JPH0615595B2 - Block copolymer - Google Patents
Block copolymerInfo
- Publication number
- JPH0615595B2 JPH0615595B2 JP1948784A JP1948784A JPH0615595B2 JP H0615595 B2 JPH0615595 B2 JP H0615595B2 JP 1948784 A JP1948784 A JP 1948784A JP 1948784 A JP1948784 A JP 1948784A JP H0615595 B2 JPH0615595 B2 JP H0615595B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl aromatic
- weight
- block copolymer
- aromatic compound
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 本発明は新規なビニル芳香族化合物−共役ジエンブロッ
ク共重合体に関し、さらに詳しくは、両端に非エラスト
マー性ビニル芳香族化合物ブロックを有し、中央に共役
ジエンを主体としたビニル芳香族化合物と共役ジエンの
エラストマー性共重合体ブロックを有するブロック共重
合体に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel vinyl aromatic compound-conjugated diene block copolymer, more specifically, it has non-elastomeric vinyl aromatic compound blocks at both ends and mainly contains a conjugated diene. The present invention relates to a block copolymer having an elastomeric copolymer block of a vinyl aromatic compound and a conjugated diene.
最近、熱溶融型粘着剤の分野では初期粘着力とはくり強
度とダイカット性とに優れた特性を持つ熱可塑性エラス
トマーの要求が高まっている。Recently, in the field of hot-melt adhesives, there is an increasing demand for thermoplastic elastomers having excellent properties such as initial adhesive strength, peel strength and die-cutting property.
ビニル芳香族化合物と共役ジエンから成る直鎖状ブロッ
ク共重合体はアニオン重合の技術分野では公知のもので
あり、例えば特公昭40−23798、特公昭46−32415に開示
されている。しかしこれらの方法で得られるブロック共
重合体は粘着剤として用いた場合、初期粘着力とはくり
強度とダイカット性のバランスの点で未だ十分満足出来
るものではない。A linear block copolymer composed of a vinyl aromatic compound and a conjugated diene is known in the technical field of anionic polymerization and is disclosed, for example, in Japanese Examined Patent Publication Nos. 40-23798 and 46-32415. However, when the block copolymer obtained by these methods is used as a pressure-sensitive adhesive, it is still not sufficiently satisfactory in terms of the balance between initial pressure-sensitive adhesive strength, peel strength and die-cutting property.
そこで本発明者らは粘着剤として用いた場合、初期粘着
力とはくり強度とダイカット性にすぐれたブロック共重
合体を得るべく鋭意検討した結果、本発明に到達した。
即ち本発明は炭化水素溶媒中で有機リチウム化合物を開
始剤として重合して得られるビニル芳香族化合物含量が
１０重量％以上２５重量％未満のビニル芳香族化合物−
共役ジエンブロック共重合体であって、眼共重合体が一
般式 Ａ−Ｂ−Ａ （式中Ａはビニル芳香族化合物重合体ブロックであっ
て、両端のＡの合計量はビニル芳香族化合物全体の５０
〜９７重量％を含み、Ｂは共役ジエンを主体とするビニ
ル芳香族化合物との共重合体であって、ビニル芳香族化
合物が漸増するテーパーブロックを３〜１０個有する） であり、該共重合体はモノマー単位で１〜４個連らなっ
たビニル芳香族化合物の連鎖の量が全ビニル芳香族化合
物含量の５〜３０重量％であることを特徴とするブロッ
ク共重合体である。Therefore, the present inventors arrived at the present invention as a result of earnest studies to obtain a block copolymer having excellent initial adhesive strength, peeling strength and die-cutting property when used as an adhesive.
That is, the present invention provides a vinyl aromatic compound having a vinyl aromatic compound content of 10% by weight or more and less than 25% by weight, which is obtained by polymerizing an organic lithium compound as an initiator in a hydrocarbon solvent.
