JPH11286526A - Thermoplastic block copolymer - Google Patents
Thermoplastic block copolymerInfo
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- JPH11286526A JPH11286526A JP10420998A JP10420998A JPH11286526A JP H11286526 A JPH11286526 A JP H11286526A JP 10420998 A JP10420998 A JP 10420998A JP 10420998 A JP10420998 A JP 10420998A JP H11286526 A JPH11286526 A JP H11286526A
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- hydrogenation
- block copolymer
- molecular weight
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱可塑性ブロック
共重合体に関する。さらに詳しくは、特定のブロック共
重合体の不飽和オレフィン部及び芳香環を水素添加し、
且つ水素添加反応時の数平均分子量減少がほとんどない
分子量分布の小さい熱可塑性水素添加ブロック共重合体
であって、強度、耐熱性、成型加工性に極めて優れてい
ることを特徴とする熱可塑性ブロック共重合体に関す
る。[0001] The present invention relates to a thermoplastic block copolymer. More specifically, hydrogenating the unsaturated olefin portion and the aromatic ring of the specific block copolymer,
A thermoplastic hydrogenated block copolymer having a small molecular weight distribution with little decrease in the number average molecular weight during the hydrogenation reaction, and having extremely excellent strength, heat resistance, and moldability. It relates to a copolymer.
【０００２】[0002]
【従来の技術】ビニル芳香族炭化水素化合物及び共役ジ
エン化合物からなるブロック共重合体は、従来より、弾
性材料、樹脂改質、粘接着剤、透明樹脂等の分野で広く
利用されており、また近年、共役ジエン部の二重結合を
水素添加し、飽和型とすることで耐熱性を向上せしめた
水素添加ブロック共重合体も、樹脂改質材、成型材料等
広範囲に使用されている。特にビニル芳香族炭化水素化
合物として、スチレン系化合物、共役ジエン化合物とし
てブタジエン、イソプレン系化合物からなるブロック共
重合体及びそのジエン部を水素添加せしめたブロック共
重合体は、エラストマーとしては、その耐熱性、耐候
性、強度、柔軟性が、樹脂としては、その透明性、耐衝
撃性が優れており、各種材料に使用されている。2. Description of the Related Art Block copolymers composed of a vinyl aromatic hydrocarbon compound and a conjugated diene compound have been widely used in the fields of elastic materials, resin modification, adhesives, transparent resins, and the like. In recent years, hydrogenated block copolymers having improved heat resistance by hydrogenating the double bond of a conjugated diene portion to form a saturated type have also been widely used in resin modifiers, molding materials and the like. Particularly, a block copolymer comprising a styrene compound as a vinyl aromatic hydrocarbon compound, butadiene as a conjugated diene compound and an isoprene compound, and a block copolymer obtained by hydrogenating the diene portion thereof have the heat resistance as an elastomer. The resin is excellent in transparency, impact resistance and weather resistance, strength and flexibility, and is used for various materials.
【０００３】また、これらのスチレン系ブロック共重合
体及びその水素添加重合体に熱可塑性樹脂等をブレンド
させたブロック共重合体組成物はさらなる耐熱性、流動
性、粘着特性等の諸物性を改良するものとして、広く実
施されている。しかし、近年、高分子材料に対する市場
要求は益々高度になってきており、耐熱性をより高めつ
つ、且つ成型加工性を向上させることが強く望まれてい
る。このような要求に対しては従来のスチレン−共役ジ
エンブロック共重合体では到底満たすことは困難であ
り、そのジエン部を水素添加せしめたブロック共重合体
にしても同様で、高温下の物性低下が著しく、また物性
向上のために分子量を増大させた場合、流動性が極めて
低くなり、成型加工性の大幅な低下を招くものであっ
た。Further, a block copolymer composition obtained by blending a thermoplastic resin or the like with these styrene-based block copolymers and hydrogenated polymers thereof further improves various physical properties such as heat resistance, fluidity and adhesive properties. This is widely practiced. However, in recent years, the market requirements for polymer materials have become increasingly sophisticated, and it is strongly desired to improve the heat resistance and improve the moldability. Conventional styrene-conjugated diene block copolymers are difficult to meet such demands at all, and the same applies to block copolymers in which the diene portion has been hydrogenated. When the molecular weight was increased in order to improve the physical properties, the flowability was extremely low, and the molding processability was greatly reduced.
【０００４】そこで、耐熱性の大幅な向上のために、ス
チレンの芳香環をも水素添加し、Ｔｇを高める手法が考
えられ、既に幾つかの検討がなされている。例えば、米
国特許第３３３３０２４号明細書には比較的低分子量の
スチレン−イソプレン−スチレンブロック共重合体のス
チレン芳香環及び不飽和オレフィン部を水素添加した実
施例が記載されているが、高分子量ブロック共重合体の
例はなく、また、記載されている水素添加方法では反応
時分子鎖切断が生じるため得られるブロック共重合体は
物性の低下したものとなる。[0004] In order to greatly improve the heat resistance, a method of increasing the Tg by hydrogenating the aromatic ring of styrene has also been considered, and some studies have already been made. For example, U.S. Pat. No. 3,333,024 describes an example in which a styrene aromatic ring and an unsaturated olefin moiety of a styrene-isoprene-styrene block copolymer having a relatively low molecular weight are hydrogenated. There is no example of a copolymer, and in the hydrogenation method described, molecular chain scission occurs during the reaction, so that the obtained block copolymer has reduced physical properties.
【０００５】さらに、米国特許第５３５２７４４号明細
書、ＷＯ９６／３４８９６号明細書には、比較的低分子
量のスチレン−イソプレン−スチレンブロック共重合体
のスチレン芳香環及び不飽和オレフィン部を水素添加す
る方法が記載され、スチレンブロック部のＴｇ向上を確
認している。しかしながら、これらの特許明細書には、
特に高分子量のエラストマーの記載がなく、また水素添
加前のスチレンブロックの分子量も低く耐熱性向上効果
も本発明の程度ではない。Further, US Pat. Nos. 5,352,744 and WO 96/34896 disclose a method of hydrogenating a styrene aromatic ring and an unsaturated olefin moiety of a styrene-isoprene-styrene block copolymer having a relatively low molecular weight. And the improvement in Tg of the styrene block portion was confirmed. However, in these patent specifications,
In particular, there is no description of a high molecular weight elastomer, the molecular weight of the styrene block before hydrogenation is low, and the effect of improving heat resistance is not at the level of the present invention.
