styrene resin (HIPS); Acrylonitrile-butadiene-styrene (ABS) copolymer resin (ABS); Methacrylic ester-butadiene-styrene copolymer resin (MBS); Olefin polymer; Cyclic olefin resinoids such as ethylene-norbornene resin; The polybutene resinoid; The polyvinyl chloride resinoid; The polyvinyl acetate resinoid; The polymkeric substance of vinylformic acid and ester thereof and acid amides; The polyacrylic ester resinoid; The polymkeric substance of vinyl cyanide and/or methacrylonitrile; These vinyl cyanide monomers and can with the monomeric multipolymer of its copolymerization, and contain the nitrile resin of the above vinyl cyanide monomeric unit of 50 weight %; Polyamide-based resin; Polyester resin; The thermoplastic polyurethanes resin; Polycarbonate polymer; Thermoplasticity polysulfones such as polyethersulfone and polyene propyl group sulfone; The polyoxymethylene resinoid; The polyhenylene ether resin; Polyhenylene sulfuration thing resinoids such as polyhenylene sulfuration thing and poly-4,4 '-two penylene sulfide; Polyene propyl diester resinoid; Polyetherketone polymkeric substance or multipolymer; The polyketone resinoid; Fluoro-resin; Polyoxy benzoyl polymkeric substance; Polyimide based resin; Having the polymkeric substance that replaces the structure partly or completely of chain hydrocarbon macromolecular compound hydrogen with fluorine, is fluoro-resin such as tetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer specifically; 1, polyhutadiene resinoids such as 2-polyhutadiene, trans polybutadiene etc.These thermoplastic resins also can be with above-mentioned twice-modified dose of composition (III) modification.The number-average molecular weight of these thermoplastic resins is normally more than 1000, and preferably 5000～5,000,000, be more preferably 10,000～1,000,000.

In the above-mentioned thermoplastic resin, preferred polyester resinoid, polyamide-based resin, polycarbonate resin, polyurethanes resin, polyhenylene ether resin, polyoxymethylene resinoid.These thermoplastic resins all contain functional group.Above-mentioned thermoplastic resin can separately or mix more than two kinds and use.Contain the thermoplastic resin of functional group and second-order modified block copolymer (composition (I)) reaction or react by this, can significantly improve the intermiscibility of composition with a modified block copolymer (composition (I-1)) and twice-modified dose (composition (III)).

In addition, when with second-order modified block copolymer of the present invention and rubbery polymer mixing, can obtain tensile strength and tensile elongation, the outstanding polymer composition of shaping processability.

Rubbery polymer as composition (II) uses comprises divinyl rubber and hydride thereof; Styrene butadiene rubbers and hydride thereof (but different) with second-order modified block copolymer of the present invention; Synthetic polyisoprene; Acrylonitrile-butadiene rubber and hydride thereof; Olefin type elastomers such as neoprene, ethylene-propylene rubber, ethylene-propylene-dience rubber, ethene-butylene-dience rubber, ethene-butene rubber, ethene-hexene rubber, ethylene-octene rubber; Isoprene-isobutylene rubber; Acrylic rubber; Viton; Silicone rubber; Chlorinated polyethylene rubber; Epoxy propane rubber; α, alpha, beta-unsaturated nitriles-acrylate-conjugated diolefine copolymerization rubber; Urethanes; Polysulfide rubber; Styrene-butadiene block copolymer and hydride thereof; Styrenic such as styrene-isoprene block copolymer and hydride thereof elastomerics; Natural rubber etc.These rubbery polymers also can be the modified rubbers of introducing functional group, for example, these rubbery polymers are carried out the rubber of modification with composition (III).As preferred modified rubber, can exemplify the olefin type elastomer such as ethylene-propylene rubber, ethylene-propylene-dience rubber that is selected from the functional group of hydroxyl, carboxyl, anhydride group, isocyanate group, epoxy group(ing), amino, alkoxysilane group for introducing; Styrene-butadiene copolymer and hydride thereof (but different) with modified block copolymer of the present invention; Styrenic elastomericss such as styrene-isoprene multipolymer and hydride thereof; Divinyl rubber; Synthetic polyisoprene etc.The number-average molecular weight of these rubbery polymers is preferred more than 10,000, and more preferably 2～1,000,000, further preferred 3～800,000.

In addition, these thermoplastic resins and rubbery polymer also can mix use as required more than two kinds.Mix the not restriction especially of different polymkeric substance such as composition (II).For example, as composition (II), no matter be to use between the thermoplastic resin composition or between the rubbery polymer composition.Also have, the mixing of thermoplastic resin and rubbery polymer is used and also can.

In the present invention, also provide polymer composition, it comprises:

With respect to the total amount of composition (I-1) and composition (II) be 1～99 weight %, preferred 2～90 weight %, more preferably 5～70 weight % an above-mentioned modified block copolymer composition (I-1) and

With respect to the total amount of composition (I-1) and composition (II) be 99～1 weight %, preferred 98～10 weight %, more preferably 95～30 weight % at least a polymkeric substance that is selected from thermoplastic resin and rubbery polymer and

With respect to the composition (I-1) that amounts to 100 weight parts and composition (II) is 0.1～20 weight part, preferred 0.02～10 weight part, the more preferably twice-modified dose of composition (III) of 0.05～7 weight part, and wherein twice-modified dose composition (III) has the functional group with the functional group reactions of a properties-correcting agent base of this modified block copolymer (I-1).

When composition (II) when being thermoplastic resin, the mixed weight ratio of suggestion composition (I-1)/composition (II) is 2/98～90/10, and is preferred 5/95～60/40, more preferably 10/90～40/60.

In above-mentioned polymer composition, the thermoplastic resin in the preferred component (II) is the thermoplastic resin that contains functional group, and the rubbery polymer in the composition (II) is the rubbery polymer that contains functional group.In addition, when composition (II) when having functional group, twice-modified dose (III) with the functional group of all reacting with the functional group of the functional group of composition (I) and composition (II) used in suggestion, perhaps has twice-modified dose (III) all reacting with the functional group of the functional group of a properties-correcting agent base of composition (I-1) and composition (II).

Thermoplastic resin as containing functional group comprises polyester resin; Polyamide-based resin; Polycarbonate resin; The polyurethanes resin; The polymkeric substance that has imide bond in the main chain, for example polyimide, poly-amino dimaleimide (poly-dimaleimide), dimaleimide cyanate resin, polyimide resin polyimide based resins such as (imide or polyetherimides); The polymkeric substance of formaldehyde or trioxane, the polyoxymethylene resinoids such as multipolymer of formaldehyde or trioxane and other aldehyde, cyclic ethers, epoxide, isocyanic ester, vinyl compound etc.; Polysulfones resins such as polyethersulfone and polyene propyl group sulfone; Polyhenylene ether resins such as poly-(2,6-dimethyl-1,4-penylene) ether; Polyhenylene sulfuration thing resinoids such as polyhenylene sulfuration thing, poly-4,4 '-two penylene sulfide; Polyene propyl diester resinoid as the polycondensation base polymer of forming by dihydroxyphenyl propane and phthalic acid; The polyketone resinoid.

In addition, the example that contains the thermoplastic resin of functional group, comprise vinyl aromatic compounds and the vinyl monomer (being different from vinyl aromatic compounds) of at least one, the copolymer resin of vinyl-acetic ester, vinylformic acid or acrylate acrylate, vinyl cyanide, methacrylonitriles etc. such as (for example, methyl acrylates) for example; Acrylonitrile-butadiene-styrene copolymer resin (ABS); Methacrylate butadi ene styrene copolymer resin (MBS); As ethene with and and the ethylene unit that contains of copolymerizable other monomeric multipolymer be resin more than the 50 weight %, (for example vinyl-vinyl acetate copolymer and hydrolysate thereof); Deng polythylene resin (for example, ethylene-acrylic acid ionomer); As propylene with and and the propylene units that contains of copolymerizable other monomeric multipolymer be resin more than the 50 weight %, polypropylene-based resin such as propylene-ethyl acrylate copolymer for example; As vinyl-acetic ester with and and the vinyl acetate unit that contains of copolymerizable other monomeric multipolymer be polyvinyl acetate esters resin and hydrolysate thereof more than the 50 weight %.

In addition, the example that contains the thermoplastic resin of functional group also comprises the polymkeric substance of vinylformic acid and ester and acid amides; The polymkeric substance of methacrylic acid and ester thereof and acid amides; As these (methyl) acrylic monomers with and and the acrylic monomer amount of copolymerizable other monomeric multipolymer be polyacrylate(s) monomer more than the 50 weight %; The polymkeric substance of vinyl cyanide and/or methacrylonitrile; As these (methyl) vinyl cyanide monomers with and and (methyl) vinyl cyanide monomer amount of copolymerizable other monomeric multipolymer be the above nitrile monomers of 50 weight %; Use P-hydroxybenzoic acid, terephthalic acid, m-phthalic acid, 4, polyoxy benzoyl base polymers such as 4 '-dihydroxybiphenyl or these derivative, the polymkeric substance by the polycondensation preparation or multipolymer etc.

The polyester resin that uses among the present invention contains ester bond at intramolecularly, the polyester resin of representative has the structure that dicarboxylic acid and ethylene glycol carry out polycondensation, and it carries out polycondensation by dicarboxylic acid, its lower member ester, its acid halide or acid anhydrides and ethylene glycol and obtains.Aromatic series or aliphatic dicarboxylic acid as the raw material that becomes this polyester resin, comprise oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, pimelic acid, suberic acid, hexanodioic acid, sebacic acid, nonane diacid, 1,9-nonane dicarboxylic acid, 1,10-decane dicarboxylic acid, 1,16-hexadecane dicarboxylic acid, terephthalic acid, m-phthalic acid, right, right '-dicarboxylate biphenyl, to carboxyl phenylium, 2,6-naphthalene dicarboxylic acids etc., these can use separately or with arbitrary combination.Wherein preferred terephthalic acid and m-phthalic acid.Also have, also these arbitrary combination can be used.In addition, ethylene glycol (perhaps glycol) as another raw material of polyester resin has aromatic series or aliphatic, for example comprise ethylene glycol, 1, ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,4-cyclohexanediol, 1,10-decanediol, neopentyl glycol, p-Xylol ethylene glycol etc., these can use separately or with arbitrary combination.Wherein preferred ethylene glycol, 1, ammediol and 1,4-butyleneglycol.

As other useful polyester resin, also comprise in addition, for example the polylactone that obtains of ring-opening polymerizations such as pivalolactone, beta-propiolactone, 6-caprolactone by the cyclic lactone.These polyester resins can be used in combination separately or more than two kinds.

The polyamide-based resin that uses among the present invention is the polycondensate of dicarboxylic acid and diamines, the polycondensate of alpha-amino carboxylic acid, the ring-opening polymerization polymer of cyclic lactames etc.Specifically, comprise nylon-4,6, nylon-6, nylon-6,6, nylon-6,10, nylon-11, PA-12 etc. and these multipolymer (for example, nylon-6-nylon-6,6 multipolymers, nylon-6-PA-12 multipolymer).The fusing point of these polyamide resins is preferably 150～270 ℃, when requiring more outstanding processibility, more preferably has the polyamide-based resin of fusing point below 260 ℃.And above-mentioned polyamide-based resin can be used in combination separately or more than two kinds.