A conjugated diene block copolymer, wherein the ophthalmic copolymer has the general formula A-B-A (where A is a vinyl aromatic compound polymer block, and the total amount of A at both ends is the entire vinyl aromatic compound). Of 50
˜97% by weight, B is a copolymer with a vinyl aromatic compound mainly containing a conjugated diene, and has 3 to 10 tapered blocks in which the vinyl aromatic compound gradually increases). The combination is a block copolymer characterized in that the amount of chains of vinyl aromatic compounds in which 1 to 4 monomer units are connected is 5 to 30% by weight based on the total vinyl aromatic compound content.
本発明のブロック共重合体はビニル芳香族化合物が２５
重量％未満、好ましくは１０重量％以上２５重量％未
満、更に好ましくは１５重量％以上２５重量％未満であ
る。ビニル芳香族化合物が少なすぎると、粘着剤として
用いた場合はくり強度とダイカット性が劣り、２５重量
％以上では初期粘着力が十分でない。The block copolymer of the present invention has a vinyl aromatic compound content of 25
It is less than 10% by weight, preferably 10% by weight or more and less than 25% by weight, and more preferably 15% by weight or more and less than 25% by weight. If the vinyl aromatic compound content is too low, the peel strength and die-cutting property will be poor when used as a pressure-sensitive adhesive, and if it is 25% by weight or more, the initial pressure-sensitive adhesive strength will be insufficient.
ここでいうダイカット性とは、粘着ラベル製造時に、は
くり紙に貼り合わされた粘着シート上で所望の形のラベ
ルとなるようにダイで粘着基材を打ち抜き、不要な部分
をはくり紙から取り除くが、この時、ダイカット性が悪
いとダイに粘着基材が付着し、粘着ラベルとして必要な
部分までがはくり紙からはがれてしまうことを言う。こ
のダイカット性の悪さが熱可塑性ブロック共重合体を用
いた熱溶融型粘着剤を粘着ラベル用途へ応用する時の最
も大きな欠点となっている。The term "die-cutting property" as used herein means that when a pressure-sensitive adhesive label is produced, the pressure-sensitive adhesive base is punched out with a die so that the label has a desired shape on the pressure-sensitive adhesive sheet attached to the peeling paper, and unnecessary portions are removed from the peeling paper. However, at this time, if the die-cutting property is poor, the adhesive base material adheres to the die, and the portion required for the adhesive label is peeled off from the peeling paper. This poor die-cutting property is the greatest drawback when applying the hot-melt pressure-sensitive adhesive using a thermoplastic block copolymer to adhesive label applications.
本発明のブロック共重合体の特徴は一般式Ａ−Ｂ−Ａに
おいてＢ部分が特定範囲のテーパーブロック数を有し、
しかも該ブロック共重合体は特定範囲のビニル芳香族化
合物の連鎖分布を有した共重合体であることにある。こ
れらの特徴により粘着剤として用いた場合、初期粘着力
とはくり強度とダイカット性が著しく改善される。The feature of the block copolymer of the present invention is that the B portion in the general formula A-B-A has a number of tapered blocks in a specific range,
Moreover, the block copolymer is a copolymer having a chain distribution of vinyl aromatic compounds in a specific range. Due to these characteristics, when used as an adhesive, the initial adhesive strength, peeling strength and die-cutting property are remarkably improved.
本発明のブロック共重合体のＡ部分のビニル芳香族化合
物が全ビニル芳香族化合物の５０〜９７重量％で、好ま
しくは７０〜９６重量％である。５０重量％未満では粘
着剤として用いた場合、はくり強度と保持力が劣る。９
７重量％を超えるとダイカット性が劣る。Ｂ部分はビニ
ル芳香族化合物が漸増するテーパーブロックからなり、
そのテーパーブロックの数は３〜１０個、好ましくは３
〜７個が良い。テーパーブロックの数が３未満では粘着
剤として用いた場合ダイカット性が劣り、１０を超える
と粘着剤として用いた場合、はくり強度が劣る。The vinyl aromatic compound in the A portion of the block copolymer of the present invention is 50 to 97% by weight, preferably 70 to 96% by weight, based on the total vinyl aromatic compounds. If it is less than 50% by weight, the peel strength and the holding power will be poor when used as an adhesive. 9
If it exceeds 7% by weight, the die cut property is poor. Part B consists of a taper block in which vinyl aromatic compounds gradually increase,
The number of tapered blocks is 3 to 10, preferably 3.