【０００６】またさらに、特開平３−１６００５１号公
報には、高スチレン含有率のスチレン−ブタジエンブロ
ック共重合体のスチレン芳香環及び不飽和オレフィン部
を水素添加し、耐熱性を向上せしめ、光学材料への展開
を行っている旨が記載されているが、記載されている水
素添加方法では反応時の分子鎖切断が激しく、反応後の
数平均分子量減少率が１０％を大きく上回り、得られた
ブロック共重合体の強度等の物性向上は小さい。いずれ
にしても現状では、より高い耐熱性と成型加工性をあわ
せもつブロック共重合体は得られておらず、また特に弾
性にも優れる高分子量エラストマーにいたっては、まっ
たく得られていないのが実状である。Further, Japanese Patent Application Laid-Open No. Hei 3-160051 discloses that an styrene aromatic ring and an unsaturated olefin portion of a styrene-butadiene block copolymer having a high styrene content are hydrogenated to improve heat resistance and to improve the optical material. However, in the hydrogenation method described, the molecular chain was severely cut during the reaction, and the number-average molecular weight reduction rate after the reaction greatly exceeded 10%. Improvement of physical properties such as strength of the block copolymer is small. In any case, at present, block copolymers having both higher heat resistance and moldability have not been obtained, and high-molecular-weight elastomers with particularly excellent elasticity have not been obtained at all. It is a fact.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記従来技術
の状況に鑑み、耐熱性、成型加工性に優れ、且つ強度等
の物性に優れる熱可塑性ブロック共重合体を提供するも
のである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has as its object to provide a thermoplastic block copolymer which is excellent in heat resistance, molding workability and physical properties such as strength.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するため
に、本発明者らは鋭意検討を重ねた結果、特定の構造を
有するビニル芳香族炭化水素化合物−共役ジエン化合物
ブロック共重合体の芳香環及び不飽和オレフィン部が高
度に水素添加され、且つ水素添加反応時分子鎖切断のな
いブロック共重合体が、耐熱性が向上するうえにさらに
極めて流動性が高く成型加工性に優れ、且つ極めて高強
度となることを見出した。さらに驚くべきことに、ビニ
ル芳香族炭化水素化合物含有率５０％以下の数平均分子
量２００，０００を超える高分子量ブロック共重合体で
も十分な成型加工性を示すことを見出し本発明を完成し
た。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and as a result, have found that the aromatic copolymer of a vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer having a specific structure has A block copolymer in which the ring and unsaturated olefin moieties are highly hydrogenated, and which has no molecular chain breakage during the hydrogenation reaction, has improved heat resistance and has extremely high fluidity and excellent molding processability, and is extremely excellent. It was found that the strength was high. More surprisingly, the present inventors have found that even a high molecular weight block copolymer having a vinyl aromatic hydrocarbon compound content of 50% or less and a number average molecular weight of more than 200,000 shows sufficient moldability, and completed the present invention.
【０００９】即ち本発明は、一般式 （Ａ−Ｂ）n −Ａ、（Ａ−Ｂ）n+1 、（Ａ−Ｂ）n+1 −
Ｘ、｛（Ａ−Ｂ）n+1 ｝m −Ｘ （式中、Ａは水素添加されたビニル芳香族炭化水素化合
物を主体とする重合体ブロック、Ｂは水素添加された共
役ジエン化合物を主体とする重合体ブロック、Ｘは多官
能性のカップリング剤残基、ｎ及びｍは１以上の整数で
ある。）で表され、重合体ブロックＡ中の水素添加前の
ビニル芳香族炭化水素化合物重合体の数平均分子量が１
４，０００を超え、またＮＭＲ測定によって得られる水
素添加率が、全芳香環の少なくとも８０％以上、全オレ
フィン性不飽和二重結合の少なくとも９０％以上であ
り、且つ水素添加反応後の数平均分子量減少率が１０％
未満であるブロック共重合体であって、水素添加前の共
重合体中のビニル芳香族炭化水素化合物と共役ジエン化
合物との重量比が１０／９０〜９０／１０である熱可塑
性ブロック共重合体である。That is, the present invention relates to the general formulas (AB) n -A, (AB) n + 1 , (AB) n + 1-
X, {(AB) n + 1 } m- X (where A is a polymer block mainly composed of a hydrogenated vinyl aromatic hydrocarbon compound, and B is mainly composed of a hydrogenated conjugated diene compound) X is a polyfunctional coupling agent residue, and n and m are integers of 1 or more.), And a vinyl aromatic hydrocarbon compound in the polymer block A before hydrogenation. Number average molecular weight of the polymer is 1
The hydrogenation rate obtained by NMR measurement is at least 80% or more of all aromatic rings, at least 90% or more of all olefinically unsaturated double bonds, and the number average after hydrogenation reaction is more than 4,000. 10% reduction in molecular weight
Is a block copolymer having a weight ratio of a vinyl aromatic hydrocarbon compound to a conjugated diene compound in the copolymer before hydrogenation of from 10/90 to 90/10. It is.
【００１０】以下本発明を詳細に説明する。本発明は、
特定の構造を有するビニル芳香族炭化水素化合物−共役
ジエン化合物ブロック共重合体の芳香環及び不飽和オレ
フィン部が水素添加され、且つ水素添加反応時に分子鎖
切断が実質的にない熱可塑性ブロック共重合体である。
本発明は該ブロック共重合体中の水素添加前のビニル芳
香族炭化水素化合物重合体の数平均分子量が１４，００
０を超えるものであって、それ以下の分子量である場
合、ブロック共重合体は耐熱性向上の程度が低いものと
なる。また、本発明は水素添加反応後の数平均分子量減
少率が１０％未満のブロック共重合体であって、数平均
分子量減少率が１０％を超えるものは分子鎖切断が激し
く生じており、強度、弾性等が低いものとなる。Hereinafter, the present invention will be described in detail. The present invention
Thermoplastic block copolymer in which the aromatic ring and unsaturated olefin moiety of the vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer having a specific structure are hydrogenated and the molecular chain is substantially not broken during the hydrogenation reaction. It is united.
In the present invention, the number average molecular weight of the vinyl aromatic hydrocarbon compound polymer before hydrogenation in the block copolymer is 14,00.
When the molecular weight is more than 0 and is less than 0, the degree of improvement in heat resistance of the block copolymer is low. Further, the present invention relates to a block copolymer having a number average molecular weight reduction rate of less than 10% after the hydrogenation reaction, and a block copolymer having a number average molecular weight reduction rate of more than 10% has severely broken molecular chains, , Elasticity and the like are low.
【００１１】以下本発明をさらに詳細に説明する。本発
明のブロック共重合体は水素添加されたビニル芳香族炭
化水素化合物を主体とする重合体ブロックＡと水素添加
された共役ジエン化合物を主体とする重合体ブロックＢ
とから構成されるものである。ビニル芳香族炭化水素化
合物としては、例えばスチレン、α−メチルスチレン、
ｐ−メチルスチレン、ｐ−ターシャルブチルスチレン等
のアルキルスチレン、パラメトキシスチレン、ビニルナ
フタレン等のうちから１種または２種以上が選ばれ、中
でもスチレンが好ましい。Hereinafter, the present invention will be described in more detail. The block copolymer of the present invention comprises a polymer block A mainly composed of a hydrogenated vinyl aromatic hydrocarbon compound and a polymer block B mainly composed of a hydrogenated conjugated diene compound.
It is composed of Examples of the vinyl aromatic hydrocarbon compound include styrene, α-methylstyrene,
One or more kinds are selected from alkylstyrenes such as p-methylstyrene and p-tert-butylstyrene, paramethoxystyrene, vinylnaphthalene and the like, and styrene is particularly preferred.
【００１２】また、本発明においては、ビニル芳香族炭
化水素化合物を主体とする重合体とは、ビニル芳香族炭
化水素化合物の１種または２種以上からなる場合、もし
くはこれらとリビングアニオン重合する他の化合物が共
重合されている場合も含まれる。これら共重合可能な化
合物としては、共役ジエン化合物、メチルメタクリレー
ト、ブチルメタクリレート等のメタクリル酸エステル、
シクロヘキサジエン、カプロラクトン等があげられる。
共重合の形態としては、ランダム、交互、テーパー等い
かなる形態でもよく、また重合体ブロックＡが複数個あ
る場合はそれぞれの組成、分子量等が異なってもよい。In the present invention, the polymer mainly composed of a vinyl aromatic hydrocarbon compound refers to a case in which one or more vinyl aromatic hydrocarbon compounds are used, or a polymer which is subjected to living anion polymerization with these compounds. The case where the compound of (1) is copolymerized is also included. Examples of these copolymerizable compounds include conjugated diene compounds, methyl methacrylate, methacrylates such as butyl methacrylate,
Cyclohexadiene, caprolactone and the like can be mentioned.