The polycarbonate resin that uses among the present invention specifically, is the polymkeric substance that the precursors reaction of above phenolic compound of divalent and carbonic ether is obtained.Various divalent phenolic compound are arranged, can give an example, for example 2,2-two (4-hydroxy phenyl) propane (being commonly referred to as " dihydroxyphenyl propane "), two (4-hydroxy phenyl) methane, 2,2-two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane, 2,2-two (4-hydroxy-3-methyl phenyl) propane, two (4-hydroxy phenyl) sulfone, 1,1-two (4-hydroxy phenyl) ethane, 1,1-two (4-hydroxy phenyl) hexanaphthene, 1,1-two (4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane etc.

As preferred divalent phenol, comprise two (4-hydroxy phenyl) alkane, particularly dihydroxyphenyl propane.Also have above-mentioned divalent phenol both can use separately and also can make up use more than two kinds.As carbonate precursor, comprise carbonylic halide, carbonyl ester or haloformate in addition.More specifically, can be bishaloformate of being selected from carbonyl chloride, biphenyl carbonate, divalent phenol and composition thereof.

The viscosity-average molecular weight of the polycarbonate resin that uses among the present invention is from the intensity and the stable on heating viewpoint of the composition that obtains, preferably more than 10,000, in addition from the viewpoint of processibility, preferably below 60,000, be more preferably 12000～45000, further preferably 13000～35000.And the viscosity-average molecular weight among the present invention (M) is to calculate from the specific viscosity of obtaining by the methylene dichloride that the 0.7g polycarbonate resin is dissolved in 100ml under 20 ℃.

The polyurethanes resin that uses among the present invention can obtain by vulcabond and glycol are carried out polyaddition, for example comprises the polymer blocks (as soft segment) of polyalcohols (polyester or polyethers) and comprises vulcabond and the polymer blocks of ethylene glycol (as hard segment).As the polyester glycol that becomes this polyurethanes resin raw material, comprise poly-(1,4-butylene adipate ester), poly-(1,6-hexane adipic acid ester), polycaprolactone etc.As polyether glycol, comprise polyoxyethylene glycol, polypropylene glycol, polyoxy tetramethylene ethylene glycol etc.

In addition as glycol, comprise ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycols etc. as vulcabond, have aromatic series, alicyclic and aliphatic vulcabond, tolylene diisocyanate, 4 for example, 4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate and isophorone diisocyanate etc.

The resinoid weight-average molecular weight of the urethane that uses among the present invention, the viewpoint from the mechanical characteristics of the composition that obtains is preferably 5000～500,000, and more preferably 1～300,000,

As the polyhenylene ether resin, be not particularly limited can use known.As concrete example, comprise poly-(2,6-dimethyl-1, the 4-phenylene ether), poly-(2-methyl-6-ethyl-1,4-phenylene ether), poly-(2,6-phenylbenzene-1, the 4-phenylene ether), poly-(2-methyl-6-phenyl-1, the 4-phenylene ether), poly-(2,6-two chloro-1,4-phenylene ether) etc. and these modifier (for example maleic anhydride modified thing etc.), also comprise 2 in addition, the multipolymer of the phenols of 6-xylenol and other (for example 2,3,6-pseudocuminol or 2-methyl-6-butylphenol).Wherein, preferred poly-(2,6-dimethyl-1,4-phenylene ether), 2,6-xylenol and 2,3, the multipolymer of 6-pseudocuminol and these modifier.The reduced viscosity of suggestion polyhenylene ether resin (measuring down at 30 ℃ in the 0.5g/dl chloroformic solution) is preferably 0.05～0.70, and more preferably 0.10～0.60, further preferred 0.15～0.60.When obtaining the outstanding polymer composition of physical strength, it is 0.30～0.60 polyhenylene ether that reduced viscosity is used in suggestion.

As the polyoxymethylene resinoid that uses among the present invention, comprise homopolymer, and be the multipolymer of main component with above-mentioned monomer with the polymerization of formaldehyde or trioxane preparation.Homopolymer as polyformaldehyde resin uses with the modified form that the end group with polymkeric substance is transformed to ester group or ether, and then improves the thermotolerance and the chemical resistant properties of polymkeric substance.As the resinoid multipolymer of polyoxymethylene, comprise formaldehyde or trioxane and be selected from other aldehyde, cyclic ether, cyclic carbonate, epoxide, isocyanic ester, the multipolymer of vinyl compound at least.

In the present invention, can mix additive arbitrarily as required.The kind of additive is restriction especially not, as long as can mix use just passable usually with thermoplastic resin and rubbery polymer.

Additive for example comprises arbitrarily, mineral filler and organic fillers such as metal hydroxides, silica-based inorganic filler, metal oxide.From the action effect that produces by these fillers and the balance of processibility, with respect to the composition (I) or the composition (I-1) of 100 weight parts, the amount of mineral filler and organic filler is 0.5～2000 weight part, preferred 1～1000 weight part, more preferably 3～500 weight parts.

The metal hydroxides of using as mineral filler is a hydration class inorganic filler, can use the hydrate etc. of the inorganic metal compound such as hydrate, borax of for example aluminium hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminium silicate, hydrated magnesium silicate, alkaline magnesium carbonate, hydrotalcite, calcium hydroxide, hydrated barta, stannic oxide.Can also use the mixture of mixture, metal hydroxides and the metal hydroxides inorganic filler in addition of the metal oxide more than two kinds.

As the silica type inorganic filler, can use with chemical formula SiO ₂Perhaps Si ₃Al is as the solids of the main component of structural unit, and for example the silica type inorganic filler comprises inorganic fibrous materials such as silicon oxide, clay, talcum, kaolin, mica, wollastonite, wilkinite, polynite, zeolite, diatomite, synthetic silica, granulated glass sphere, glass sphere, sheet glass and glass fibre etc.Also can use the surface-hydrophobicized silica type inorganic filler and the mixture of the inorganic filler beyond mixture, silica type inorganic filler and the silica type of silica type inorganic filler more than two kinds.As silicon oxide, can use desiccating method white carbon(ink), wet method white carbon(ink), synthetic silicic acid salt white carbon(ink), so-called colloidal silica etc.

As metal oxide, can use with chemical formula M _xO _y(M is an atoms metal, and x, y are respectively 1～6 integer) is the solids of the main component of structural unit, for example aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, ferric oxide etc.Can also use the mixture of mixture, metal oxide and the metal oxide inorganic filler in addition of the metal oxide more than two kinds.

These mineral fillers can be a kind of separately or be used in combination more than two kinds.As other mineral filler, comprise inorganic fillers such as lime carbonate, magnesiumcarbonate, barium carbonate, Calucium Silicate powder, calcium sulfate, calcium sulfite, titanium oxide, potassium titanate, barium sulfate, barium titanate, zinc oxide, asbestos, slag wool in addition.

Organic filler comprises organic fillers such as carbon black, acetylene black, furnace black.As carbon black, can comprise the carbon black of various level other FT, SRF, FEF, HAF, various grades such as ISAF, SAF, the preferred nitrogen adsorption specific surface area is the above carbon black of 50mg/g.

In the present invention, also can use lipid acid or its metal-salts such as stearic acid, oleic acid, palmitinic acid; Paraffin, wax, polyethylene wax or these modifier; Organometallic compound such as organo-borane, organic titanate; Silane coupling agents etc. carry out surface treatment to the surface of mineral filler.

As silane coupling agent, can use and fill the mineral fillers of using such as silane, comprise for example 3-sulfydryl propyl trimethoxy silicane, 3-mercapto methyl dimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane etc.Particularly preferred silane coupling agent is to have silanol base or alkoxysilane group among the present invention, has sulfydryl simultaneously or/and the compound of the polysulfide key of two above sulphur connections.As such silane coupling agent, comprise for example 3-sulfydryl propyl trimethoxy silicane, the 3-aminopropyltriethoxywerene werene, two [3-(triethoxysilyl) propyl group] tetrasulfide, two [3-(triethoxysilyl) propyl group] disulphide, two [3-(triethoxysilyl) propyl group] trisulphide, two [3-(triethoxysilyl) ethyl] tetrasulfide, 3-triethoxysilylpropyltetrasulfide-N, N '-dimethylamino thiocarbonyl group-tetrasulfide, 3-trimethoxy-silylpropyl-N, N '-dimethylamino thiocarbonyl group-tetrasulfide, 3-triethoxysilylpropyltetrasulfide benzothiazole tetrasulfide, 3-trimethoxy-silylpropyl benzothiazole tetrasulfide etc.

In order to give full play to the stiffening effect that is produced by weighting agents such as mineral fillers in polymer composition, the combined amount of silane coupling agent is 0.1～20 weight % with respect to filler, more preferably 0.5～18 weight %, further preferred 1～15 weight %.And, when using silane coupling agent, also can use sulphur and organo-peroxide simultaneously.

In the present invention, can be in order to improve processibility mixed rubber with tenderizer (VII) (following also usually be called " composition (VII) ").As softener of rubber (VII), be fit to use mineral oil or aqueous or low-molecular-weight synthetic tenderizer, can use softening, the increase-volume that is generally used for rubber, the mineral oils softener of rubber that is called as " process oil " or " extending oil " that improves processibility and polybutene, low molecular weight polybutadiene, whiteruss, mineral oil, organopolysiloxane, Viscotrol C, linseed oil wet goods tenderizer.These tenderizers also can just add in the modified block copolymer of the present invention after segmented copolymer preparation of the present invention.As the softener of rubber of the present invention's use, from the viewpoint of color, preferred naphthenic tenderizer and paraffin class tenderizer.The combined amount of these tenderizers is the 0-200 weight part with respect to the composition (I) or the composition (I-1) of 100 weight parts, preferred 0-100 weight part.

In the present invention, as other additive, the antioxidant that comprises " Gomu PurasuchikkuHaigou Yakuhin (Additives for Rubber and Plastic) " (published byRubber Digest Co., Ltd., Japan (1968)) etc.; UV light absorber; Photostabilizer; Lubricants such as stearic acid, behenic acid, Zinic stearas, calcium stearate, Magnesium Stearate or ethene distearyl acid amides; Remover; Paraffin; Plasticizer; Fire retardant; Static inhibitor; Tougheners such as organic fibre, charcoal fiber, whisker; Pigment; Tinting material etc.

The preparation method of polymer composition of the present invention has no particular limits, and can use known method.For example, can use closed mixing machine, single pole forcing machine, two bar forcing machine, associating kneader, many bars forcing machine etc. to use the fusing kneading method of general mixing machine; With after dissolving of each composition or the dispersing and mixing, add the method for heat extraction solvent etc.In the present invention, from the viewpoint of productivity, uniform mixing, preferably use the fusing kneading method of forcing machine.Shape for the polymer composition that obtains has no particular limits, but comprises ball shape, sheet, wire, shred etc.In addition, can also after mediating, fusing directly form molding.

When preparation polymer composition of the present invention, the interpolation order of each composition for example can adopt the method with all the components mixed once without limits in addition, perhaps optional ingredients is pre-mixed afterwards, adds the blending means that remaining one-tenth grades.Particularly preferred method is the method that composition (I) and composition (II) are mediated in fusing, and perhaps the method for composition (I-1), composition (II) and composition (III) is mediated in fusing.