~ 7 is good. When the number of taper blocks is less than 3, die cut property is poor when used as an adhesive, and when it exceeds 10, peel strength is poor when used as an adhesive.
ブロック共重合体のビニル芳香族化合物の連鎖分布はモ
ノマー単位で１〜４個連らなったビニル芳香族化合物の
連鎖の量が全ビニル芳香族化合物含量の５〜３０重量
％、好ましくは１５〜３０重量％である。４以下の連鎖
が５重量％未満では粘着剤として用いた場合はくり強度
が劣り、３０重量％を超えると粘着剤として用いた場合
は、初期粘着強度とダイカット性が劣る。The chain distribution of the vinyl aromatic compound in the block copolymer is such that the amount of the chain of the vinyl aromatic compound having 1 to 4 chained monomer units is 5 to 30% by weight of the total vinyl aromatic compound content, preferably 15 to It is 30% by weight. When the chain of 4 or less is less than 5% by weight, the peel strength is poor when it is used as an adhesive, and when it exceeds 30% by weight, the initial adhesive strength and the die cut property are poor when it is used as an adhesive.
本発明のブロック共重合体は次の様な方法で製造するこ
とが出来る。The block copolymer of the present invention can be produced by the following method.
すなわち、炭化水素溶媒中にエーテルまたは第３級アミ
ンを添加し、有機リチウム化合物を開始剤として用い、 (1)まずビニル芳香族化合物を全モノマー使用量の５〜
１２重量％、好ましくは７〜１２重量％を重合し、重合
反応が実質的に終了した後 (2)共役ジエン８５〜９９重量％とビニル芳香族化合物
１〜１５重量％の混合物を３回〜１０回に分けて重合
し、必要ならその後１回ブタジエンを添加して重合す
る。That is, an ether or a tertiary amine is added to a hydrocarbon solvent, and an organolithium compound is used as an initiator.
After polymerizing 12% by weight, preferably 7 to 12% by weight, the polymerization reaction is substantially completed. (2) A mixture of 85 to 99% by weight of the conjugated diene and 1 to 15% by weight of the vinyl aromatic compound is added three times or more. Polymerization is carried out in 10 batches, and if necessary, butadiene is added once to polymerize.
(3)最後にビニル芳香族化合物を全モノマー使用量に対
し５〜１２重量％、好ましくは７〜１２重量％を重合す
る方法が使用できる。(3) Finally, a method of polymerizing the vinyl aromatic compound in an amount of 5 to 12% by weight, preferably 7 to 12% by weight, based on the total amount of the monomers used can be used.
上記の共役ジエンとビニル芳香族化合物の混合物を３回
〜１０回に分けて重合する工程において各回の単量体使
用量は同程度の方が好ましく、また各回においてほぼ１
００％の重合を行なうことが望ましい。また３〜１０回
に分けてモノマーを添加する方法としてモノマー混合物
を添加する方法、または共役ジエンとビニル芳香族化合
物を同時に添加する方法等が用いられる。In the step of polymerizing the above-mentioned mixture of the conjugated diene and the vinyl aromatic compound in three to ten times, it is preferable that the amount of the monomer used in each time is approximately the same, and the amount of the monomer used is approximately 1 in each time.
It is desirable to carry out a polymerization of 00%. As a method of adding the monomer in 3 to 10 times, a method of adding a monomer mixture, a method of simultaneously adding a conjugated diene and a vinyl aromatic compound, or the like is used.