The form of copolymerization may be any form such as random, alternating, or tapered, and when there are a plurality of polymer blocks A, the composition, molecular weight and the like of each may be different.
【００１３】また、本明細書中のビニル芳香族炭化水素
化合物を主体とするという意味は、水素添加されたビニ
ル芳香族炭化水素化合物が重合体ブロックＡ中、少なく
とも５０モル％以上、好ましくは７０モル％以上を占め
るということである。また、共役ジエン化合物として
は、例えばブタジエン、イソプレン、１，３−シクロヘ
キサジエン、１，３−ペンタジエン、２，３−ジメチル
−１，３−ブタジエン等のうちから１種または２種以上
が選ばれ、中でもブタジエン、イソプレン及びこれらの
組み合わせが好ましい。そして、水素添加される前の共
役ジエン化合物は、そのブロックにおけるミクロ構造を
任意に選ぶことができ、例えば、ポリブタジエンブロッ
クの場合は、側鎖の１，２結合量が１０モル％以上９０
モル％未満であることが好ましく、特に弾性材料用途と
しては２０モル％以上６０モル％未満が好ましい。[0013] The term "mainly composed of a vinyl aromatic hydrocarbon compound" in the present specification means that the hydrogenated vinyl aromatic hydrocarbon compound is at least 50 mol% or more, preferably 70 mol% or more, in the polymer block A. More than mol%. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-cyclohexadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, butadiene, isoprene and a combination thereof are preferred. The microstructure of the conjugated diene compound before hydrogenation can be arbitrarily selected. For example, in the case of a polybutadiene block, the amount of 1,2 bonds in the side chain is 10 mol% or more and 90 mol% or more.
It is preferable that it is less than 20 mol%, and especially for elastic material use, it is preferably 20 mol% or more and less than 60 mol%.
【００１４】また、本発明においては、共役ジエン化合
物を主体とする重合体とは、共役ジエン化合物とリビン
グアニオン重合する他の化合物が共重合されている場合
も含まれる。これら共重合可能な他の化合物としては、
ビニル芳香族炭化水素化合物、メチルメタクリレート、
ブチルメタクリレート等のメタクリル酸エステル、シク
ロヘキサジエン、カプロラクトン等があげられる。共重
合の形態としては、ランダム、交互、テーパー等いかな
る形態でもよく、また、重合体ブロックＢが複数個ある
場合はそれぞれの組成、分子量等が異なってもよい。In the present invention, the polymer mainly composed of a conjugated diene compound also includes a case where another compound capable of living anionic polymerization with the conjugated diene compound is copolymerized. These other copolymerizable compounds include:
Vinyl aromatic hydrocarbon compound, methyl methacrylate,
Examples include methacrylates such as butyl methacrylate, cyclohexadiene, caprolactone, and the like. The form of copolymerization may be any form such as random, alternating, or tapered, and when there are a plurality of polymer blocks B, the composition, molecular weight, etc. of each may be different.
【００１５】また、本明細書中の共役ジエン化合物を主
体とするという意味は水素添加された共役ジエン化合物
が重合体ブロックＢ中、少なくとも５０モル％以上、好
ましくは７０モル％以上を占めるということである。本
発明において重合体ブロックＡに含まれる水素添加され
る前のビニル芳香族炭化水素化合物重合体の数平均分子
量は１４，０００を超えるものである。１４，０００以
下であると、芳香環水素添加後のＴｇが低く、高温下の
強度等耐熱性の改良効果が低く市場要求を満たすものと
はならない。また、分子量の上限は特にないが、５０
０，０００を超えると、耐熱性改良効果は十分である
が、成型加工性等に問題が生じる場合がある。Further, in the present specification, the meaning of mainly comprising a conjugated diene compound means that the hydrogenated conjugated diene compound accounts for at least 50 mol% or more, preferably 70 mol% or more in the polymer block B. It is. In the present invention, the number average molecular weight of the vinyl aromatic hydrocarbon compound polymer before hydrogenation contained in the polymer block A is more than 14,000. If it is 14,000 or less, the Tg after hydrogenation of the aromatic ring is low, and the effect of improving heat resistance such as strength at a high temperature is low, so that it does not satisfy market requirements. Although there is no particular upper limit for the molecular weight,
If it exceeds 000, the effect of improving heat resistance is sufficient, but problems may occur in molding workability and the like.
【００１６】本発明のブロック共重合体のポリスチレン
換算の数平均分子量は３５，０００以上であることが好
ましい。分子量の上限は特にないが６００，０００以下
が好ましく、さらに好適な分子量は５０，０００以上４
００，０００以下であることが望ましい。３５，０００
以下であると、強度、弾性が小さく、また、６００，０
００を超えると耐熱性改良効果は十分であるが、成型加
工性等に問題が生じる場合がある。The block copolymer of the present invention preferably has a number average molecular weight in terms of polystyrene of 35,000 or more. Although there is no particular upper limit for the molecular weight, it is preferably 600,000 or less, and more preferably 50,000 or more.
Desirably, it is not more than 00,000. 35,000
When it is below, strength and elasticity are small, and 600,0
When it exceeds 00, the effect of improving heat resistance is sufficient, but problems may occur in molding workability and the like.
【００１７】本発明におけるブロック共重合体の構造
は、例えば、線状、分岐状、放射状、櫛形状あるいはこ
れらの混合物などいかなる形態であっても構わない。好
ましい構造としては、Ａ−Ｂ−Ａ、Ａ−Ｂ−Ａ−Ｂ、
（Ａ−Ｂ）4 −Ｘなどがあげられる。また、これらにＡ
−Ｂ構造のブロック共重合体が含まれていてもよい。ま
た、各ブロックの境界がランダム共重合体となりしかも
その組成が徐々に変わっていくテーパードブロック共重
合体も含まれる。The structure of the block copolymer in the present invention may be in any form such as linear, branched, radial, comb-shaped or a mixture thereof. Preferred structures include ABA, ABAB,
(AB) 4- X and the like. In addition, A
A block copolymer having a -B structure may be contained. Further, a tapered block copolymer in which the boundary between each block becomes a random copolymer and its composition gradually changes is also included.
【００１８】本発明の水素添加前のブロック共重合体中
に含まれるビニル芳香族炭化水素化合物と共役ジエン化
合物との重量比は１０／９０〜９０／１０の間で任意に
選ばれる。ビニル芳香族炭化水素化合物含有量が１０％
未満であると、耐熱性の改良効果が得られず、９０％を
超えると耐衝撃性の低いものとなり好ましくない。ま
た、特に弾性材料用途としては該重量比が１０／９０〜
５０／５０であると耐熱性、強度、成型加工性及び、弾
性とのバランスに優れるものとなるが、さらに好ましく
は、２０／８０〜４０／６０が弾性材料として優れる。The weight ratio of the vinyl aromatic hydrocarbon compound to the conjugated diene compound contained in the block copolymer of the present invention before hydrogenation is arbitrarily selected between 10/90 and 90/10. 10% vinyl aromatic hydrocarbon compound content
If it is less than 90%, the effect of improving heat resistance cannot be obtained, and if it exceeds 90%, impact resistance becomes low, which is not preferable. In particular, for elastic materials, the weight ratio is 10/90 to
When the ratio is 50/50, the balance between heat resistance, strength, moldability and elasticity is excellent, but more preferably, 20/80 to 40/60 is excellent as an elastic material.