In the present invention, fusing is mediated temperature and can be selected according to the softening temperature of thermoplastic resin that uses and rubbery polymer and fusing point etc., but melt viscosity from thermoplastic resin, and the viewpoint of the thermal ageing of rubbery polymer and second-order modified block copolymer composition (I), a modified block copolymer composition (I-1) or its hydride, usually preferred 50～350 ℃, more preferably 100～330 ℃, further preferred 130～300 ℃.In addition, viewpoint such as aging from mixedness (dispersiveness) and productivity, mixing element, the fusing kneading time (perhaps the mean residence time of operation is mediated in fusing) generally is preferably 0.2～60 minute, and more preferably 0.5～30 minute, further preferred 1～20 minute.

Second-order modified block copolymer of the present invention and polymer composition, as former state ground or mixed the composition of various additives, known method before can using, for example, extrusion molding, injection molding, double-colored injection molding, interlayer shaping, hollow forming, compression molding, vacuum forming, spinning-shaping, powder slush molding, foaming and molding, laminating molding, press polish shaping etc. are processed as useful especially molding.In addition, as required, also can foam, pulverize, stretch, adhere, processing such as printing, painted, plating.By this manufacturing process, can form thin slice, film, different shape injection molding product, hollow forming product, press empty molding, vacuum forming product, extrusion molded article, expansion-molded article, non-woven fabrics and various molding such as fibrous molding, synthetic leather.These molding can be used for starting material such as packaging material for food, medical device, tame electrical article and parts, electronics and parts thereof, trolley part, industrial part, household supplies, toy, footwear starting material, tackiness agent starting material, asphalt modifier etc.

Below, the present invention mixed to second-order modified block copolymer or in polymer composition other additive composition, use these various uses to specifically describe.

[flame-retardant polymer composition]

Flame-retardant polymer composition of the present invention obtains by any method of using following (i)～(iii):

(i) with second-order modified block copolymer of the present invention (I) and mineral filler (VI) and olefin polymer blended method;

The polymer composition of the present invention and mineral filler (VI) the blended method that (ii) will comprise composition (I) and composition (II); With

The polymer composition of the present invention and mineral filler (VI) the blended method that (iii) will comprise composition (I-1), composition (II) and composition (III).

In flame-retardant polymer composition of the present invention, the atomic group X that contains functional group in the second-order modified block copolymer ¹Functional group can with the thermoplastic resin that contains functional group and/or rubbery polymer, mineral filler (VI) reaction, simultaneously owing in second-order modified block copolymer, contain nitrogen-atoms and Sauerstoffatom or carbonyl, so between the polar group of these atoms and group and thermoplastic resin and/or rubbery polymer, mineral filler (VI), can produce effectively because the interaction of physics avidity, hydrogen bond etc. for example, thus flame retardant resistance composition outstanding, high tenacity become.

In flame-retardant polymer composition of the present invention, flame retardant effect and the tensile strength of fracture and the balance of tensile elongation from composition, the amount of mineral filler (VI), with respect to the composition (I) of 100 weight parts, with respect to the polymer composition of the present invention that comprises composition (I) and composition (II) of 100 weight parts or with respect to the polymer composition of the present invention that comprises composition (I-1), composition (II) and composition (III) of 100 weight parts, be generally 10～2000 weight parts, preferred 20～1000 weight parts, more preferably 25～500 weight parts.

(VI) can use above-mentioned mineral filler as mineral filler.

In flame-retardant polymer composition of the present invention, in order to improve flame retardant resistance, as mineral filler (VI), in above-mentioned mineral filler, the preferred hydration class mineral fillers such as hydrate of using inorganic metal compounds such as aluminium hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminium silicate, hydrated magnesium silicate, alkaline magnesium carbonate, hydrotalcite, calcium hydroxide, hydrated barta, aqua oxidation tin, borax, more preferably magnesium hydroxide, aluminium hydroxide.These mineral fillers can be a kind of separately or be used in combination more than two kinds.

In addition in flame-retardant polymer composition of the present invention, in order to improve flame retardant effect, also can use phosphorus type flame retardants such as ammonium polyphosphate based flame retardant, phosphoric acid ester, silicone compounds, silica glass etc. as required, in addition as fire retardant, also can use liquid glass, frit etc., in addition, in order to prevent to drip, also can use silicon nitride staple fibre etc.

As the example of the olefin polymer that in flame-retardant polymer composition of the present invention, uses, can use linear alpha-olefins such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-good fortune alkene; 4-methyl-1-pentene, 2-methyl isophthalic acid-propylene, 3-Methyl-1-pentene, 5-methyl isophthalic acid-hexene, 4-methyl isophthalic acid-hexene, 4,4 '-dimethyl-polymkeric substance and multipolymers such as side chain alpha-olefin such as 1-amylene.When above-mentioned olefin-copolymerization is fashionable,, for example, can choose wantonly from random copolymers, segmented copolymer, graft copolymer and these mix-configuration for the not restriction especially of structure of multipolymer.Object lesson as olefin polymer comprises polyethylene; Contain ethene and be the above ethene of 50 weight % and can with the monomeric multipolymer of its copolymerization, for example ethylene-propylene copolymer, ethylene-butene copolymer, ethene-hexene copolymer, ethylene-octene copolymer; Polyvinyl resins such as chlorinatedpolyethylene; Polypropylene; Contain propylene and be the above propylene of 50 weight % and can with the monomeric multipolymer of its copolymerization, for example propylene-ethylene copolymers, propylene-ethyl acrylate copolymer; Acrylic resins such as Chlorinated Polypropylene III; Poly-1-butylene etc.

As particularly preferred olefin polymer, comprise polyethylene, polypropylene, poly-1-butylene, propylene-ethylene copolymers, propylene-butene-1 copolymer, 1-fourth-ethene alkene copolymer, propylene-ethylene-butene-1 copolymer etc.

These olefin polymers can be a kind of separately or be used in combination more than two kinds.

From the tensile strength of composition and the balance of tensile elongation, the combined amount of the olefin polymer in the flame-retardant polymer composition of the present invention is with respect to the second-order modified block copolymer (I) of 100 weight parts, be generally 0～1000 weight part, preferred 2～1000 weight parts, more preferably 5～800 weight parts, further preferred 10～500 weight parts.

Flame-retardant polymer composition of the present invention has outstanding flame retardant resistance, even simultaneously when burning, can not produce toxic gases such as halogen gas yet, in addition, demonstrate well-balanced mechanical characteristics, thus can be as the material that is suitable for interior distribution of machine and purposes such as industrial material such as line for cars bundle isoelectric line coating material, insulation tape.

[crosslinked]

Of the present invention crosslinked be to comprise following (i) or polymer composition of the present invention (ii), it is mediate to obtain by fusing in the presence of vulcanizing agent.

(i) comprise composition (I) (second-order modified block copolymer of the present invention) and be selected from thermoplastic resin and the bridging property material of the component of polymer (II) that rubbery polymer is at least a; Perhaps

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

Of the present invention crosslinked in, the atomic group X that contains functional group in the second-order modified block copolymer (I) ¹Functional group can with reactions such as thermoplastic resin that contains functional group and/or rubbery polymer.In addition, second-order modified block copolymer contains nitrogen-atoms and Sauerstoffatom or carbonyl.Between these atoms and group and thermoplastic resin and/or rubbery polymer isopolarity group, can produce effectively because the interaction of physics avidity, hydrogen bond etc. for example, thus become good compositions such as physical strength and oil-proofness.

In above-mentioned bridging property material, the weight ratio of composition (I) and composition (II) is generally 10/90～100/0, and is preferred 20/80～90/10, and more preferably 30/70～80/20.Above-mentioned bridging property material also can contain the composition (III) of 0.01～20 weight part with respect to the composition (I) of 100 weight parts.

In addition, of the present invention when crosslinked when obtaining by the polymer composition of the present invention that comprises composition (I-1), composition (II) and composition (III), the weight ratio of composition (I-1) and composition (II) is generally 10/90～100/0, and is preferred 20/80～90/10, and more preferably 30/70～80/20.The amount of composition (III) is generally 0.01～20 weight part, preferred 0.02～10 weight part, more preferably 0.05～7 weight part with respect to the composition (I-1) and the composition (II) that amount to 100 weight parts.

Mediating in the fusing in the presence of the vulcanizing agent is to carry out under the temperature condition that vulcanizing agent reacts under the melted state, can cause dispersion and crosslinked thus simultaneously.Mediate for the fusing in the presence of vulcanizing agent, at length be recorded in the document Rub.Chem.AndTechnol.vol.53 of A.Y.Coran etc., in 141 (1980).The kneader that uses during fusing in the presence of vulcanizing agent is mediated uses kneader, single pole and two bar extrusion machines etc. as sealings such as closed mixing machine, adding pressure type kneaders to carry out usually.Normally 130～300 ℃ of temperature, preferred 150～250 ℃ are mediated in fusing.Normally 1～30 minute kneading time of fusing.Usually, organo-peroxide and phenolic resin linking agent are as vulcanizing agent.

Organo-peroxide as vulcanizing agent, can use " Gomu PurasuchikkuHaigou Yakuhin (Addiitives for Rubber and Plastic) " (published byRubber Digest Co., Ltd., etc. known material Japan (1968)).Wherein, preferred dicumyl peroxide, ditertiary butyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexin, 1,3-two (t-butyl peroxy sec.-propyl) benzene, 1,1-two (t-butyl peroxy)-3,3, the 5-trimethyl-cyclohexane, normal-butyl-4,4-two (t-butyl peroxy) valerate, ditertiary butyl peroxide etc.

When using above-mentioned organo-peroxide to carry out the desired cross-linking agent of crosslinked acquisition, preferred also with organo-peroxide and crosslinking coagent, for example sulphur, p-benzoqui(o)none dioxime, P, P '-DBQD, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine and TriMethylolPropane(TMP)-N, N '-peroxide crosslinking coagents such as a penylene maleimide; Vinylstyrene; Triallyl cyanurate; Multi-functional methacrylate monomer such as Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), polydimethyl vinylformic acid glycol ester, trimethylolpropane trimethacrylate and allyl methacrylate(AMA); Multi-functional vinyl monomers such as butylation ethene, stearic acid vinyl ester etc.

In the presence of vulcanizing agent, melt when mediating, the usage quantity of vulcanizing agent is the composition (I) of 100 weight parts when not containing composition (II) usually, the polymer composition of 100 weight parts when perhaps containing composition (II), be generally 0.01～15 weight part, the ratio of preferred 0.04～10 weight part.

Of the present invention crosslinked in, in the scope of not damaging its characteristic, can before crosslinked, be pre-mixed additive as required.Additive comprises additives such as tenderizer, heat-resisting stabilizing agent, static inhibitor, weather resistance agent, antiaging agent, weighting agent, tinting material, lubricant.

For the hardness of regulating product and mobile and blended tenderizer as required can use above-mentioned composition (VII).Its add-on is generally 0～200 weight part with respect to the composition (I) or the composition (I-1) of 100 weight parts, preferred 10～150 weight parts, more preferably 20～100 heavy parts.

In addition, as weighting agent, comprise lime carbonate, talcum, clay, Calucium Silicate powder, magnesiumcarbonate, magnesium hydroxide etc.The add-on of these weighting agents is generally 0～200 weight part, preferred 10～150 weight parts, more preferably 20～100 weight parts with respect to the composition (I) or the composition (I-1) of 100 weight parts.