好ましいビニル芳香族化合物の連鎖分布を有するビニル
芳香族化合物と共役ジエンの共重合体は、炭化水素溶媒
中にエーテルまたは第３級アミンを添加して重合するこ
とによって得られる。エーテルまたは第３級アミンを添
加するとビニル芳香族化合物の１〜４の連鎖量が増加す
るが、この連鎖量はビニル芳香族化合物含量の５〜３０
重量％が好ましく、更に好ましくは１５〜３０重量％で
ある。The vinyl aromatic compound-conjugated diene copolymer having a preferable vinyl aromatic compound chain distribution can be obtained by adding an ether or a tertiary amine to a hydrocarbon solvent and polymerizing. The addition of ethers or tertiary amines increases the chain amount of vinyl aromatic compounds 1 to 4, which is 5 to 30% of the vinyl aromatic compound content.
The weight% is preferable, and more preferably 15 to 30% by weight.
ビニル芳香族化合物の連鎖分布を調節する観点から、エ
ーテルまたは第３級アミンの使用量はモノマー１００重
量部当り0.００５〜５重量部が好ましく、更に好ましく
は0.００５〜0.５重量部である。From the viewpoint of controlling the chain distribution of the vinyl aromatic compound, the amount of ether or tertiary amine used is preferably 0.005 to 5 parts by weight, more preferably 0.005 to 0.5 parts by weight, based on 100 parts by weight of the monomer. Is.
本発明に使用するビニル芳香族化合物としては、スチレ
ン、α−メチルスチレン、ｐ−メチルスチレン、ｍ−メ
チルスチレン、ｏ−メチルスチレン、ｐ−tert−ブチル
スチレン、ジメチルスチレン、ビニルナフタレン等が使
用出来る。このうちスチレンが好ましい。また共役ジエ
ンとしては、ブタジエン、イソプレン、ピペリレンなど
が使用出来る。このうちイソプレンが好ましいものとし
て挙げられる。As the vinyl aromatic compound used in the present invention, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tert-butylstyrene, dimethylstyrene, vinylnaphthalene and the like can be used. . Of these, styrene is preferred. As the conjugated diene, butadiene, isoprene, piperylene, etc. can be used. Of these, isoprene is preferred.
本発明のブロック共重合体の重量平均分子量は好ましく
は10,000〜500,000、更に好ましくは50,000〜300,000で
ある。このうちＡ部分の重量平均分子量は3,000〜50,00
0、Ｂ部分の重量平均分子量は44,000〜200,000が好まし
い。The weight average molecular weight of the block copolymer of the present invention is preferably 10,000 to 500,000, more preferably 50,000 to 300,000. The weight average molecular weight of A part is 3,000-50,00
The weight average molecular weights of 0 and B are preferably 44,000 to 200,000.
本発明のブロック共重合体は等温重合法でも、断熱重合
法でも得られる。また好ましい重合温度範囲は３０〜１
２０℃である。The block copolymer of the present invention can be obtained by either an isothermal polymerization method or an adiabatic polymerization method. The preferred polymerization temperature range is 30 to 1
It is 20 ° C.
本発明のブロック共重合体の製造に用いられる炭化水素
溶媒として、例えばシクロペンタン、シクロヘキサン、
ベンゼン、エチルベンゼン、キシレン及びこれらとペン
タン、ヘキサン、ヘプタン、ブタンなどの混合物が用い
られる。As the hydrocarbon solvent used in the production of the block copolymer of the present invention, for example, cyclopentane, cyclohexane,
Benzene, ethylbenzene, xylene and mixtures thereof with pentane, hexane, heptane, butane and the like are used.
有機リチウム化合物としては例えばｎ−ブチルリチウ
ム、sec−ブチルリチウム、tert−ブチルリチウム、ｎ
−ヘキシルリチウム、iso−ヘキシルリチウム、フェニ
ルリチウム、ナフチルリチウム等があり、モノマー１０
０重量部当り、0.０４〜1.０重量部で用いられる。Examples of the organic lithium compound include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n
-Hexyl lithium, iso-hexyl lithium, phenyl lithium, naphthyl lithium, etc.
It is used in an amount of 0.04 to 1.0 part by weight per 0 part by weight.