【００１９】本発明のブロック共重合体は、全芳香環の
うち８０％以上、好ましくは９０％以上が水素添加さ
れ、且つ全オレフィン性不飽和二重結合のうち９０％以
上、好ましくは９５％以上が水素添加されたものであ
る。全オレフィン性不飽和二重結合の水素添加率が９０
％未満であると、熱、光などによる劣化が激しく、熱可
塑性の低下、物性の低下を招く。一方、全芳香環の水素
添加率が８０％未満であると、Ｔｇが低く、耐熱性、強
度が劣り、また成型加工性にも劣るものとなる。水素添
加率はＮＭＲによって測定できる。The block copolymer of the present invention is obtained by hydrogenating at least 80%, preferably at least 90%, of all aromatic rings, and at least 90%, preferably at least 95%, of all olefinically unsaturated double bonds. The above is the result of hydrogenation. Hydrogenation rate of all olefinically unsaturated double bonds is 90
%, Deterioration by heat, light, etc. is severe, leading to a decrease in thermoplasticity and physical properties. On the other hand, when the hydrogenation rate of the wholly aromatic ring is less than 80%, Tg is low, heat resistance and strength are poor, and moldability is poor. The hydrogenation rate can be measured by NMR.
【００２０】また、本発明のブロック共重合体は、水素
添加反応後の数平均分子量減少率が１０％未満でなけれ
ばならない。好ましくは５％未満、さらに好ましくは３
％未満である。水素添加反応後の数平均分子量減少率が
１０％以上の場合、水素添加反応時に分子鎖切断が激し
く生じているため、物性の低下、殊に強度、永久伸び等
の弾性的性質の低下が激しく、もはや本発明のような効
果は全く得られないものとなる。水素添加反応後の数平
均分子量減少率はゲルパーミエーションクロマトグラフ
ィー（ＧＰＣ）法によって測定できる。The block copolymer of the present invention must have a number-average molecular weight reduction rate of less than 10% after the hydrogenation reaction. Preferably less than 5%, more preferably 3%
%. When the number-average molecular weight reduction rate after the hydrogenation reaction is 10% or more, the molecular chains are severely cut during the hydrogenation reaction, and the physical properties, particularly the strength and the elastic properties such as permanent elongation, are significantly reduced. Thus, the effect of the present invention can no longer be obtained. The number-average molecular weight reduction after the hydrogenation reaction can be measured by gel permeation chromatography (GPC).
【００２１】水素添加前のブロック共重合体の製造方法
としては例えば特公昭３６−１９２８６号公報、特公昭
４３ー１４９７９号公報、特公昭４９−３６９５７号公
報などに記載された方法があげられる。これらは炭化水
素溶媒中でアニオン重合開始剤として有機リチウム化合
物等を用い、ジエチルエーテル、テトラヒドロフラン等
のエーテル化合物、トリエチルアミン、テトラメチルエ
チレンジアミン等の第３級アミンなどを添加し、共役ジ
エン化合物ブロックの側鎖結合量、結合様式を制御し、
また、必要に応じてカップリング剤として、エポキシ化
ダイズ油、四塩化ケイ素等の多官能性化合物を用い、ビ
ニル芳香族炭化水素化合物と共役ジエン化合物をブロッ
ク共重合する方法であり、直鎖状、分岐状、あるいは放
射状の構造を有する水素添加前のブロック共重合体が得
られる。Examples of the method for producing the block copolymer before hydrogenation include the methods described in JP-B-36-19286, JP-B-43-14979, and JP-B-49-36957. These use an organolithium compound or the like as an anionic polymerization initiator in a hydrocarbon solvent, add an ether compound such as diethyl ether or tetrahydrofuran, or a tertiary amine such as triethylamine or tetramethylethylenediamine to the side of the conjugated diene compound block. Controls the amount of chain binding and the binding mode,
In addition, if necessary, a polyfunctional compound such as epoxidized soybean oil or silicon tetrachloride is used as a coupling agent, and a vinyl aromatic hydrocarbon compound and a conjugated diene compound are block-copolymerized. A block copolymer before hydrogenation having a branched or radial structure is obtained.
【００２２】ブロック共重合体の水素添加方法として
は、ブロック共重合体中の共役ジエン化合物のオレフィ
ン性二重結合とビニル芳香族炭化水素化合物の芳香環を
一段で水素添加する方法が用いられる。例えば炭化水素
溶媒中、アルミナ担体に担持したＰｄ、Ｒｈ等の金属触
媒を、ブロック共重合体に対し１重量％〜１００重量％
添加し、反応温度を１２０℃〜２５０℃、好ましくは１
３０℃〜２２０℃で、水素分圧２ＭＰａ〜２５ＭＰａ、
好ましくは３ＭＰａ〜２０ＭＰａで反応させる方法が用
いられる。また、反応終了後は、公知の方法で触媒の分
離を行い、触媒をリサイクルさせることが好ましい。ま
た、ブロック共重合体中の共役ジエン化合物のオレフィ
ン性二重結合をまず公知の方法で水素添加し、その後ビ
ニル芳香族炭化水素化合物の芳香環を上記の方法で水素
添加するという二段階の水素添加方法でもよい。しかし
ながら、プロセスの簡便さ、生産性等を考慮すると、一
段反応がより好ましい。As a method for hydrogenating the block copolymer, a method is used in which the olefinic double bond of the conjugated diene compound and the aromatic ring of the vinyl aromatic hydrocarbon compound in the block copolymer are hydrogenated in one step. For example, in a hydrocarbon solvent, a metal catalyst such as Pd or Rh supported on an alumina carrier is added in an amount of 1% to 100% by weight based on the weight of the block copolymer.
And the reaction temperature is from 120 ° C. to 250 ° C., preferably 1 ° C.
30 ° C. to 220 ° C., hydrogen partial pressure 2 MPa to 25 MPa,
Preferably, a method of reacting at 3 MPa to 20 MPa is used. After completion of the reaction, it is preferable to separate the catalyst by a known method and to recycle the catalyst. In addition, a two-stage hydrogenation method in which the olefinic double bond of the conjugated diene compound in the block copolymer is first hydrogenated by a known method, and then the aromatic ring of the vinyl aromatic hydrocarbon compound is hydrogenated by the above method. The addition method may be used. However, considering the simplicity of the process, the productivity and the like, the one-step reaction is more preferable.
【００２３】本発明のブロック共重合体は必要に応じて
無機充填剤、安定剤、滑剤、着色剤、シリコンオイル、
ミネラルオイル、難燃剤等を添加することができる。無
機充填剤としては、例えば炭酸カルシウム、炭酸マグネ
シウム、タルク、水酸化マグネシウム、マイカ、硫酸バ
リウム、ホワイトカーボン、酸化チタン、カーボンブラ
ック等があげられる。安定剤としては、ヒンダードフェ
ノール系酸化防止剤、りん系熱安定剤、ヒンダードアミ
ン系光安定剤、ベンゾトリアゾール系ＵＶ吸収剤等があ
げられる。滑剤としては、ステアリン酸、ステアリン酸
エステル、ステアリン酸アミド、ステアリン酸金属塩な
どがあげられる。ミネラルオイルとしては、パラフィン
成分、ナフテン成分、アロマ成分が任意の割合で用いる
ことができる。上記各成分と本発明のブロック共重合体
とを混合する場合、例えばバンバリーミキサー、ラボプ
ラストミル、単軸押出機、二軸押出機等いずれの混練装
置を使用してもよい。The block copolymer of the present invention may contain, if necessary, an inorganic filler, a stabilizer, a lubricant, a coloring agent, silicone oil,
Mineral oil, flame retardants and the like can be added. Examples of the inorganic filler include calcium carbonate, magnesium carbonate, talc, magnesium hydroxide, mica, barium sulfate, white carbon, titanium oxide, and carbon black. Examples of the stabilizer include a hindered phenol-based antioxidant, a phosphorus-based heat stabilizer, a hindered amine-based light stabilizer, and a benzotriazole-based UV absorber. Examples of the lubricant include stearic acid, stearic acid ester, stearic acid amide, metal stearate and the like. As the mineral oil, a paraffin component, a naphthene component, and an aroma component can be used in an arbitrary ratio. When mixing the above components with the block copolymer of the present invention, any kneading apparatus such as a Banbury mixer, a Labo Plastomill, a single screw extruder, and a twin screw extruder may be used.