Gel content (still, wherein do not contain not tolerant grade such as mineral filler and do not allow composition) in crosslinked of the present invention is preferably 5～80 weight %, more preferably 10～70 weight %, further preferred 20～60 weight %.Here, so-called gel content is measured with following method.Use ebullient dimethylbenzene in cable-styled extractor, crosslinked sample (1g) to be refluxed 10 hours, residue is filtered with 80 mesh wire cloths, measurement remains in the dry weight (g) of the insolubles on the mesh, and the ratio of dry weight that calculates and example weight (weight %).The ratio that is obtained is defined as crosslinked gel content.

Of the present invention crosslinked be good compositions such as physical strength and oil-proofness, can be used for above-mentioned various uses.

[binder composition]

Can be by in composition (I) (second-order modified block copolymer), perhaps mix tackifier (VIII) (the following composition (VIII) that usually is called) in the mixture of composition (I-1) (modified block copolymer or its hydride) and twice-modified dose of composition (III), obtain binder composition of the present invention.

In binder composition of the present invention, the atomic group X that contains functional group in the second-order modified block copolymer ¹Functional group or twice-modified dose (III) can with the adhesive reaction that contains functional group, simultaneously owing in second-order modified block copolymer or in the reactant of a modified block copolymer (composition (I-1)) and twice-modified dose (composition (III)), contain nitrogen-atoms and Sauerstoffatom or carbonyl, so between the polar group of these atoms and group and tackiness agent (VIII), can produce effectively because the interaction of physics avidity, hydrogen bond etc. for example, thus the outstanding composition in balance aspect of adhesiveness such as clinging power, confining force become.

In binder composition of the present invention, can use above-mentioned composition (I) or composition (I-1), the basic segmented copolymer of special preferred component (I) or composition (I-1), it comprises:

(a) 20～90 weight %, the segmented copolymer of preferred 25～80 weight %, this segmented copolymer a polymer blocks A who mainly contains the vinyl aromatic hydrocarbon and mainly contain conjugated diolefine a polymer blocks B multipolymer as basic framework and

(b) 80～10 weight %, the segmented copolymer of preferred 75～20 weight %, this segmented copolymer at least two polymer blocks A that mainly contain the vinyl aromatic hydrocarbon and the multipolymer of at least one polymer blocks B that mainly contains conjugated diolefine as basic framework

Comprise above-mentioned basic segmented copolymer composition (a) and basic segmented copolymer (b) if use, then can obtain the outstanding especially binder composition of balance of confining force, tackiness and melt viscosity.These molecular weight are (in using the mensuration of GPC, the peak molecular weight that uses polystyrene standard to convert), composition (a) is 3～150,000, preferred 4～140,000, more preferably 5～130,000, and composition (b) is 10～300,000, preferred 12～280,000, more preferably 14～260,000, and, also adopt these preferred from the viewpoint of confining force and adhesive balance and melt viscosity.

As the composition that uses among the present invention (VIII) (tackifier), kind is restriction especially not, can use tackifier resins arbitrarily, for example known tackifier resins such as colophony type terpine resin, hydrogenant colophony type terpine resin, coumarone resin, resol, terpenes-phenolic resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin.These tackifier also can mix more than two kinds.As the object lesson of tackifier, can use above-mentioned " Gomu PurasuchikkuHaigou Yakuhin (Additives for Rubber and Plastic) " (published byRubber Digest Co., Ltd., Japan (1968)).From the tackiness of binder composition and the balance quality of confining force, with respect to the composition (I) or the composition (I-1) of 100 weight parts, the usage quantity of tackifier is 20～400 weight parts, preferred 50～350 weight parts.

In binder composition of the present invention, can add above-mentioned composition (VII) (Rubber Softener) as tenderizer in addition, owing to can reduce the viscosity of binder composition by adding tenderizer, and then when improving processibility, improved tackiness.From the tackiness of binder composition and the balance quality of confining force, with respect to the composition (I) or the composition (I-1) of 100 weight parts, the usage quantity of tenderizer is 0～200 weight part, preferred 0～100 weight part.

In addition, in binder composition of the present invention, also can add stablizer as required, for example antioxidant, photostabilizer UV light absorber etc. can be used the material of " Gomu ... (1968) " record particularly.In addition, in binder composition of the present invention, also can add wax classes such as solid paraffin, Microcrystalline Wax, low molecular weight polyethylene wax as required; Polyolefins or low-molecular-weight vinyl aromatic analog thermoplastic resins such as amorphous polyolefin, ethylene-ethyl acrylate multipolymer; Natural rubber; Synthetic rubber such as styrene butadiene class beyond polyisoprene rubber, polybutadiene rubber, styrene butadiene rubbers, ethylene-propylene rubber, neoprene, acrylic rubber, isoprene-isobutene rubber, polypentenamer rubber, half modified block copolymer of the present invention or the modified block copolymer or styrene-isoprene based block copolymer.

Binder composition of the present invention can use known mixing machine, kneader etc. to modulate by mixed uniformly method under heating.Heating temperature is generally 150～210 ℃.

Binder composition of the present invention has improved softening temperature, and demonstrated the balance excellent characteristic of adhesiveness such as clinging power and confining force, thereby it is fixing fixing with the fixing raw material with back adhesive etc. of back adhesive, patch block with back adhesive, carpet to be used as various adhesive tape labels class, pressure-sensitive binding property thin plate, pressure-sensitive binding property sheet, various lightweight plastic material molding, particularly is advantageously used for the adhesive tape label.

[surface protection binder film]

By on resin molding, forming the binder layer that comprises the binder layer of mentioned component (I) and composition (VIII) or comprise composition (I-1), composition (III) and composition (VIII), can obtain surface protection binder film of the present invention.Use in the binder film atomic group X that contains functional group in the second-order modified block copolymer in surface protection of the present invention ¹Functional group can react with the tackifier that contain functional group (composition (VIII)); simultaneously owing in second-order modified block copolymer, contain nitrogen-atoms and Sauerstoffatom or carbonyl; so between the polar group of these atoms and group and tackiness agent; can produce effectively because the interaction of physics avidity; hydrogen bond etc. for example, thus the outstanding surface protection binder film of anchoring strength obtained.

With in the binder film, the thickness of binder layer is normally below the 200 μ m in surface protection of the present invention, preferred 5～50 μ m.In addition, thickness of resin film is generally below the 300 μ m, preferred 10～100 μ m.

Use in the binder film in surface protection of the present invention; consider adhesive power after surface protection is with the clinging power of binder film and long-term the attaching, remaining glue etc. when peeling off; is 3～200 weight parts as the combined amount of the tackifier composition (VIII) (tackifier) of one of constituent of binder layer with respect to the composition (I) or the composition (I-1) of 100 weight parts; preferred 5～150 weight parts, more preferably 10～120 weight parts.In addition, the combined amount of composition (VIII) is 0.01～20 weight part with respect to the composition (I-1) of 100 weight parts.

Use in the binder film in surface protection of the present invention, as the non-polar resin or the polar resin of resin molding use.Non-polar resin comprises polystyrene resins, polyolefin resin etc.As polystyrene resins, comprise the polymkeric substance of the block copolymerization resin of polystyrene, vinylbenzene and conjugated diene compound, above-mentioned vinyl aromatic compounds, above-mentioned vinyl aromatic compounds and other vinyl monomer, for example copolymer resin of ethene, propylene, butylene, vinylchlorid, vinylidene chloride etc., rubber-modified styrene resin (HIPS), acrylonitrile-butadiene-styrene (ABS) copolymer resin (ABS), methacrylic ester-butadiene-styrene copolymer resin (MBS) etc.The polyolefin resin of the non-polar resin that uses as resin also can contain the copolymer rubber more than two kinds or three kinds of alpha-olefin, perhaps olefin hydrocarbons thermoplasticity elastic bodies such as alpha-olefin and other monomeric multipolymer.As these copolymer rubbers, comprise ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), ethylene-octene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM) etc.

On the other hand, with in the binder film, the polar resin that uses as resin molding is the above-mentioned described thermoplastic resin that contains functional group in surface protection of the present invention.

Use in the binder film in surface protection of the present invention, as the resin that uses in the resin molding, even in these non-polar resins or polar resin, also preferably can make the resin of resin molding by melt-extruded shaping, from performance with wait in price, comprise the homopolymer or the segmented copolymer of polyethylene, propylene; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate; Polyamide-based resin; Ethylene-vinyl acetate copolymer and hydrolysate etc. thereof.

Surface protection of the present invention can be carried out by example described as follows like that with the manufacturing of binder film.

Promptly; by using fusing-co-extrusion press; binder constituents and thermoplastic resin composition are divided into two fluids; promptly; form to form with fluid and form single fluid and push by in ダイスロ, adding adhesive agent layer with fluid and resin molding, and with binder layer and the compound acquisition surface protection binder film of making of resin film layer.Can certainly also can be easy to make by applying adhesive layer composition on resin molding.

The surface protection binder film that uses method of the present invention to obtain; because anchoring strength (adhesivity of binder layer and resin molding) is good; so use binder film in enterprising andante metalworkings such as metal sheets surface protection; when perhaps metal sheet is placed for a long time, also have the characteristics that can not produce remaining glue.

[bituminous composition]

By in composition (I) (second-order modified block copolymer), adding pitch (the following composition (IX) that usually is called), perhaps composition (I-1), composition (III) and composition (IX) are mixed, can obtain bituminous composition of the present invention.In bituminous composition of the present invention, the atomic group X that contains functional group in the second-order modified block copolymer ¹Functional group or twice-modified dose (III) can with the functional group reactions in the pitch (composition (IX)), simultaneously owing in modified block copolymer or in the reactant of half modified block copolymer (composition (I-1)) and twice-modified dose (composition (III)), contain nitrogen-atoms and Sauerstoffatom, perhaps carbonyl, so between these atoms and group and bituminous polar group, can produce effectively because the interaction of physics avidity, hydrogen bond etc. for example, thereby obtained softening temperature, extensibility, flexible, the polymer certainty is good, and the bituminous composition of high-temperature storage excellent in stability.

In table bituminous composition of the present invention, can use composition (I) or composition (I-1), and particularly preferably be the basic segmented copolymer of composition (I) or composition (I-1), it comprises:

Comprise above-mentioned basic segmented copolymer composition (a) and basic segmented copolymer (b) if use, then can obtain softening temperature and the good bituminous composition of balance quality of the stability that is separated.These molecular weight are (in using the mensuration of GPC, the peak molecular weight that uses polystyrene standard to convert), composition (a) is 3～150,000, preferred 4～140,000, more preferably 5～130,000, and composition (b) is 10～300,000, preferred 12～280,000, more preferably 14～260,000, and, also adopt these preferred from the viewpoint of the balance quality of the softening temperature of bituminous composition and the stability that is separated.

The pitch (composition (IX)) that is used for bituminous composition comprises petroleum pitch (by product during petroleum refinement), perhaps natural rock asphalt, and the perhaps mixture of these and oil, its main component is that pitch (bitumen) gets final product.Particularly, can comprise straight chain pitch, half oxidized bitumen, oxidized bitumen, tar, tar-bitumen, the fluxed asphalt that has added oil, asphalt emulsion etc.These pitches can also can mix use separately.Preferred in the present invention pitch is that penetration coefficient (measuring according to JIS-K 2207) is 30～300, preferred 40～200, more preferably 45～150 straight chain pitch.In bituminous composition of the present invention, the blending ratio of composition (I) or composition (I-1) is 0.5～50 weight part with respect to the composition (IX) (pitch) of 100 weight parts, preferred 1～30 weight part, more preferably 3～20 weight parts.