エーテルまたは第３級アミンとして例えばテトラハイド
ロフラン、ジエチルエーテル、アニソール、ジメトキシ
ベンゼン、エチレングリコールジメチルエーテル、トリ
エチルアミン、Ｎ−ジメチルアニリン、ピリジンなどの
エーテル化合物、及び第３級アミン化合物が用いられ
る。As the ether or tertiary amine, for example, an ether compound such as tetrahydrofuran, diethyl ether, anisole, dimethoxybenzene, ethylene glycol dimethyl ether, triethylamine, N-dimethylaniline, pyridine, or the like, and a tertiary amine compound are used.
本発明のブロック共重合体は主に熱溶融型粘着剤に用い
られる。The block copolymer of the present invention is mainly used for hot-melt pressure-sensitive adhesives.
そのほか本発明のブロック共重合体の用途は広範囲な領
域にわたるが、その例を示すならば履物、容器などの射
出成形品、玩具、家庭用品などのフロー成形品、パッキ
ング、シート、プレートなどの圧搾成型品等に好適に使
用することができる。更に本発明のブロック共重合体は
ＳＢＲやＮＢＲなどの他のゴム、ポリスチレンなどのプ
ラスチック等に混合しその物性を改変されるものにも用
いられる。例えばゴム用途としてはクレープ調スポン
ジ、プラスチック用途として汎用ポリスチレンの耐衝撃
性等の向上剤として利用される。更に本発明のブロック
共重合体はアスファルトに混合してアスファルトの耐寒
性を改良するために利用される。In addition, the use of the block copolymer of the present invention covers a wide range of areas, and if examples thereof are shown, injection molded products such as footwear and containers, flow molded products such as toys and household products, compression products such as packing, sheets and plates. It can be suitably used for molded products and the like. Furthermore, the block copolymer of the present invention can also be used for those whose physical properties are modified by mixing with other rubbers such as SBR and NBR, and plastics such as polystyrene. For example, it is used as a crepe-like sponge for rubber applications, and as a general-purpose polystyrene for plastic applications as an agent for improving impact resistance and the like. Further, the block copolymer of the present invention can be used in admixture with asphalt to improve the cold resistance of the asphalt.
以下に本発明の実施例をあげて詳細に説明するが、本発
明の主旨を越えない限り、本発明が限定されるものでは
ない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited as long as the gist of the present invention is not exceeded.
なお各種測定は下記の方法によった。Various measurements were made by the following methods.
初期粘着力は傾斜式ホールタック測定法に拠った。傾斜
角度３０゜、測定温度２５℃。The initial adhesive strength was based on the inclined Hall tack measurement method. Tilt angle 30 °, measurement temperature 25 ° C.
はくり強度はＪＩＳ Ｚ１５２２に準拠した。（１８０
゜定速はくり強度試験、測定温度２５℃。） 保持力はＪＩＳ Ｚ１５２４に準拠した。ただし、貼り
付け面積は１５×１０m/mで、１Kgのおもりが落下する
までの時間を測定した。測定温度２５℃。The peel strength complies with JIS Z1522. (180
° Constant speed peel strength test, measurement temperature 25 ℃. ) The holding power is based on JIS Z1524. However, the attachment area was 15 × 10 m / m, and the time until a 1 kg weight fell was measured. Measurement temperature 25 ° C.
ダイカット性の良否の判断は以下に示す方法で行なっ
た。すなわち、上質紙に所定の厚みに粘着剤をホットメ
ルトコーティングし、これをはくり紙に貼り合わせた
後、２０cm×４cmの大きさに切断する。次に1.５cm×1.
５cmの大きさの打ち抜き刃により、上質紙のみが切断さ
れるように１０個ずつ２列合計２０個の小片を打ち抜
く、その後、余分な部分を手ではくり紙よりはがす時、
一緒にはがれた粘着ラベルの数が０〜１枚のときに〇
印、２〜３枚のときに△印、４枚以上のときに×印を付
し、ダイカット性の良否を判定した。The quality of the die-cutting property was judged by the method described below. That is, a high-quality paper is hot-melt coated with a pressure-sensitive adhesive to a predetermined thickness, which is attached to a paper strip and then cut into a size of 20 cm × 4 cm. Next 1.5 cm x 1.