【００２４】[0024]
【発明の実施の形態】以下、実施例により本発明を具体
的に説明するが、本発明はこれらの例のみによって何ら
制限されるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
【実施例】（ブロック共重合体の分析及び物性評価方
法） ブロック共重合体のスチレン含有量の定量：紫外分光光
度計を用い、ブロック共重合体のクロロホルム溶液の吸
光度を測定し、スチレン量と吸光度の関係をあらかじめ
測定した検量線から、ブロック共重合体中のスチレン含
有量を求めた。[Example] (Method of analysis of block copolymer and evaluation of physical properties) Determination of styrene content of block copolymer: Using a UV spectrophotometer, the absorbance of a chloroform solution of the block copolymer was measured, and the styrene content was determined. The styrene content in the block copolymer was determined from a calibration curve in which the relationship between absorbances was measured in advance.
【００２５】ブロック共重合体の分子量及び水素添加前
のスチレンブロック鎖長：ゲルパーミエイションクロマ
トグラフィー（ＧＰＣ）法により、市販のＧＰＣ検量線
作成用の標準ポリスチレンを用い算出した。水素添加前
のスチレンブロック鎖長は、水素添加前のブロック共重
合体をクロロホルム中でオスミウム酸分解を行って得た
スチレンブロックをＧＰＣ法で測定した。 ブロック共重合体の水素添加率：Ｈ−ＮＭＲスペクトル
より測定した。 メルトフローレート（ＭＦＲ）：ＪＩＳ Ｋ７２１０に
準拠し、２．１６ｋｇ荷重、２３０℃の条件で測定し
た。Molecular weight of block copolymer and styrene block chain length before hydrogenation: Calculated by gel permeation chromatography (GPC) using commercially available standard polystyrene for preparing a GPC calibration curve. The styrene block chain length before hydrogenation was measured by a GPC method on a styrene block obtained by subjecting a block copolymer before hydrogenation to osmate decomposition in chloroform. Hydrogenation rate of block copolymer: measured from H-NMR spectrum. Melt flow rate (MFR): Measured under the conditions of 2.16 kg load and 230 ° C. according to JIS K7210.
【００２６】硬度：ＪＩＳ Ｋ６３０１、Ａタイプによ
り測定した。 破断強度、伸度：ＪＩＳ Ｋ６３０１に準拠し、試料は
２ｍｍ厚の圧縮成型シートを用い、試験片は３号ダンベ
ルとした。 永久伸び：ＪＩＳ Ｋ６３０１に準拠し、試料は２ｍｍ
厚の圧縮成型シートを用い、試験片は３号ダンベルと
し、１００％伸長後の残留歪みを測定した。 反発弾性：ダンロップトリプソメーターにて測定した。
試料は４ｍｍ厚の圧縮成型シートを用いた。Hardness: Measured according to JIS K6301, A type. Breaking strength and elongation: Based on JIS K6301, a sample was a compression molded sheet having a thickness of 2 mm, and the test piece was a No. 3 dumbbell. Permanent elongation: According to JIS K6301, sample is 2mm
Using a thick compression molded sheet, the test piece was a No. 3 dumbbell, and the residual strain after 100% elongation was measured. Rebound resilience: measured with a Dunlop trypsometer.
The sample used was a compression molded sheet having a thickness of 4 mm.
【００２７】（ブロック共重合体の重合方法）窒素置換
した４０ｌのオートクレーブに乾燥、精製したシクロヘ
キサン２６ｌ、テトラヒドロフラン６５ｇ、スチレン６
２０ｇを仕込み、６０℃に昇温した後、ｎ−ブチルリチ
ウム２．７ｇを含むシクロヘキサン溶液を添加、重合を
開始、スチレンの重合が終了後、次いでブタジエンを１
９４０ｇ添加し、重合が完結した後さらにスチレン６２
０ｇを添加し、重合反応を完結させ、数平均分子量１０
６，０００、スチレン含有率３９％、スチレンブロック
鎖長１５，２００、ブタジエン部の側鎖が３２モル％の
トリブロック共重合体（ＳＢＳ）を得た（ブロック共重
合体Ａ−１）。(Method of polymerizing block copolymer) In a 40-liter autoclave purged with nitrogen, 26 l of purified and purified cyclohexane, 65 g of tetrahydrofuran, styrene 6
After charging 20 g, the temperature was raised to 60 ° C., a cyclohexane solution containing 2.7 g of n-butyllithium was added, polymerization was started, and after the polymerization of styrene was completed, butadiene was added in 1 part.
940 g was added, and after the polymerization was completed, styrene 62 was added.
0 g was added to complete the polymerization reaction, and the number average molecular weight was 10
A triblock copolymer (SBS) having a styrene content of 6,000, a styrene content of 39%, a styrene block chain length of 15,200, and a side chain of a butadiene portion of 32 mol% was obtained (block copolymer A-1).
【００２８】以下、テトラヒドロフラン、ｎ−ブチルリ
チウム、スチレン、ブタジエンの添加量を変更し、それ
以外は同様の手法で重合、また場合によってはスチレ
ン、ブタジエン、スチレン、ブタジエンを逐次重合した
テトラブロック共重合体等を表−１に示す種々の水素添
加前のブロック共重合体（Ａ−１〜Ａ−７）を得た。ま
た、窒素置換した４０Ｌのオートクレーブに乾燥、精製
したシクロヘキサン２６Ｌ、テトラヒドロフラン８８
ｇ、スチレン９９０ｇを仕込み、６０℃に昇温した後、
ｎ−ブチルリチウム３．５ｇを含むシクロヘキサン溶液
を添加、重合を開始、スチレン重合終了後、次いでブタ
ジエンを２２１０ｇ添加し、重合が完結した後、四塩化
ケイ素２．２ｇを添加し、カップリング反応を完結さ
せ、数平均分子量３２０，０００、スチレン含有率３１
％、スチレンブロック鎖長１６，９００、ブタジエン部
の側鎖が３８モル％で、ジブロック共重合体５％を含む
放射状トリブロック共重合体（（ＳＢ4 ）−Ｓｉ＋Ｓ
Ｂ、Ａ−８）を得た。Hereinafter, the amounts of tetrahydrofuran, n-butyllithium, styrene, and butadiene were changed, and polymerization was carried out in the same manner except for the above. In some cases, styrene, butadiene, styrene, and butadiene were successively polymerized. As a result, various block copolymers (A-1 to A-7) before hydrogenation shown in Table 1 were obtained. In a 40 L autoclave purged with nitrogen, 26 L of cyclohexane and 88 L of tetrahydrofuran were purified and dried.
g, 990 g of styrene, and the temperature was raised to 60 ° C.