When bituminous composition of the present invention comprises composition (I-1), composition (IX) and composition (III), the combined amount of composition (III) is 0.01～5 weight part with respect to the pitch composition (IX) of 100 weight parts, preferred 0.05～5 weight part, more preferably 0.1～5 weight part, more preferably 0.2～3 weight part, further preferred 0.5～2 weight part.And, comprise the bituminous composition of composition (I) and composition (IX), can also mix the composition (III) of 0.1～5 weight part with respect to the composition (IX) of 100 weight parts.

In bituminous composition of the present invention, can mix the composition (following usually be called " composition (X) ") that contains sulphur as required.As composition (X), can be powder sulphur, sedimentary sulphur, gelationus sulphur, surface-treated sulphur, insoluble sulphur, inertia sulphur etc., can use sulfocompounds such as sulfur subchloride, sulfurous gas, morpholine disulphide, alkylphenol disulphide, polymer polysulfide etc. in addition.In addition, composition (X) can mix use with an amount of crosslinking accelerator.As crosslinking accelerator, can use sulphinyl amide accelerant, guanidine acclerators, thiuram type accelerator, aldehyde amine(type)accelerators, aldehyde ammonia class promotor, thiazole accelerator, Thiourea accelerator, dithiocarbamate promotor, xanthate acid class promotor etc.As the object lesson of linking agent, comprise diphenylguanidine, normal-butyl aldehyde-aniline condensation thing, vulkacit H, 2-mercaptobenzothiazole, N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine, diphenyl thiourea, tetra methylthiuram monosulphide, Sodium dimethyldithiocarbamate 40min, sec.-propyl sulfonic acid zinc.The amount of sulphur is 0.01～10 weight part with respect to the composition (IX) of 100 weight parts in the composition (X), preferred 0.05～5 weight part, more preferably 0.1～2 weight part.In addition, when using crosslinking accelerator, its usage quantity is generally 0.01～10 weight part with respect to the composition (IX) of 100 weight parts, preferred 0.05～5 weight part, more preferably 0.1～2 weight part.

In addition, in bituminous composition of the present invention, can add silane coupling agent.As silane coupling agent, can use above-mentioned silane coupling agent, its combined amount is generally 0.01～20 weight part with respect to the composition (IX) of 100 weight parts, preferred 0.05～10 weight part, more preferably 0.1～5 weight part.

In bituminous composition of the present invention, from the viewpoint of certainty, tensio-active agents such as mixed anion tensio-active agent, cats product and nonionogenic tenside as required.As the object lesson of tensio-active agent, comprise the copolymerization oligopolymer of the metal-salt, monoamine compound, diamine compound, polyamine compound of higher fatty acid, higher fatty acid, poly-oxyethylene and poly-propylene oxide etc.In addition, can use acid organo phosphorous compounds, the mixture of acid organo phosphorous compounds and inorganic phosphorous compound, polycarboxylic acid and acid anhydrides thereof, aliphatic phosphate ester, high alcohol phosphates such as stearyl phosphoric acid ester, the mixture of higher alcohols and phosphated alcohol, gallic acid or its derivative, Tall oil resin acid or its derivative, the condenses of polyalkylene polyamine and lipid acid, liquid epoxy resin, the modified by maleic acid anhydride graft polypropylene, modified by maleic acid anhydride graft SBS (styrene-butadiene block copolymer), modified by maleic acid anhydride graft SEBS (styrene-ethylene/butylene block-copolymer), modified by maleic acid anhydride graft SEPS (styrene-ethylene/propylene-based block copolymer) etc.

In bituminous composition of the present invention, can mix additive arbitrarily as required.The kind of additive is so long as normally used just passable in the mixing of thermoplastic resin and rubbery polymer, restriction especially.For example, can add vulcanizing agent, peroxide crosslinking used additives, multi-functional vinyl monomer, other above-mentioned various additives such as stablizer, organo-peroxide and phenolic resin crosslinking agent such as inorganic filler components (VI) and other mineral filler, organic filler, silane coupling agent, softener of rubber composition (VII), tackifier composition (VIII), antioxidant.Also can add composition (II) as required.

Bituminous composition of the present invention obtained softening temperature, extensibility, flexible, certainty is good, and the bituminous composition of high-temperature storage excellent in stability can be widely used for paving the way, purposes such as waterproof thin plate, sound insulation thin plate, roof cladding.

Bituminous composition of the present invention is because high-temperature storage stability, extensibility, low-temperature flexibility, certainty are good, so be suitable for use as the tackiness agent in the drainage road roads such as road that the many overweight automobiles such as road, expressway, point of crossing and turning place of the volume of traffic meet easily.

Drainage road road of the present invention is the drainage road road that the drainage road layer of hole is used in a plurality of drainings that has that comprises road and formation thereon, this drainage road layer by a plurality of gather materials and tackiness agent form, this tackiness agent is made up of bituminous composition of the present invention.

Cold propertys such as the drainage road road that bituminous composition of the present invention is used as tackiness agent is difficult to break when having good anti-rut, water-permeable, reduction Traffic noise, low temperature.

Usually, the bituminous pavement road is formed by following method.In the mixture of the coarse aggregate with suitable size-grade distribution (rubble), fine aggregate (sand, broken sand, stone flour) etc., add the tackiness agent under the heated condition (temperature is generally 150～210 ℃), and then acquisition asphalt mixture (amount of binder is 5.3～6.5%, preferred 5.5～6%).The asphalt mixture that obtains is covered on the road surface, and the asphalt mixture layer on the road surface is planished, thereby obtained the bituminous pavement road with roller etc.

Drainage road road of the present invention is formed by following method.In the mixture of the coarse aggregate with suitable size-grade distribution (rubble), fine aggregate (sand, broken sand, stone flour) etc., add the bituminous composition of the present invention under the heated condition (temperature is generally 150～210 ℃) as tackiness agent, and then acquisition asphalt mixture (amount of binder is 4.5～5.5%, preferred 4.7～5.3%).The asphalt mixture that obtains (containing bituminous composition of the present invention) is covered on the road surface, and the asphalt mixture layer on the road surface is planished, thereby obtained drainage road road of the present invention with roller etc.With many void ratios on the supercrust of the prevailing roadway road that uses common asphalt mixture to form, the drainage road layer of drainage road road of the present invention has very many successive holes that is used for draining.Because this characteristic, drainage road road of the present invention has demonstrated remarkable performance, for example prevent to produce the drainage of rain pool, by preventing that rain on the road surface from forming continuous moisture film guarantee the to walk ability of security, and the performance that reduces Traffic noise (for example, exhaust noise or tire contact the noise that produces with the road surface).Also has the size (particle diameter) that porosity can be gathered materials by control and gather materials and bituminous mixes and recently obtains desirable value.Using the porosity of the drainage road layer that bituminous composition of the present invention forms is 5～35%, more preferably 10～30%, further preferred 12～28%.

The porosity of bituminous composition defines with following formula.

= \frac{V_{v}}{V} \times 100 = (1 - \frac{ρ_{m}}{D}) \times 100

In the formula, ρ _mExpression asphalt mixture density (g/cm ³), V represents the volume (cm of asphalt mixture ³), V _vVolume of voids (the cm of expression asphalt mixture ³), D represents the theoretical maximum density (g/cm of asphalt mixture ³).

The best form of implementation of invention

Specifically describe the present invention by following examples, but the present invention is not subjected to any qualification of these examples.

1. the characteristic of segmented copolymer and hydride thereof

(1) styrene content

(FDAC is made made, and the absorption intensity of mensuration segmented copolymer UV200) is calculated styrene content to use ultraviolet spectrophotometer at 262nm.

(2) styrene block rate

Accurately (chloroform of 30～50mg) segmented copolymer and the about 10ml of adding to wherein adding perosmic anhydride (catalyzer) and tertiary butyl hydroxyl peroxide (oxygenant), boiled under 100 ℃ 20 minutes the weighing specified amount, made the segmented copolymer oxygenolysis.In the reaction mixture that obtains, add 200ml methyl alcohol, thereby make precipitate of polystyrene.Use 11G4 (Japanese bavin field instruments for scientific research industry (strain) system) filtering precipitate, obtain the filtration residue formed by polystyrene, the weight of the polystyrene that mensuration obtains.Styrene block rate (weight %) is calculated by following formula

Styrene block rate (weight %)=(the unitary gross weight of styrene monomer in the segmented copolymer of the weight of filtration residue/afore mentioned rules amount) * 100

(3) vinyl bonds resultant and hydrogenation ratio

(German BRUKER society system DPX-400) is measured to use nuclear magnetic resonance device.

(4) weight-average molecular weight

With GPC (device: the system LC10 of Shimadzu Seisakusho Ltd. of Japan, post: the system Shimpac GPC805+GPC804+GPC804+GPC803 of Shimadzu Seisakusho Ltd. of Japan) measure.Use tetrahydrofuran (THF) as solvent, under 35 ℃ of temperature, measure.Weight-average molecular weight is used the typical curve that is obtained by commercially available single decentralized standard polystyrene sample, by the GPC chromatographic determination of peak value display molecular weight.

(5) ratio of unmodified segmented copolymer

For in the 20ml tetrahydrofuran (THF), containing the sample solution that 10mg modified block copolymer and 10mg weight-average molecular weight are mark polystyrene in 8000 the lower molecular weight, measure the chromatogram that obtains by using the method identical to carry out GPC, obtain the ratio (a) of modified block copolymer with respect to polystyrene standard with above-mentioned (4).In addition, for said sample solution, except the device Zorbax of use U.S. DuPont society system with the post of silica gel as weighting agent, measure the chromatogram that obtains by using the method identical to carry out GPC with above-mentioned (4), obtain the ratio (b) of unmodified segmented copolymer with respect to polystyrene standard.Owing to (a) be modified block copolymer part and unmodified segmented copolymer summation partly, (b) only be unmodified segmented copolymer part, so, can obtain the ratio of unmodified segmented copolymer in modified block copolymer by this two ratios (a) and (b).

2. the modulation of hydrogenation catalyst

The hydrogenation catalyst that uses in the hydrogenation is modulated with following method.

(1) hydrogenation catalyst I

In nitrogen metathetical reactor, add dry, 1 liter of hexanaphthene of purified, add two (η of 100 mmoles then ⁵-cyclopentadienyl) titanium dichloride Yi Bian fully stir, Yi Bian add the hexane solution that contains 200 mmole trimethyl ammoniums, at room temperature makes its reaction 3 days, and then obtains hydrogenation catalyst I.

(2) hydrogenation catalyst II

In nitrogen metathetical reactor, add dry, 2 liters of hexanaphthenes of purified, then with two (η of 40 mmoles ⁵-cyclopentadienyl) 1 of two-(p-methylphenyl) titanium and 150g molecular weight about 1000,2-polyhutadiene (1,2-vinyl bonds resultant about 85%) after the dissolving, add the cyclohexane solution that contains 60 mmole n-Butyl Lithiums, at room temperature make its reaction 5 minutes, add the propyl carbinol of 40 mmoles then immediately, stir simultaneously, and then obtain hydrogenation catalyst II, at room temperature preserve.