With a punching blade of 5 cm in size, 20 pieces of 2 pieces in a row are punched out so that only high-quality paper is cut. After that, when the extra part is peeled off by hand,
When the number of the adhesive labels peeled off together was 0 to 1, the number was 0, the number was 2 to 3, and the mark was 4 or more, and the number was x, and the quality of the die-cutting property was judged.
スチレン連鎖は農工大田中教授等によって開発された方
法（高分子学会予稿集、第２９巻７号2055頁）に準拠し
た。The styrene chain was based on the method developed by Professor Tanaka of Agricultural Science and Technology (Proceedings of the Polymer Society of Japan, Vol. 29, No. 7, page 2055).
全スチレン含量は赤外法により求めた。The total styrene content was determined by the infrared method.
実施例１ 洗滌、乾燥した撹拌機、ジャケット付きのオートクレー
プに窒素雰囲気下でシクロヘキサン4,500ｇ、テトラハ
イドロフラン１ｇを仕込んだ後、内温を７０℃にした。Example 1 After washing, drying, a stirrer and an autoclave with a jacket were charged with 4,500 g of cyclohexane and 1 g of tetrahydrofuran under an atmosphere of nitrogen, the internal temperature was raised to 70 ° C.
次にｎ−ブチルリチウム0.４ｇを含むヘキサン溶液を添
加後スチレンを５０ｇ添加し、６０分重合した。スチレ
ンの重合転化率は１００％であった。次いでスチレン１
０ｇ、イソプレン１６０ｇの混合物を添加して６０分重
合した。スチレン、イソプレンの重合転化率は１００％
であった。更にこの操作を２回繰返した。次いでイソプ
レンを１６０ｇ添加して重合転化率１００％まで重合さ
せた。その後更にスチレンを５０ｇ添加して６０分重合
した。転化率は１００％であった。Next, a hexane solution containing 0.4 g of n-butyllithium was added, and then 50 g of styrene was added, followed by polymerization for 60 minutes. The polymerization conversion rate of styrene was 100%. Then styrene 1
A mixture of 0 g and 160 g of isoprene was added and polymerized for 60 minutes. Polymerization conversion rate of styrene and isoprene is 100%
Met. Further, this operation was repeated twice. Next, 160 g of isoprene was added and polymerization was performed to a polymerization conversion rate of 100%. After that, 50 g of styrene was further added and polymerization was carried out for 60 minutes. The conversion rate was 100%.
なお重合中は温度を常に７０℃になる様に調節した。重
合終了後、重合体溶液に2,６−ジ−tert−ブチルｐ−ク
レゾールを添加した後、シクロヘキサンを加熱除去して
ブロック共重合体を得た。During the polymerization, the temperature was constantly adjusted to 70 ° C. After completion of the polymerization, 2,6-di-tert-butyl p-cresol was added to the polymer solution, and then cyclohexane was removed by heating to obtain a block copolymer.
実施例２〜８、比較例１〜８ 表−１に示した所定量のスチレン、イソプレン、テトラ
ハイドロフラン等を用い、実施例１と同様の処方によっ
て重合した。Examples 2 to 8 and Comparative Examples 1 to 8 Polymerization was carried out in the same manner as in Example 1 using the predetermined amounts of styrene, isoprene, tetrahydrofuran and the like shown in Table-1.
実施例２，３：Ａ部分の結合スチレンをそれぞれ９１％
と６０％にした例 〃 ４ ：Ａ部分のモノマー添加回数を７回とした
例 〃 ５，６：全結合スチレンをそれぞれ１２％と２２
％にした例 〃 ７ ：スチレンの代りにパラメチルスチレンを
使用した例 比較例１，２：全結合スチレンをそれぞれ７％と３０％
にした例 〃 ３，４：テトラハイドロフランの添加なしと大過
剰（6.５ｇ／100ｇモノマー）にした例 〃 ５，６：Ｂ部分のモノマー添加回数をそれぞれれ
２回と２０回にした例 〃 ７，８：Ａ部分の結合スチレンをそれぞれ４０％
と９９％にした例。 Examples 2 and 3: 91% of the bound styrene in the A part respectively.