A cyclohexane solution containing 3.5 g of n-butyllithium was added, polymerization was started, and after styrene polymerization was completed, 2210 g of butadiene was added. After the polymerization was completed, 2.2 g of silicon tetrachloride was added, and the coupling reaction was performed. Completed, number average molecular weight 320,000, styrene content 31
%, A styrene block chain length of 16,900, a side chain of a butadiene portion of 38 mol%, and a radial triblock copolymer ((SB 4 ) -Si + S) containing 5% of a diblock copolymer.
B, A-8).
【００２９】[0029]
【表１】 [Table 1]
【００３０】（実施例１）２ｌのオートクレーブ中に、
重合終了後、Ｌｉに対して１．２等量のメタノールを添
加して成長末端を停止させた１３．５重量％のブロック
共重合体Ａ−１のシクロヘキサン溶液を１２００ｇ仕込
み、エヌ・イー・ケムキャット社製の５％パラジウムア
ルミナ粉末（粒径２０ミクロン）を４８ｇ添加後、系内
を水素置換し、１８０℃に昇温し、水素圧８．３ＭＰ
ａ、６時間水素添加反応を行い、不飽和オレフィン部分
の水素添加率１００％、芳香環の水素添加率９９．４％
で、水素添加後のポリマーの数平均分子量が１０４，０
００で水素添加前に比較し数平均分子量減少率が１．９
％、分子量分布が１．０３である水素添加ブロック共重
合体を得た。Example 1 In a 2 l autoclave,
After completion of the polymerization, 1200 g of a 13.5% by weight cyclohexane solution of 13.5% by weight of the block copolymer A-1 in which the growth terminal was terminated by adding 1.2 equivalents of methanol to Li was added. After adding 48 g of 5% palladium alumina powder (particle diameter 20 microns) manufactured by the company, the inside of the system was replaced with hydrogen, the temperature was raised to 180 ° C., and the hydrogen pressure was 8.3 MPa.
a, A hydrogenation reaction was performed for 6 hours, and the hydrogenation rate of the unsaturated olefin portion was 100%, and the hydrogenation rate of the aromatic ring was 99.4%.
The number average molecular weight of the polymer after hydrogenation is 104,0
00, the number average molecular weight reduction rate was 1.9 compared to that before hydrogenation.
%, And a hydrogenated block copolymer having a molecular weight distribution of 1.03 was obtained.
【００３１】（実施例２）実施例１と同様の手法を用い
て、ブロック共重合体Ａ−２について水素添加反応を行
い、不飽和オレフィン部分の水素添加率は１００％、芳
香環の水素添加率は９９．２％、水素添加後のポリマー
の数平均分子量は１３８，０００で水素添加前に比較し
数平均分子量減少率が１．４％、分子量分布が１．０４
の水素添加ブロック共重合体を得た。Example 2 A hydrogenation reaction was carried out on the block copolymer A-2 using the same method as in Example 1, and the hydrogenation rate of the unsaturated olefin portion was 100%, and the hydrogenation of the aromatic ring was 100%. The ratio was 99.2%, the number average molecular weight of the polymer after hydrogenation was 138,000, and the number average molecular weight reduction rate was 1.4% and the molecular weight distribution was 1.04 compared to that before hydrogenation.
Was obtained.
【００３２】（実施例３）５％パラジウムアルミナ粉末
の量を９６ｇとした以外は実施例１と同様の手法を用い
て、ブロック共重合体Ａ−３について水素添加反応を行
い不飽和オレフィン部分の水素添加率は９９．８％、芳
香環の水素添加率は９９．３％、水素添加後のポリマー
の数平均分子量は２１７，０００で水素添加前に比較し
数平均分子量減少率が２．４％、分子量分布が１．０５
の水素添加ブロック共重合体を得た。Example 3 A block copolymer A-3 was subjected to a hydrogenation reaction using the same procedure as in Example 1 except that the amount of the 5% palladium alumina powder was changed to 96 g, to thereby obtain an unsaturated olefin portion. The hydrogenation rate was 99.8%, the hydrogenation rate of the aromatic ring was 99.3%, the number average molecular weight of the polymer after hydrogenation was 217,000, and the number average molecular weight reduction rate was 2.4 compared to that before hydrogenation. %, Molecular weight distribution is 1.05
Was obtained.
【００３３】（実施例４）実施例３と同様の手法を用い
て、ブロック共重合体Ａ−４について水素添加反応を行
い、不飽和オレフィン部分の水素添加率は９９．７％、
芳香環の水素添加率は９９．２％、水素添加後のポリマ
ーの数平均分子量は２２６，０００万で水素添加前に比
較し数平均分子量減少率が２．２％、分子量分布が１．
０５の水素添加ブロック共重合体を得た。Example 4 A block copolymer A-4 was subjected to a hydrogenation reaction in the same manner as in Example 3, and the hydrogenation rate of the unsaturated olefin portion was 99.7%.
The hydrogenation rate of the aromatic ring was 99.2%, the number average molecular weight of the polymer after hydrogenation was 226,000 million, and the number average molecular weight reduction rate was 2.2% and the molecular weight distribution was 1.20 compared to that before hydrogenation.
Thus, a hydrogenated block copolymer No. 05 was obtained.
【００３４】（実施例５）実施例３と同様の手法を用い
て、ブロック共重合体Ａ−８について水素添加反応を行
い、不飽和オレフィン部分の水素添加率９９．７％、芳
香環の水素添加率９９．２％で、水素添加後のポリマー
の数平均分子量が３１５，０００で水素添加前に比較し
数平均分子量減少率が１．６％、分子量分布が１．１１
である水素添加ブロック共重合体を得た。Example 5 A hydrogenation reaction was carried out on the block copolymer A-8 using the same method as in Example 3, and the hydrogenation rate of the unsaturated olefin portion was 99.7% and the hydrogen content of the aromatic ring was 9 At an addition rate of 99.2%, the number average molecular weight of the polymer after hydrogenation was 315,000, the number average molecular weight reduction rate was 1.6%, and the molecular weight distribution was 1.11 compared to before the hydrogenation.
Was obtained.
【００３５】（比較例１）実施例１と同様の手法を用い
て、ブロック共重合体Ａ−１について、１６０℃で４．
８時間水素添加反応を行い、不飽和オレフィン部分の水
素添加率が９９．４％、芳香環の水素添加率が６２．６
％の部分水素添加ブロック共重合体を得た。(Comparative Example 1) Using the same procedure as in Example 1, block copolymer A-1 was heated at 160 ° C. at 4.degree.
A hydrogenation reaction was performed for 8 hours, and the hydrogenation rate of the unsaturated olefin portion was 99.4%, and the hydrogenation rate of the aromatic ring was 62.6.
% Of partially hydrogenated block copolymer was obtained.
【００３６】（比較例２）実施例１と同様の手法を用い
て、ブロック共重合体Ａ−２について、１６０℃で３．
６時間水素添加反応を行い、不飽和オレフィン部分の水
素添加率が９９．３％、芳香環の水素添加率が４１．２
％の部分水素添加ブロック共重合体を得た。(Comparative Example 2) Using the same procedure as in Example 1, block copolymer A-2 was treated at 160 ° C. with 3.
A hydrogenation reaction was performed for 6 hours, and the hydrogenation rate of the unsaturated olefin portion was 99.3%, and the hydrogenation rate of the aromatic ring was 41.2%.
% Of partially hydrogenated block copolymer was obtained.
【００３７】（比較例３）５％パラジウムアルミナ粉末
に変えてエヌ・イー・ケムキャット社製の５％ルテニウ
ムアルミナ粉末（粒径２０ミクロン）を用いた以外は実
施例１と同様の手法を用いてブロック共重合体Ａ−２に
ついて水素添加反応を行い、不飽和オレフィン部分の水
素添加率１００％、芳香環の水素添加率９８．８％、水
素添加後のポリマーの数平均分子量が１２１，０００で
水素添加前に比較し数平均分子量減少率が１３．６％、
分子量分布１．２０の水素添加ブロック共重合体を得
た。(Comparative Example 3) The same procedure as in Example 1 was used except that 5% ruthenium alumina powder (particle size: 20 microns) manufactured by NE Chemcat was used instead of 5% palladium alumina powder. A hydrogenation reaction was performed on the block copolymer A-2, and the hydrogenation rate of the unsaturated olefin portion was 100%, the hydrogenation rate of the aromatic ring was 98.8%, and the number average molecular weight of the polymer after hydrogenation was 121,000. The number average molecular weight reduction rate is 13.6% compared to before hydrogenation,
A hydrogenated block copolymer having a molecular weight distribution of 1.20 was obtained.
【００３８】（比較例４）５％パラジウムアルミナ粉末
に変えて日産ガードラー社製６５％ニッケル珪藻土２０
０ｇを用いた以外は実施例１と同様の手法を用いてブロ
ック共重合体Ａ−−３にについて水素添加反応を行い、
不飽和オレフィン部分の水素添加率１００％、芳香環の
水素添加率９８．６％、水素添加後のポリマーの数平均
分子量が１７４，０００で水素添加前に比較し数平均分
子量減少率が２１．６％、分子量分布１．３１の水素添
加ブロック共重合体を得た。Comparative Example 4 Nissan Gardler Co., Ltd. 65% nickel diatomaceous earth 20 instead of 5% palladium alumina powder
A block copolymer A--3 was subjected to a hydrogenation reaction using the same method as in Example 1 except that 0 g was used,
The hydrogenation rate of the unsaturated olefin portion is 100%, the hydrogenation rate of the aromatic ring is 98.6%, the number average molecular weight of the polymer after hydrogenation is 174,000, and the number average molecular weight reduction rate is 21. A 6% hydrogenated block copolymer having a molecular weight distribution of 1.31 was obtained.
【００３９】（比較例５）実施例１と同様の手法を用い
て、ブロック共重合体Ａ−６について水素添加反応を行
い、不飽和オレフィン部分の水素添加率は１００％、芳
香環の水素添加率は９９．６％、水素添加後のポリマー
の数平均分子量は１００，５００で水素添加前に比較し
数平均分子量減少率が０．５％、分子量分布が１．０３
の水素添加ブロック共重合体を得た。Comparative Example 5 A block copolymer A-6 was subjected to a hydrogenation reaction in the same manner as in Example 1. The hydrogenation rate of the unsaturated olefin portion was 100%, and the hydrogenation of the aromatic ring was 100%. The ratio was 99.6%, the number average molecular weight of the polymer after hydrogenation was 100,500, and the number average molecular weight reduction rate was 0.5% and the molecular weight distribution was 1.03 compared to that before hydrogenation.
Was obtained.
【００４０】（比較例６）実施例１と同様の手法を用い
て、ブロック共重合体Ａ−７について水素添加反応を行
い、不飽和オレフィン部分の水素添加率は１００％、芳
香環の水素添加率は９９．６％、水素添加後のポリマー
の数平均分子量は１１４，０００で水素添加前に比較し
数平均分子量減少率が０．９％、分子量分布が１．０３
の水素添加ブロック共重合体を得た。本発明の物性評価
結果を表−２に示す。Comparative Example 6 A block copolymer A-7 was subjected to a hydrogenation reaction in the same manner as in Example 1. The hydrogenation rate of the unsaturated olefin portion was 100%, and the hydrogenation of the aromatic ring was 100%. The ratio was 99.6%, the number average molecular weight of the polymer after hydrogenation was 114,000, and the number average molecular weight reduction rate was 0.9% and the molecular weight distribution was 1.03 compared with that before hydrogenation.
Was obtained. Table 2 shows the physical property evaluation results of the present invention.
【００４１】[0041]
【表２】 [Table 2]
【００４２】芳香環を９０％以上水素添加することによ
り、耐熱性が大幅に向上し、高温引張強度が極めて高
く、かつ、流動性が極端に向上し、成型加工性が極めて
優れたブロック共重合体となる。比較例にあるように、
水素添加前のスチレンブロック鎖長が本発明の範囲内に
あっても芳香環の水素添加率が低いブロック共重合体
や、芳香環がほぼ完全に水素添加されていてもスチレン
ブロック鎖長が１４，０００以下のブロック共重合体で
は、耐熱性が低く、高温時の引張強度は極端に低く、ま
た、変形やべたつきが生じるものとなる。また、芳香環
水素添加率が低い場合、流動性の改良効果も乏しく、物
性バランスの劣るものとなる。一方、水素添加後の数平
均分子量減少率が大きかったブロック共重合体は、水素
添加反応時分子鎖切断が激しく生じていたものであり、
物性の低下、殊に強度、永久伸び、反発弾性の低下が激
しく、もはや本発明と同様の効果は到底発揮されないも
のとなる。By hydrogenating the aromatic ring by 90% or more, the heat resistance is greatly improved, the high-temperature tensile strength is extremely high, the flowability is extremely improved, and the block coexistence with excellent moldability is extremely high. Merge. As in the comparative example,
Even if the styrene block chain length before hydrogenation is within the range of the present invention, the block copolymer having a low hydrogenation rate of the aromatic ring or the styrene block chain length of 14 even when the aromatic ring is almost completely hydrogenated. With a block copolymer having a molecular weight of 2,000 or less, the heat resistance is low, the tensile strength at high temperatures is extremely low, and deformation and stickiness occur. Further, when the aromatic ring hydrogenation rate is low, the effect of improving the fluidity is poor and the balance of physical properties is poor. On the other hand, the block copolymer in which the number-average molecular weight reduction rate after hydrogenation was large was one in which the molecular chain was severely broken during the hydrogenation reaction,
The physical properties, especially the strength, the permanent elongation, and the rebound resilience are drastically reduced, and the same effects as those of the present invention can no longer be exhibited.
【００４３】（実施例６）実施例１と同様の手法を用い
て、ブロック共重合体Ａ−５について水素添加反応を行
い、不飽和オレフィン部分の水素添加率は１００％、芳
香環の水素添加率は９９．７％、水素添加後のポリマー
の数平均分子量は７０，６００で水素添加前に比較し数
平均分子量減少率は０．０６％、分子量分布が１．０３
の水素添加ブロック共重合体を得た。本ブロック共重合
体は、大幅に耐熱性が向上し、かつ成型加工性の良好な
熱可塑性ブロック共重合体であった。Example 6 A hydrogenation reaction was carried out on the block copolymer A-5 using the same procedure as in Example 1, and the hydrogenation rate of the unsaturated olefin portion was 100% and the hydrogenation of the aromatic ring was 100%. The ratio was 99.7%, the number average molecular weight of the polymer after hydrogenation was 70,600, and the number average molecular weight reduction rate was 0.06% and the molecular weight distribution was 1.03 compared to that before hydrogenation.
Was obtained. This block copolymer was a thermoplastic block copolymer having significantly improved heat resistance and good moldability.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐々木 洋朗 岡山県倉敷市潮通３丁目13番１ 旭化成工 業株式会社内 (72)発明者 加藤 清雄 神奈川県川崎市川崎区夜光１丁目３番１号 旭化成工業株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroaki Sasaki 3-13-1, Ushidori, Kurashiki-shi, Okayama Prefecture Asahi Kasei Corporation (72) Inventor Kiyoo Kato 1-3-1, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa No. Asahi Kasei Kogyo Co., Ltd.
Claims (3)
Ｘ、｛（Ａ−Ｂ）n+1 ｝m −Ｘ （式中、Ａは水素添加されたビニル芳香族炭化水素化合
物を主体とする重合体ブロック、Ｂは水素添加された共
役ジエン化合物を主体とする重合体ブロック、Ｘは多官
能性のカップリング剤残基、ｎ及びｍは１以上の整数で
ある。）で表され、重合体ブロックＡ中の水素添加前の
ビニル芳香族炭化水素化合物重合体の数平均分子量が１
４，０００を超え、またＮＭＲ測定によって得られる水
素添加率が、全芳香環の少なくとも８０％以上、全オレ
フィン性不飽和二重結合の少なくとも９０％以上であ
り、且つ、水素添加反応後の数平均分子量減少率が１０
％未満であるブロック共重合体であって、水素添加前の
共重合体中のビニル芳香族炭化水素化合物と共役ジエン
化合物との重量比が１０／９０〜９０／１０である熱可
塑性ブロック共重合体。1. The general formula (AB) n -A, (AB) n + 1 , (AB) n + 1 −
X, {(AB) n + 1 } m- X (where A is a polymer block mainly composed of a hydrogenated vinyl aromatic hydrocarbon compound, and B is mainly composed of a hydrogenated conjugated diene compound) X is a polyfunctional coupling agent residue, and n and m are integers of 1 or more.), And a vinyl aromatic hydrocarbon compound in the polymer block A before hydrogenation. Number average molecular weight of the polymer is 1
The hydrogenation rate obtained by NMR measurement is at least 80% or more of all aromatic rings, at least 90% or more of all olefinically unsaturated double bonds, and the number after hydrogenation reaction is more than 4,000. Average molecular weight reduction rate is 10
% Of the block copolymer, wherein the weight ratio of the vinyl aromatic hydrocarbon compound to the conjugated diene compound in the copolymer before hydrogenation is 10/90 to 90/10. Coalescing.
化水素化合物と共役ジエン化合物との重量比が１０／９
０〜５０／５０である請求項１記載の熱可塑性ブロック
共重合体。2. The weight ratio of the vinyl aromatic hydrocarbon compound to the conjugated diene compound in the copolymer before hydrogenation is 10/9.
The thermoplastic block copolymer according to claim 1, wherein the ratio is 0 to 50/50.
物の側鎖が２０モル％〜６０モル％である請求項２記載
の熱可塑性ブロック共重合体。3. The thermoplastic block copolymer according to claim 2, wherein the side chain of the conjugated diene compound in the copolymer before hydrogenation is 20 mol% to 60 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10420998A JPH11286526A (en) | 1998-04-01 | 1998-04-01 | Thermoplastic block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10420998A JPH11286526A (en) | 1998-04-01 | 1998-04-01 | Thermoplastic block copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11286526A true JPH11286526A (en) | 1999-10-19 |
Family
ID=14374587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10420998A Pending JPH11286526A (en) | 1998-04-01 | 1998-04-01 | Thermoplastic block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11286526A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6350820B1 (en) | 1999-06-11 | 2002-02-26 | The Dow Chemical Company | Hydrogenated block copolymers and optical media discs produced therefrom |
| US6376621B1 (en) | 1999-08-16 | 2002-04-23 | The Dow Chemical Company | Hydrogenated block copolymers and optical media discs produced therefrom |
| US6426390B1 (en) | 1999-06-11 | 2002-07-30 | Dow Global Technology Inc. | Hydrogenated block copolymer compositions |
| WO2002059173A1 (en) * | 2001-01-25 | 2002-08-01 | Teijin Limited | Improved hydrogenated styrene/conjugated diene/styrene block copolymer and process for production thereof |
| US6429260B1 (en) | 2000-05-31 | 2002-08-06 | The Dow Chemical Company | Olefinic polymer compositions |
| US6451924B1 (en) | 1999-06-11 | 2002-09-17 | Dow Global Technologies Inc. | Hydrogenated block copolymers and optical media discs produced therefrom |
| JP2003502471A (en) * | 1999-06-11 | 2003-01-21 | ザ ダウ ケミカル カンパニー | Compositions comprising hydrogenated block copolymers and their end uses |
| US6632890B1 (en) | 1999-03-19 | 2003-10-14 | Dow Global Technologies Inc. | Hydrogenated block copolymer compositions |
| KR100415151B1 (en) * | 2001-10-15 | 2004-01-16 | 주식회사 엘지화학 | Transparent high impact polystyrenic resins composition with good mold release and their prodution method |
| US6815475B2 (en) | 1999-06-11 | 2004-11-09 | Dow Global Technologies Inc. | Compositions comprising hydrogenated block copolymers and end-use applications thereof |
| US6914091B2 (en) | 1999-06-11 | 2005-07-05 | The Dow Chemical Company | Compositions comprising hydrogenated block copolymers and end-use applications thereof |
| JP2017177367A (en) * | 2016-03-28 | 2017-10-05 | 日本ゼオン株式会社 | Optical laminate, polarizing plate and liquid crystal display device |
-
1998
- 1998-04-01 JP JP10420998A patent/JPH11286526A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632890B1 (en) | 1999-03-19 | 2003-10-14 | Dow Global Technologies Inc. | Hydrogenated block copolymer compositions |
| US6815475B2 (en) | 1999-06-11 | 2004-11-09 | Dow Global Technologies Inc. | Compositions comprising hydrogenated block copolymers and end-use applications thereof |
| US6426390B1 (en) | 1999-06-11 | 2002-07-30 | Dow Global Technology Inc. | Hydrogenated block copolymer compositions |
| US6350820B1 (en) | 1999-06-11 | 2002-02-26 | The Dow Chemical Company | Hydrogenated block copolymers and optical media discs produced therefrom |
| US6451924B1 (en) | 1999-06-11 | 2002-09-17 | Dow Global Technologies Inc. | Hydrogenated block copolymers and optical media discs produced therefrom |
| JP2003502471A (en) * | 1999-06-11 | 2003-01-21 | ザ ダウ ケミカル カンパニー | Compositions comprising hydrogenated block copolymers and their end uses |
| US6914091B2 (en) | 1999-06-11 | 2005-07-05 | The Dow Chemical Company | Compositions comprising hydrogenated block copolymers and end-use applications thereof |
| US6376621B1 (en) | 1999-08-16 | 2002-04-23 | The Dow Chemical Company | Hydrogenated block copolymers and optical media discs produced therefrom |
| JP2003534412A (en) * | 2000-05-19 | 2003-11-18 | ダウ グローバル テクノロジーズ インコーポレーテッド | Hydrogenated block copolymer composition |
| US6429260B1 (en) | 2000-05-31 | 2002-08-06 | The Dow Chemical Company | Olefinic polymer compositions |
| WO2002059173A1 (en) * | 2001-01-25 | 2002-08-01 | Teijin Limited | Improved hydrogenated styrene/conjugated diene/styrene block copolymer and process for production thereof |
| KR100415151B1 (en) * | 2001-10-15 | 2004-01-16 | 주식회사 엘지화학 | Transparent high impact polystyrenic resins composition with good mold release and their prodution method |
| JP2017177367A (en) * | 2016-03-28 | 2017-10-05 | 日本ゼオン株式会社 | Optical laminate, polarizing plate and liquid crystal display device |
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