3. the preparation of the reactive polymer of segmented copolymer

The preparation of polymkeric substance 1 (the following P-1 that usually is called):

To have stirrer and protective sleeve autoclave washing, dry, with the nitrogen displacement, then add and contain the 10 weight parts cinnamic cyclohexane solution of purified (concentration of styrene 20 weight %) in advance.Add n-Butyl Lithium and Tetramethyl Ethylene Diamine (as vinylated dose and randomization agent) according to the amount of table 1 respectively then, 70 ℃ of following polymerizations after 1 hour, add and contain the 80 weight parts cyclohexane solution of purified divinyl (butadiene concentration 20 weight %) in advance, and 70 ℃ of following polymerizations 1 hour, add again in addition and contain the cyclohexane solution of 10 parts by weight of styrene and, thereby obtain polymkeric substance 1 (P-1) as the reactive polymer of segmented copolymer 70 ℃ of following polymerizations 1 hour.The characteristic of polymkeric substance 1 has been shown in the table 1.

Polymkeric substance 2～polymkeric substance 23 (the following preparation that usually is called P-2～P-23):

Except change adding monomeric amount, use the method identical with polymkeric substance 1, obtain to have polymkeric substance 2～polymkeric substance 23 (following P-2～P-23) of usually being called of reactive polymer of the segmented copolymer of characteristic shown in the table 1.

4. the preparation of modified block copolymer and hydride thereof

One time modified block copolymer prepares by the following method.In the solution of the reactive polymer 1～23 that contains above-mentioned segmented copolymer respectively, a properties-correcting agent that adds the specified amount shown in table 2, table 5, table 8, table 13, table 15, table 21, the table 23 makes its reaction obtain one time modified block copolymer in 20 minutes respectively under 70 ℃.

The hydride of a modified block copolymer prepares by the following method.By in the solution of an above-mentioned modified block copolymer, adding hydrogenation catalyst I or II in Ti 100ppm, under 0.7MPa hydrogen pressure, 65 ℃, carry out 1 hour hydrogenation, obtain the hydride of a modified block copolymer.

In the solution of modified block copolymer or its hydride, add the methyl alcohol with respect to 10 times of moles of the n-Butyl Lithium that uses in the polymerization separately, add soda water then, regulating pH is below 8.

The modified block copolymer that obtains or the characteristic of its hydride are shown in table 2, table 5, table 8, table 13, table 15, table 21, the table 23.

5. the preparation of second-order modified block copolymer

Second-order modified block copolymer prepares by the following method.In the above-mentioned modified block copolymer or its hydride that obtains, make and twice-modified dose of reaction with fusing kneading method or solution method respectively, obtain second-order modified block copolymer.

Under the situation of fusing kneading method, respectively in the above-mentioned modified block copolymer or its hydride solution that obtains, segmented copolymer with respect to 100 weight parts, add the octadecyl-3-(3 of 0.3 weight part as stablizer, the 5-di-tert-butyl-hydroxy phenyl) behind the propionic ester, by adding the heat extraction solvent.In the modified block copolymer that obtains or its hydride, mix twice-modified dose that is shown in specified amount in table 2, table 5, table 8, table 13, table 15, table 21, the table 23, with the two bar extrusion machines of 30mm φ under 220 ℃, make its reaction by the fusing kneading with 100rpm screw threads revolution.

Under the situation of solution method, in modified block copolymer or its hydride solution, adding is with respect to the methyl alcohol of 10 times of moles of the n-Butyl Lithium that uses in the polymerization, add soda water then, after regulating pH and be below 8, in this solution, add twice-modified dose that is shown in specified amount in table 2, table 5, table 8, table 13, table 15, table 21, the table 23, under about 60 ℃, make its reaction 30 minutes.With respect to the segmented copolymer of 100 weight parts, add octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester of 0.3 weight part as stablizer after, by adding the heat extraction solvent, obtain second-order modified block copolymer.

The characteristic of the second-order modified block copolymer that obtains is shown in table 2, table 5, table 8, table 13, table 15, table 21, the table 23.

6. (relation of the structure of M1～M5) and twice-modified dose (D1, D2) and a modified block copolymer obtaining and the structure of second-order modified block copolymer is as follows for a properties-correcting agent that uses among the embodiment.

Properties-correcting agent (M1～M5) and the relation of structure:

M1: when M1 was used as a properties-correcting agent, a modified block copolymer that obtains had the structure with formula (8) expression, wherein C ²In expression (d-1) unit and formula (e-1) unit any one, D ²Expression (f-1) unit.

M2: when M2 was used as a properties-correcting agent, a modified block copolymer that obtains had the structure with formula (6) or (7) expression, wherein A ²In expression (a-1) unit and formula (b-1) unit any one, B ²Expression (c-1) unit.

M3: when M3 was used as a properties-correcting agent, a modified block copolymer that obtains had the structure with formula (10) expression, wherein E ²Expression (g-1) unit, F ²Expression (h-1), (I-1) and (j-1) any one in the unit.

M4: when M4 was used as a properties-correcting agent, a modified block copolymer that obtains had the structure with formula (9) expression, wherein C ²In expression (d-1) unit and formula (e-1) unit any one, D ²Expression (f-1) unit.

M5: when M5 was used as a properties-correcting agent, a modified block copolymer that obtains had the structure with formula (10) expression, wherein E ²Expression (g-1) unit, F ²Expression (h-1) unit.

The relation of twice-modified dose (D1, D2) and structure:

D1: (after any one of M1～M5) carried out a modification, it was twice-modified to use D1 to carry out, and then can obtain having X if use an above-mentioned properties-correcting agent ¹Second-order modified block copolymer for formula (n) modular construction.

D2: (after any one of M1～M5) carried out a modification, it was twice-modified to use D2 to carry out, and then can obtain having X if use an above-mentioned properties-correcting agent ¹Second-order modified block copolymer for formula (p) modular construction.

Thermoplastic resin composition's embodiment and comparative example

(1) modified block copolymer

The modified block copolymer that uses has been shown in the table 2.

(2) thermoplastic resin

PET: the Mitsui Chemicals system Mitsui ペ of Japan Star ト SA135

Polymeric amide: nylon 6 (the beautiful system アミラ Application CM1017 in east of Japan)

(3) physical property measurement

Flexible rate (MPa): with ASTM-D790 is standard.

The Izod shock strength (J/m) that has otch: with JIS K-7110 is standard.

Embodiment 1～8, comparative example 1～6

Embodiment 1～8 and comparative example 1～6th are according to the mixing formula shown in the table 3, thermoplastic resin with specified amount, modified block copolymer or unmodified segmented copolymer, and twice-modified dose of dry mixed, mixture with respect to 100 weight parts, the 2-tert-pentyl-6-[1-(3 that adds 0.3 weight part again as stablizer, 5-two tert-pentyls-2-hydroxy phenyl) ethyl]-uncle's 4-aminophenyl acrylate, with the two bar extrusion machines of 30mm φ be at thermoplastic resin under the situation of PET under 250 ℃, and at thermoplastic resin be under the situation of polymeric amide under 260 ℃, mediate by fusing with 250rpm screw threads revolution and to obtain resin combination.The rerum natura of the composition that obtains is shown in Table 3.

Embodiment 9～13, comparative example 7,8

In embodiment 9～13 and comparative example 7 and 8, use second-order modified block copolymer or unmodified segmented copolymer, use the method identical to obtain resin combination according to the mixing formula shown in the table 4 with embodiment 1～8.The composition of composition is shown in table 4 with transitivity.Also have, " P-2/D2 (1.2mol/Li) " of the comparative example 7 of table 4 and comparative example 8 refers to " mixture of polymer P-2 and twice-modified dose is the butyllithium that 1.2 moles/mole add in the concentration of preparation polymer P-2 o'clock D2 ".

From the result of embodiment 1～13 and comparative example 1～8, the present invention's segmented copolymer of containing functional group can improve the shock strength of thermoplastic resin effectively as can be known.

The embodiment of flame-retardant polymer composition and comparative example

(1) modified block copolymer

The modified block copolymer that uses is shown in Table 5.

(2) inorganic combustion inhibitor

X-1: with higher fatty acid carry out surface treatment magnesium hydroxide (Japan's consonance chemistry (strain) system KISUMA5A)

X-2: untreated magnesium hydroxide (Japan's consonance chemistry (strain) system KISUMA5A)

(3) olefin polymer

The system PM801A of polypropylene Moutell SDK society

(4) physical property measurement

Tensile strength:, measure breaking tenacity (MPa) and fracture percentage of elongation (%) according to JIS K7210.

Oxygen index (O.I.): measure according to JIS K7210.So-called oxygen index refers to adding polymer samples, N in drum ladle ₂And O ₂Mixture after seal, and when making sample combustion, the N that the sample continuous burning was measured more than 3 minutes ₂/ O ₂Oxygen concn in the mixture.Oxygen index is high more, and flame retardant resistance is high more.Measure oxygen index, according to following standard, with ◎, zero, * three levels estimate.

◎: more than 28%

Zero: 24% above less than 28%

*: less than 24%

Embodiment 14～21, comparative example 9～11

Embodiment 14～21, comparative example 9～11st are according to the flame-retardant polymer composition of the cooperation of the mixing formula shown in the table 6, hydride with respect to a modified block copolymer of 100 weight parts, add specified amount inorganic combustion inhibitor, twice-modified dose and polypropylene, also have the 2-tert-pentyl-6-[1-(3 as stablizer of 0.03 weight part, 5-two tert-pentyls-2-hydroxy phenyl) ethyl]-uncle's 4-aminophenyl acrylate, obtain the flame-retardant polymer composition particle by melting to mediate with the two bar extrusion machines of 30mm φ down at 220 ℃.Be pressed into shape and make the sample that evaluation of physical property is used by the particle that obtains is penetrated.The rerum natura of composition is shown in Table 6.

Embodiment 22～24, comparative example 12

In embodiment 22～24, comparative example 12, use the method identical to obtain flame-retardant polymer composition with embodiment 14～21 according to the mixing formula shown in the table 7.The composition of composition, be shown in Table 7 with transitivity.Also have, " 1P-10/D1 (2.1mol/Li) " of the comparative example 12 of table 7 is meant that " mixture of polymkeric substance 1P-10 and twice-modified dose of D1, the concentration of D1 is the butyllithium that 2.1 moles/mole add when preparation polymkeric substance 1P-10.”

Result from embodiment 14～24 and comparative example 9～12, the flame retardant resistance of finding flame-retardant polymer composition of the present invention is good, even when burning, can not produce toxic gas (halogen gas etc.) simultaneously yet, the balance of mechanical properties is good in addition, therefore is suitable for distribution and purposes such as industrial material such as automotive wire bundle isoelectric line coating material, insulation tape in the machine.

The surface protection embodiment and the comparative example of binder film

(1) segmented copolymer

The modified block copolymer that uses is shown in Table 8.

(2) physical property measurement

Surface protection is as follows with the physical property measurement of binder film.To take out with melted state with the binder composition that following method obtains, it is coated on the resin molding of thickness 100 μ m, so that form the coating of thickness 15 μ m, and then be made into binder film, measure anchoring strength, clinging power and attach the remaining glue in back with following method.

Anchoring strength (g/20mm): behind the film of the wide 20mm that firmly adheres between the surface that has applied tackiness agent, under 20 ℃ * 65% relative humidity (RH), carry out 180 degree stripping tests with the peeling rate of 200mm/min.