And 60% 〃 4: Example where the number of times of addition of the monomer in the A portion is 7 times 〃 5,6: 12% and 22% of total bound styrene, respectively
% 7: Example of using paramethylstyrene instead of styrene Comparative Examples 1 and 2: 7% and 30% of total bound styrene, respectively.
〃 3,4: Example without addition of tetrahydrofuran and large excess (6.5g / 100g monomer) 〃 5,6: Example of adding the number of times of addition of monomer of B part to 2 times and 20 times respectively 〃 7, 8: 40% of bound styrene in A part
And 99%.
ブロック共重合体の構造を表−２、物性を表−３に示
す。Table-2 shows the structure of the block copolymer, and Table-3 shows the physical properties.
実施例１〜７は比較例１〜８に比べ、初期粘着力とはく
り強度とダイカット性のバランスの点で優れている。 Examples 1 to 7 are superior to Comparative Examples 1 to 8 in the balance of initial adhesive strength, peel strength and die-cutting property.
また図に実施例１、比較例３および比較例４の共重合体
について田中等の方法によるオゾン使用の酸化分解法に
よるスチレン連鎖分布曲線を示す。The figure also shows the styrene chain distribution curves for the copolymers of Example 1, Comparative Example 3 and Comparative Example 4 by the oxidative decomposition method using ozone by the method of Tanaka et al.
この結果は表−４のとおりであった。The results are shown in Table-4.
実施例９、比較例９ 実施例８のブロック共重合体２８重量％とポリスチレン
（三井東圧（株）製トーポレックス−５２５）７２重量
％との混合組成物を製造し、成形温度１８０℃で厚さ0.
２mmのシートについて物性を調べた。また比較のため上
記ポリスチレン単独の物性を調べた。 Example 9 and Comparative Example 9 A mixed composition of 28% by weight of the block copolymer of Example 8 and 72% by weight of polystyrene (Topolex-525 manufactured by Mitsui Toatsu Co., Ltd.) was prepared at a molding temperature of 180 ° C. Thickness 0.
The physical properties of the 2 mm sheet were examined. For comparison, the physical properties of the above polystyrene alone were examined.
結果を表−５に示す。The results are shown in Table-5.
図は実施例１、比較例３および４の共重合体について、
オゾンによる酸化分解法によるスチレン連鎖分布曲線を
示す。The figures show the copolymers of Example 1 and Comparative Examples 3 and 4,
The styrene chain distribution curve by the oxidative decomposition method by ozone is shown.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鳥居 政俊 東京都中央区築地２丁目11番24号 日本合 成ゴム株式会社内 (72)発明者 竹内 幹雄 東京都中央区築地２丁目11番24号 日本合 成ゴム株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masatoshi Torii 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (72) Inventor Mikio Takeuchi 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.
Claims (1)
始剤として重合して得られ、ビニル芳香族化合物含量が
１０重量％以上２５重量％未満の重量平均分子量１０，
０００〜５００，０００のビニル芳香族−共役ジエンブ
ロック共重合体であって、該共重合体が一般式 Ａ−Ｂ−Ａ （式中Ａはビニル芳香族重合体ブロックであって、両端
のＡの合計量はビニル芳香族化合物全体の５０〜９７重
量％を含み、Ｂは共役ジエン−ビニル芳香族共重合体ブ
ロックであって、ビニル芳香族化合物が漸増するテーパ
ーブロックを３〜１０個有する） であり、かつ該共重合体ブロックＢが、ビニル芳香族モ
ノマー単位が１〜４個連らなって構成された連鎖を全ビ
ニル芳香族化合物の５〜３０重量％含有することを特徴
とするブロック共重合体。1. A weight average molecular weight of 10, which is obtained by polymerizing an organolithium compound as an initiator in a hydrocarbon solvent and has a vinyl aromatic compound content of 10% by weight or more and less than 25% by weight.