Clinging power (g/25mm): on the SUS304 of wide 25mm steel plate, attach binder film, under 20 ℃ * 65% relative humidity (RH), carry out 180 degree stripping tests with the peeling rate of 200mm/min.

Attach the remaining glue in back: attach binder film on the SUS304 steel plate, place in 40 ℃ after 6 months, observation has or not remaining glue under 20 ℃ * 65% relative humidity (RH).

Embodiment 25～29, comparative example 13,14

At embodiment 25～29, comparative example 13, in 14, according to the mixing formula mixed adhesive composition shown in the table 9, modified block copolymer or its hydride with respect to 100 weight parts, the quantitative tackifier of hybrid regulatory and twice-modified dose, also has the 2-tert-pentyl-6-[1-(3 as stablizer of 0.3 weight part, 5-two tert-pentyls-2-hydroxy phenyl) ethyl]-uncle's 4-aminophenyl acrylate, in having the container of stirrer, descended melt-blended 2 hours, thereby obtain binder composition at 180 ℃.Binder composition and polyethylene film that use obtains are made binder film, and carry out physical property measurement.Mixing composition and rerum natura is shown in Table 9.

Embodiment 30～34, comparative example 15,16

In embodiment 30～34, comparative example 15,16,, use with the same method of embodiment 25～29 and obtain binder composition according to the mixing formula mixed adhesive composition shown in the table 10.Binder composition that use obtains and PET film are made binder film, and carry out physical property measurement.Mixing composition and rerum natura is shown in Table 10.

Embodiment 35～38, comparative example 17

In embodiment 35～38, comparative example 17,, use second-order modified block copolymer and use the method identical to obtain binder composition with embodiment 25-29 according to the mixing formula shown in the table 11.Binder composition and polyolefin film that use obtains are made binder film, and carry out physical property measurement.Mixing composition and rerum natura is shown in Table 11.Also have, " 1P-16/D1 (2.1mol/Li) " of the comparative example 17 of table 11 is meant that " mixture of polymkeric substance 1P-16 and twice-modified dose of D1, the concentration of D1 is the butyllithium that 2.1 moles/mole add when preparation polymkeric substance 1P-16.”

Embodiment 39～41, comparative example 18

In embodiment 39～41, comparative example 18,, use the method identical to obtain binder composition with embodiment 30～34 according to the mixing formula shown in the table 12.Binder composition that use obtains and PET film are made binder film, and carry out physical property measurement.Mixing composition and rerum natura is shown in Table 12.Also have, " 1P-16/D1 (2.1mol/Li) " of the comparative example 18 of table 12 is meant that " mixture of polymkeric substance 1P-16 and twice-modified dose of D1, the concentration of D1 is the butyllithium that 2.1 moles/mole add when preparation polymkeric substance 1P-16.”

As can be known, the present invention protects with the anchoring strength and the clinging power of binder film good, even and also can not produce remaining glue after the prolonged preservation from embodiment 25～41, comparative example 13-18.

Binder composition embodiment and comparative example

(1) segmented copolymer

The modified block copolymer that uses is shown in Table 13.

(2) physical property measurement of binder composition

A. softening temperature

Softening temperature is to measure according to JIS-K2207 (ring method and ball indentation method).

In addition, use the compress device that the binder composition after the just preparation that obtains under the melted state is coated on the resin molding, so that form the thickness of 50 μ m, thereby make adhesive tape, and measure rerum natura with following method.

B. clinging power (g/10mm): the sample that 25mm is wide is attached on the vinylbenzene, under 20 ℃ * 65% relative humidity (RH), carries out 180 degree stripping tests with the peeling rate of 300mm/min, and it is wide to be converted into 10mm.

C. shear clinging power (minute): according to JIS Z-1524, measure to shear clinging power.Adhesive tape sample with adhesive composition layer with 25mm * 25mm area is provided, and this adhesive tape sample is adhered on the stainless steel plate, under 60 ℃, give the heavy burden of 1kg and the time that the measurement adhesive tape comes off.

D. stripping strength: on the back up pad under 150 ℃ with thickness after the samples pre-heated of about 100 μ m, pressurization (heavy burden 1kg/cm under uniform temp ²) 5 minutes and adhere, use according to the method for the stripping test of JISK6854 and measure stripping strength.At peeling rate is to measure under the 200mm/min.

Embodiment 42～45, comparative example 19

In embodiment 42～45, comparative example 19 according to the mixing formula shown in the table 14, modified block copolymer or second-order modified block copolymer with respect to 100 weight parts, mix tackifier, as the Diana process oil PW90 (Japan's bright dipping is emerging to produce) of tenderizer, twice-modified dose, the 2-tertiary butyl-the 6-as stablizer (the 3-tertiary butyl-2-hydroxy-5-methyl base the phenmethyl)-4-aminomethyl phenyl acrylate that also mixes 1 weight part, in having the container of stirrer, descended melt-blended 2 hours, thereby obtain binder composition at 180 ℃.Mixing composition and rerum natura is shown in Table 14.

Embodiment 46

In embodiment 46,, use twice-modified block according to the mixing formula shown in the table 14

(2) physical property measurement of bituminous composition

A. softening temperature

Measure according to JIS-K2207 (ring method and ball indentation method).

B. melt viscosity

Under 180 ℃, measure with Brookfield viscometer.

C. penetration coefficient

Penetration coefficient is according to JIS-K2207, and the probe of measuring regulation thrusts the length that the bituminous composition sample that remains on 25 ℃ in water bath with thermostatic control entered during 5 seconds.

D. elongation

Elongation is according to JIS-K2207, makes the bituminous composition sample flow into mold, become the regulation shape after, in water bath with thermostatic control, remain 4 ℃, when drawing sample with the speed of 5cm/min then, measure the distance of when sample fracture, extending.

E. adhesion strength

The bituminous composition that will be dissolved in the toluene with coater is coated on the canvas, and drying at room temperature 1 hour makes its dry 7 minutes, so that toluene evaporates fully in 70 ℃ of baking ovens.Then, the canvas that applied bituminous composition was put into 70 ℃ of baking ovens 1 hour with the grouan as the surface smoothing of adherend, after the taking-up promptly the roller with heavy burden 1kg press twice.In the thermostatic chamber of 23 ℃ * 65% relative humidity (RH), carry out 180 degree stripping tests of canvas and grouan then.

F. low-temperature bending characteristic

Bituminous composition is flowed in the mold of 20mm * 20mm * 120mm, cut off superfluous bituminous composition, maintenance was promptly taken out later in 4 hours in-10 ℃ cryostat,, measured stress in bending and flexural strain (up to the displacement of yield-point) with distance 80mmm, loaded speed 100mm/min, 2 support central load modes.

G. high-temperature storage stability

After the production of bituminous composition, this bituminous composition is flowed in the aluminium pot of internal diameter 50mm, high 130mm up to the upper limit, then put into 180 ℃ of baking ovens, take out after 24 hours and make its naturally cooling.Then, employing begins 4cm, begins the bituminous composition of 4cm from the upper end from the lower end, measure the softening temperature of top section and underclad portion respectively, the yardstick of this softening temperature difference as high-temperature storage stability.

(3) characteristic of drainage road mixture

Use No. 6 rubbles (S-13 rubble) (size range: 13mm～5mm), the broken sand of about 10 weight %, the stone flour of about 5 weight % of about 85 weight %, mixing is for porosity gathering materials for about 20% Mixed Design, and be heated to 170 ℃, mix down as the bituminous composition of the heat fused of tackiness agent and at 170 ℃ to wherein adding 5 weight %, thereby be made into porosity and be about 20% drainage road mixture, and measure following characteristic.Porosity is the value of being calculated by the volume and weight of said mixture.

The a.Cantabro oral examination is tested

Cantabro test be for estimate disperse gathering materials of asphalt mixture resistivity test.Cantabro test method according to " the other volume of the test method(s) brief guide of mating formation (tentative test method) " (the road association distribution (1988) of Corporation Japan) is measured.The maintenance temperature is 0 ℃, and test temperature is 18 ℃.

B. wheel tracking test (Wheel Tracking Test)

The wheel tracking test is in order to estimate the test of asphalt mixture in the anti-flowability of indoor environment.Wheel tracking test method according to " the other volume of the test method(s) brief guide of mating formation (tentative test method) " (the road association distribution (1988) of Corporation Japan) is measured.Specifically, make the small-sized rubber wheel walking repeatedly on the sample of prescribed level with specified loads, the change amount of time per unit sample is obtained dynamic stability (DS) in the time of thus.Test temperature is 60 ± 0.5 ℃.

Embodiment 47～49, comparison are than example 20～21

In embodiment 47～49, comparative example 20～21,, in the metal tin of 750ml, add 499g straight chain pitch 60-80[Japan petroleum (strain) system according to the mixing formula shown in the table 16], in 180 ℃ oil bath, fully soak metal tin.Then, in the pitch that becomes melted state and stirring, add the segmented copolymer of specified amount and twice-modified dose bit by bit.After adding fully, stirred 90 minutes with the speed of rotation of 5990rpm, thereby make bituminous composition.Mixing composition and rerum natura is shown in Table 16.And using 1,2,4,5-benzene tertacarbonic acid dianhydride is as twice-modified dose.In addition, in embodiment 49 and comparative example 21, use

In embodiment 50 and comparative example 22,23,, use the method identical to prepare bituminous composition with embodiment 47 according to the mixing formula shown in the table 17.Mixing composition and rerum natura is shown in Table 17.

Table 17

Embodiment 51

Except the maleic anhydride that uses 2 weight parts as twice-modified dose, use the method identical to obtain bituminous composition with embodiment 47.Its rerum natura is shown in Table 18.

Embodiment 52

Except using 2P-13, use the method identical to obtain bituminous composition with embodiment 47 as the segmented copolymer.Its rerum natura is shown in Table 18.

Embodiment 53

Except using 1P-31, use the method identical to obtain bituminous composition with embodiment 47 as segmented copolymer, straight chain pitch 80-100 and as twice-modified dose the maleic anhydride.Its rerum natura is shown in Table 18.

Embodiment 54

Except using 2P-14 respectively, use the method identical to obtain bituminous composition with embodiment 53 as the segmented copolymer.Its rerum natura is shown in Table 18.

Embodiment 55

Except using tolylene diisocyanate, use the method identical to obtain bituminous composition with embodiment 47 as twice-modified dose.Its rerum natura is shown in Table 18.

Embodiment 56

With the preparation method identical with embodiment 47, acquisition is made by 100 weight part straight chain pitch 60-80[Japan petroleums (strain)], 8 weight parts are with the second-order modified block copolymer 2P-15 of solution method modification, the bituminous composition that 0.1 weight part sulphur (Jinhua seal micro mist Sulfur, the Japan crane sees chemical industry (strain) system) is formed.Its rerum natura is shown in Table 18.

Embodiment 57

With the preparation method identical, obtain by 100 weight part straight chain pitch 60-80[Japan petroleums (strain) system with embodiment 47], the bituminous composition formed with the second-order modified block copolymer 2P-16 of solution method modification of 8 weight parts.The characteristic of the drainage road mixture of the characteristic of the bituminous composition that obtains and mix asphalt composition thereof is shown in Table 19.

Comparative example 24

Except using the unmodified segmented copolymer (P-20) do not make the properties-correcting agent reaction to replace the second-order modified block copolymer 2P-16, use the method identical to prepare bituminous composition and drainage road mixture with embodiment 57.Its rerum natura is shown in Table 19.

From embodiment 47～57, comparative example 20～24 as can be seen, bituminous composition of the present invention not only demonstrates good asphalt characteristic balance, and has demonstrated remarkable high-temperature storage stability.

The crosslinked embodiment and the comparative example of modified block copolymer composition

(1) modified block copolymer

The modified block copolymer that uses is shown in Table 20.

Also have, the second-order modified block copolymer of using among the embodiment 58 (2P-17) is prepared as follows.Make as 1 of properties-correcting agent, 3-dimethyl-2-imidazolidone (a properties-correcting agent M1) and reactive polymer P-21 reaction (modification), wherein the usage quantity of properties-correcting agent is the equimolal amount with respect to the n-Butyl Lithium that uses in the polymerization, carry out hydrogenation then, in this polymers soln, add 1 mole twice-modified dose of D1 (with respect to the functional group of 1 normal and this polymer-bound) and make its reaction (twice-modified), obtain second-order modified block copolymer (2P-17).

A modified block copolymer (1P-34) that uses in the comparative example 25, except do not carry out twice-modified, use the method preparation identical with above-mentioned 2P-17.

(2) composition that uses in the crosslinked preparation

Silicon oxide: the WACKER SILICONE of Asahi Chemical Industry of Japan system polymolecularity silicon oxide HDK-N200

Acrylic resin: Sun Allomer PC600S (the Montell SDK of Japan system)

Paraffin oil: Diana technical oil PW380 (Japan's bright dipping is emerging to produce)

Organo-peroxide: PERHEXA 25B (Japan Japan grease system)

Vulcanization accelerator: Vinylstyrene

(3) physical property measurement (tensile strength (MPa), tensile elongation (%))

The anti-characteristic of opening: according to JIS K6251, use No. 3 dumbbell, measure with the tensile stress speed of 500mm/min.

Embodiment 58, comparative example 25

In embodiment 58, comparative example 25 according to the mixing formula shown in the table 20, modified block copolymer with respect to 100 weight parts, with Henschel mixer 20 weight part silicon oxide, 48 weight part polypropylene, 72 weight part paraffin oils are mixed, use the two bar extrusion machines of 30mm φ under 220 ℃, to mediate mixture before obtaining dynamic crosslinking by fusing.In this mixture, add vulcanizing agent, mediate the cross-linking agent that has obtained vulcanizing by fusing with 30mm φ two bar extrusion machines.The rerum natura of the cross-linking agent that obtains is shown in Table 20.

Embodiment 59～64

In embodiment 59～69, use modified block copolymer shown in the table 21 or second-order modified block copolymer,, use the method identical to obtain resin combination with embodiment 9～13 according to the mixing formula shown in the table 22.The composition of composition is shown in Table 22 with transitivity.

Embodiment 65～66, comparative example 26

In embodiment 65～66, comparative example 26, use the second-order modified block copolymer shown in the table 23, measure stripping strength.Stripping strength is in the polymkeric substance preheating of going up about 100 μ m with thickness at supporter (aluminium sheet, PET film, canvas) under the specified temperature shown in the table 24 after 5 minutes, by carrying out 5 minutes pressurization (load 1kg/cm ²) adhere with supporter, be the value of measuring under the 200mm/min at peeling rate.

The measurement result of expression stripping strength in the table 24.

Embodiment 67

Except making N-(1 as properties-correcting agent, the 3-dimethylbutadiene)-3-(triethoxysilyl)-1-propylamine (properties-correcting agent M5) and reactive polymer P-8 reaction, wherein the usage quantity of properties-correcting agent as beyond the equimolal amount, in the same manner obtains one time modified block copolymer with the preparation of 1P-12 (referring to table 5) with respect to the n-Butyl Lithium that uses in the polymerization; Except using this modified block copolymer replacement 1P-12, obtain flame-retardant polymer composition in the same manner with embodiment 20.Composition that obtains and the embodiment 20 the same good characteristics (breaking tenacity, fracture percentage of elongation, oxygen index) that demonstrate.

Industrial utilizability

The polymer composition that contains second-order modified block copolymer of the present invention comprises twice-modified Block copolymer and thermoplastic resin and/or rubber-like polymer, it has demonstrated outstanding rigidity Balance with resistance to impact. Above-mentioned polymeric compositions of the present invention can pass through injection molding, squeeze Pressing formations etc. are processed into the formed products of various shapes, can be advantageously used in automobile component (automobile Built-in material, automobile exterior material), various containers, electrical home appliances, the doctor such as food container Treat the various uses such as mechanical part, industrial part, toy. In addition, if above-mentioned secondary is changed The property block copolymer and the composition combination that is selected from the various compositions such as inorganic filler, tackifier, pitch, Then can obtain to have by combination the polymer composition of all-purpose good characteristic.

Claims

1. modified block copolymer comprises:

This modified block copolymer represents with the formula of following formula (5),

(5) E ¹—F ¹

E ¹The unit that representative is represented with following formula (j),

(j) —R ⁹—P ¹

Wherein, X ¹Represent unit with any one expression of following formula (n)～formula (s),

In formula (j)～formula (s),

P ¹Represent basic segmented copolymer,

R ⁴, R ⁹～R ¹⁰And R ¹³～R ²⁰Represent C respectively independently _1-48Alkylidene group,

R ¹¹Expression C _1-48Alkyl, C _6-48Aryl, by C _1-48Moieties and C _6-48The alkaryl formed of aryl moiety, by C _1-48Moieties and C _6-48The aralkyl formed of aryl moiety, perhaps C _3-48Cycloalkyl,

Wherein, R ⁴, R ⁹～R ¹⁰, R ¹³～R ¹⁵And R ¹⁷～R ²⁰Not necessarily have the hydroxyl of being selected from, epoxy group(ing), amino, silanol, C independently of one another _1-24At least a functional group of alkoxysilane groups,

R ⁵～R ⁷And R ¹²Represent hydrogen atom independently of one another, C _1-48Alkyl, C _6-48Aryl, by C _1-48Moieties and C _6-48The alkaryl formed of aryl moiety, by C _1-48Moieties and C _6-48The aralkyl formed of aryl moiety, perhaps C _3-48Cycloalkyl,

Wherein, R ⁴And R ⁹～R ²⁰Not necessarily has at least a atom that is selected from Sauerstoffatom, nitrogen-atoms, sulphur atom, Siliciumatom that is bonded on it independently of one another, described at least a atom is to be different from the mode bonding of hydroxyl, epoxy group(ing), amino, silanol and alkoxysilane groups

Y, z, α are 1 or above integer independently of one another.

2. polymer composition, comprise: with respect to the total amount of composition (I) and composition (II) be 1～99 weight % claim 1 modified block copolymer composition (I) and be at least a component of polymer (II) that is selected from thermoplastic resin and rubbery polymer of 99～1 weight % with respect to the total amount of composition (I) and composition (II).

3. the polymer composition of claim 2, wherein the thermoplastic resin in the composition (II) is the thermoplastic resin that contains functional group, the rubbery polymer in the composition (II) is the rubbery polymer that contains functional group.

4. the polymer composition of claim 3, wherein this thermoplastic resin that contains functional group comprises and is selected from least a in polyester resin, polyamide-based resin, polycarbonate resin, polyurethanes resin, polyhenylene ether resin and the polyformaldehyde resin,

5. flame-retardant polymer composition, it comprises

The modified block copolymer of the claim 1 of 100 weight parts (I),

The mineral filler of 10～2000 weight parts (VI), and

The olefin polymer of 0～1000 weight part.

6. flame-retardant polymer composition, it comprises the polymer composition of the claim 2 of 100 weight parts, and the mineral filler of 10～2000 weight parts (VI).

7. crosslinked, it is by mediating acquisition with the bridging property material melts in the presence of vulcanizing agent, and wherein the bridging property material comprises:

Total amount with respect to composition (I) and composition (II) is the modified block copolymer composition (I) of the claim 1 of 10～100 weight %, and

8. binder composition comprises:

The modified block copolymer of the claim 1 of 100 weight parts (I), and the tackifier of 20～400 weight parts (VIII).

9. surface protection binder film, it obtains by form binder layer on resin molding, and wherein binder layer comprises binder composition, and described binder composition comprises:

The modified block copolymer of the claim 1 of 100 weight parts (I), and the tackifier of 3～200 weight parts (VIII).

10. bituminous composition, it comprises:

0.5 the modified block copolymer of the claim 1 of～50 weight parts (I), and the pitch of 100 weight parts (IX).

11. drainage road, it comprises the drainage road layer that hole is used in a plurality of drainings that has of road and formation thereon, and this drainage road layer comprises multiple gathering materials and binding agent, and this binding agent comprises the bituminous composition of claim 10.

12. the drainage road of claim 11, wherein the porosity of this drainage road layer is 5～35%.

13. the method for the modified block copolymer of preparation claim 1, it comprises

(1) provide modified block copolymer one time, it comprises:

This modified block copolymer prepares by following method: prepare the basic segmented copolymer with active end by active anionic polymerization, with by making the properties-correcting agent containing functional group and the activity end addition bonding of this basis segmented copolymer, obtain one time modified block copolymer, not necessarily, subsequently with this partly or completely hydrogenation of modified block copolymer, wherein this modified block copolymer represent with the formula of following formula (10) and

(2) make modified block copolymer and be used to form the twice-modified dose of basic X that appears in the claim 1 ¹Twice-modified dose of reaction, wherein this twice-modified dose have can with the functional group of the functional group reactions of a properties-correcting agent base of this modified block copolymer, wherein this usage quantity of twice-modified dose is 0.3～10 mole with respect to the functional group of a properties-correcting agent base of 1 normal this modified block copolymer

Thereby obtained second-order modified block copolymer,

(10) E ²—F ²

E ²The unit that representative is represented with following formula (g-1),

(g—1) —R ⁹—P ¹

(h—1) —NH—R ¹⁰—Si(OR ¹¹) ₃

In formula (g-1)～formula (j-1),

P ¹Represent basic segmented copolymer,

R ⁹～R ¹⁰And R ¹³～R ¹⁵Represent C respectively independently _1-48Alkylidene group,

Wherein, R ⁹～R ¹⁰And R ¹³～R ¹⁵Not necessarily have the group, the C that are selected from hydroxyl, epoxy group(ing), amino, silane independently of one another _1-24At least a functional group of alkoxysilane groups,

R ¹²The expression hydrogen atom, C _1-48Alkyl, C _6-48Aryl, by C _1-48Moieties and C _6-48The alkaryl formed of aryl moiety, by C _1-48Moieties and C _6-48The aralkyl formed of aryl moiety, perhaps C _3-48Cycloalkyl,

Wherein, R ⁹～R ¹⁵Not necessarily have at least a atom that is selected from Sauerstoffatom, nitrogen-atoms, sulphur atom and Siliciumatom that is bonded on it independently of one another, described at least a atom is to be different from the mode bonding of hydroxyl, epoxy group(ing), amino, silanol and alkoxysilane groups.

14. the method for claim 13 wherein, in (1), after a properties-correcting agent addition that contains functional group is bonded to the activity end of basic segmented copolymer, also makes modified block copolymer obtaining and contains compound bearing active hydrogen and react,

Wherein, when carrying out the nonessential hydrogenation of this modified block copolymer, contain being reflected at before the hydrogenation or carrying out simultaneously of compound bearing active hydrogen with hydrogenation with this.