000 to 500,000 vinyl aromatic-conjugated diene block copolymer, wherein the copolymer has the general formula A-B-A (wherein A is a vinyl aromatic polymer block, and A at both ends is Contains 50 to 97% by weight of the total vinyl aromatic compound, B is a conjugated diene-vinyl aromatic copolymer block, and has 3 to 10 tapered blocks in which the vinyl aromatic compound is gradually increased). And the copolymer block B contains 5 to 30% by weight of all vinyl aromatic compounds of a chain composed of 1 to 4 vinyl aromatic monomer units. Copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1948784A JPH0615595B2 (en) | 1984-02-07 | 1984-02-07 | Block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1948784A JPH0615595B2 (en) | 1984-02-07 | 1984-02-07 | Block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60163910A JPS60163910A (en) | 1985-08-26 |
| JPH0615595B2 true JPH0615595B2 (en) | 1994-03-02 |
Family
ID=12000710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1948784A Expired - Lifetime JPH0615595B2 (en) | 1984-02-07 | 1984-02-07 | Block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615595B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105154A (en) * | 2000-10-04 | 2002-04-10 | Asahi Kasei Corp | Block copolymer and composition of the same |
| US7141621B2 (en) | 2002-02-07 | 2006-11-28 | Kraton Polymers U.S. Llc | Gels from controlled distribution block copolymers |
| US20030181584A1 (en) | 2002-02-07 | 2003-09-25 | Kraton Polymers U.S. Llc | Elastomeric articles prepared from controlled distribution block copolymers |
-
1984
- 1984-02-07 JP JP1948784A patent/JPH0615595B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60163910A (en) | 1985-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4603155A (en) | Alkenyl aromatic compound-conjugated diene block copolymer and process for the production thereof | |
| JPH0340727B2 (en) | ||
| US3949020A (en) | Thermoplastic block polymers | |
| JP3976505B2 (en) | Transparent impact resistance improved polystyrene based on styrene butadiene block copolymer, polymer mixture containing the same, method for producing and using the same | |
| JP2781791B2 (en) | Tire having a tread comprising a rubber blend comprising a rubbery polymer having a plurality of glass transition temperatures | |
| JPH0362193B2 (en) | ||
| EP0171225A1 (en) | Pressure sensitive adhesive composition and intermediate copolymers for the preparation thereof | |
| EP0014947B1 (en) | Block copolymers of diene having their terminal end blocks of a random copolymer of styrene or alkylstyrene and an alpha-methylstyrene, and their preparation | |
| EP0330764B1 (en) | Block copolymer composition | |
| US4195136A (en) | Impact-resistant styrene resin composition | |
| EP0333936B1 (en) | Block copolymer compositions and process for the preparation thereof | |
| JPH0615595B2 (en) | Block copolymer | |
| KR20020038706A (en) | Butadiene/isoprene/aromatic vinyl hydrocarbon sevenblock copolymer and the preparing method thereof | |
| US6777499B2 (en) | Multiblock interpolymers and processes for the preparation thereof | |
| JPH0621136B2 (en) | Block copolymer | |
| JP2701268B2 (en) | Block copolymer composition | |
| JPH0617431B2 (en) | Method for producing block copolymer | |
| JPH0639509B2 (en) | Block copolymer and method for producing the same | |
| JPH0639508B2 (en) | Method for producing block copolymer | |
| JPH0788458B2 (en) | Method for producing block copolymer composition | |
| JPH0674290B2 (en) | Carboxy modified block copolymer | |
| JPH0617430B2 (en) | Block copolymer and method for producing the same | |
| EP1816149B1 (en) | Process for making a coupled low vinyl block copolymer composition and the resulting composition | |
| JPH0132258B2 (en) | ||
| JPS6126647A (en) | Block copolymer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |