TWI810466B - Hydrogenated block copolymer, hydrogenated block copolymer composition, and molded article - Google Patents
Hydrogenated block copolymer, hydrogenated block copolymer composition, and molded article Download PDFInfo
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- TWI810466B TWI810466B TW109119626A TW109119626A TWI810466B TW I810466 B TWI810466 B TW I810466B TW 109119626 A TW109119626 A TW 109119626A TW 109119626 A TW109119626 A TW 109119626A TW I810466 B TWI810466 B TW I810466B
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- block copolymer
- hydrogenated block
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- hydrogenated
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- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明獲得一種形成為與聚烯烴之樹脂組合物時,提供優異之耐磨耗性及高MFR之氫化嵌段共聚物。 本發明之氫化嵌段共聚物滿足(1)~(7)之必要條件。 (1):含有至少1個(b)包含乙烯基芳香族化合物單體單元與共軛二烯單體單元之氫化共聚物嵌段。 (2):(a)以乙烯基芳香族化合物單體單元為主體之聚合物嵌段之含量為40質量%以下。 (3):Mw為20萬以下。 (4):氫化率為20%以上。 (5):於GPC曲線中,分子量為1萬~15萬之範圍之面積相對於分子量為1萬~100萬之範圍之面積之比率超過50%。 (6):乙烯基鍵結量為20質量%以上。 (7):(b)嵌段中之乙烯基芳香族化合物單體單元之含量為30質量%以上79質量%以下。The present invention obtains a hydrogenated block copolymer that provides excellent abrasion resistance and high MFR when formed into a resin composition with polyolefin. The hydrogenated block copolymer of the present invention satisfies the requirements (1) to (7). (1): Contains at least one (b) hydrogenated copolymer block comprising a vinyl aromatic compound monomer unit and a conjugated diene monomer unit. (2): (a) The content of the polymer block mainly composed of vinyl aromatic compound monomer units is 40% by mass or less. (3): Mw is 200,000 or less. (4): The hydrogenation rate is above 20%. (5): In the GPC curve, the ratio of the area of the molecular weight range of 10,000 to 150,000 to the area of the molecular weight range of 10,000 to 1,000,000 exceeds 50%. (6): The amount of vinyl bonds is 20% by mass or more. (7): The content of the vinyl aromatic compound monomer unit in the (b) block is not less than 30% by mass and not more than 79% by mass.
Description
本發明係關於一種氫化嵌段共聚物、氫化嵌段共聚物組合物、及成形體。The present invention relates to a hydrogenated block copolymer, a hydrogenated block copolymer composition, and a shaped body.
自先前以來,對汽車之內裝用材料要求耐磨耗性及機械強度之平衡。作為此種材料,主要使用烯烴系樹脂。 另一方面,為了實現汽車用零件之輕量化、再利用性及易焚燒性等環境問題之需求,以及耐熱性、耐寒性、耐熱老化性、耐光性、低臭氣性,並且謀求外觀上之廉價感等之解決,近年來,將苯乙烯系熱塑性彈性體材料(以下,有時僅簡稱為「TPS材料」)供至實用中。Conventionally, a balance between abrasion resistance and mechanical strength has been required for automotive interior materials. As such a material, olefin-based resins are mainly used. On the other hand, in order to meet the requirements of environmental issues such as lightweight, reusable and incinerable parts for automobiles, as well as heat resistance, cold resistance, heat aging resistance, light resistance, low odor, and seek excellent appearance In recent years, styrene-based thermoplastic elastomer materials (hereinafter, sometimes simply referred to as "TPS materials") have been put into practical use to solve the feeling of cheapness.
進而,近年來,伴隨共享汽車或自動駕駛汽車之需求之提昇,對汽車之內裝用材料要求一種維持高水準之耐磨耗性並且可實現優質之觸感(低硬度)或機械強度之TPS材料。 針對此種要求,例如,於專利文獻1中提出一種乙烯基芳香族烴含量為40質量%以上且未達95質量%之無規共聚物苯乙烯系彈性體與聚丙烯樹脂之組合物及該組合物之成形體,揭示該成形體之耐磨耗性優異。 [先前技術文獻] [專利文獻]Furthermore, in recent years, with the increase in demand for shared cars and self-driving cars, a TPS that maintains a high level of wear resistance and can achieve high-quality touch (low hardness) or mechanical strength is required for automotive interior materials Material. In response to this requirement, for example, a composition of a random copolymer styrene-based elastomer and a polypropylene resin with a vinyl aromatic hydrocarbon content of more than 40% by mass and less than 95% by mass is proposed in Patent Document 1 and the A molded body of the composition, and it is revealed that the molded body is excellent in abrasion resistance. [Prior Art Literature] [Patent Document]
[專利文獻1]國際公開第03/035705號[Patent Document 1] International Publication No. 03/035705
[發明所欲解決之問題][Problem to be solved by the invention]
然而,專利文獻1中記載之無規共聚物苯乙烯系彈性體對聚丙烯樹脂之分散性較低,因此於形成為與聚丙烯樹脂之組合物之情形時,具有無法獲得充分之加工性之問題。又,擠出時股線迅速斷裂,故而具有擠出成形性亦不充分之問題。 進而,近年來,伴隨上述共享汽車或自動駕駛汽車之需求之提昇,對汽車內裝用材料要求高設計性,鑒於該設計性,要求複雜形狀之成形體之製作。 複雜形狀之成形體之製作方法之主流為藉由射出成形而製作,但於該情形時,成形體之材料必須為高熔體流動速率(以下,稱為MFR)。故而,要求一種維持耐磨耗性能等要求性能並且具有更高之MFR之樹脂組合物。However, the random copolymer styrene-based elastomer described in Patent Document 1 has low dispersibility to polypropylene resin, so when it is formed into a composition with polypropylene resin, sufficient processability cannot be obtained. question. In addition, the strands were broken rapidly during extrusion, so there was a problem that the extrusion formability was not sufficient. Furthermore, in recent years, along with the above-mentioned increase in demand for shared cars and self-driving cars, high designability is required for automotive interior materials, and in view of this designability, the production of molded objects with complex shapes is required. The main method of manufacturing molded objects with complex shapes is injection molding, but in this case, the material of the molded objects must have a high melt flow rate (hereinafter referred to as MFR). Therefore, there is a demand for a resin composition that maintains required properties such as wear resistance and has a higher MFR.
於本發明中,其目的在於提供一種可提供耐磨耗性優異、MFR較高之樹脂組合物之氫化嵌段共聚物、含有該氫化嵌段共聚物之樹脂組合物、及成形體。 [解決問題之技術手段]In the present invention, an object thereof is to provide a hydrogenated block copolymer capable of providing a resin composition having excellent wear resistance and a high MFR, a resin composition containing the hydrogenated block copolymer, and a molded article. [Technical means to solve the problem]
本發明者等人為了解決上述先前技術之課題而反覆潛心研究,結果發現藉由具有特定結構,並且特定出以乙烯基芳香族化合物單體單元為主體之聚合物嵌段之含量、重量平均分子量、氫化率、特定範圍之分子量之GPC曲線中之面積、乙烯基鍵結量、及特定之聚合物嵌段中之乙烯基芳香族化合物單體單元之含量的氫化嵌段共聚物,可提供耐磨耗性及MFR得以改善之樹脂組合物,從而完成本發明。 即,本發明如下所述。The inventors of the present invention have devoted themselves to research in order to solve the above-mentioned problems in the prior art, and found that by having a specific structure, and specifying the content of polymer blocks mainly composed of vinyl aromatic compound monomer units, and the weight average molecular weight , the hydrogenation rate, the area in the GPC curve of a specific range of molecular weight, the amount of vinyl bonds, and the content of vinyl aromatic compound monomer units in a specific polymer block. Hydrogenated block copolymers can provide resistance The present invention has been accomplished by providing a resin composition with improved abrasion resistance and MFR. That is, the present invention is as follows.
[1] 一種氫化嵌段共聚物,其係含有乙烯基芳香族化合物單體單元與共軛二烯單體單元之嵌段共聚物之氫化物,並且 滿足下述(1)~(7)之必要條件; (1):含有至少1個(b)包含乙烯基芳香族化合物單體單元與共軛二烯單體單元之氫化共聚物嵌段; (2):具有(a)以乙烯基芳香族化合物單體單元為主體之聚合物嵌段,該(a)以乙烯基芳香族化合物單體單元為主體之聚合物嵌段之含量為40質量%以下; (3):重量平均分子量(Mw)為20萬以下; (4):共軛二烯單體單元之雙鍵之氫化率為20%以上; (5):於以凝膠滲透層析(GPC)測定求得之氫化嵌段共聚物之分子量曲線中,分子量為1萬~15萬之範圍之面積相對於分子量為1萬~100萬之範圍之面積之比率超過50%; (6):氫化嵌段共聚物中之乙烯基鍵結量為20質量%以上; (7):上述(b)氫化共聚物嵌段中之乙烯基芳香族化合物單體單元之含量為30質量%以上79質量%以下。 [2] 如上述[1]之氫化嵌段共聚物,其中氫化嵌段共聚物中之乙烯基鍵結量為30質量%以上。 [3] 如上述[1]或[2]之氫化嵌段共聚物,其中上述(b)氫化共聚物嵌段中之乙烯基芳香族化合物單體單元之含量為45質量%以上79質量%以下。 [4] 如上述[1]至[3]中任一項之氫化嵌段共聚物,其中於以凝膠滲透層析(GPC)測定求得之氫化嵌段共聚物之分子量曲線中,分子量為20萬~100萬之範圍之面積相對於分子量為1萬~100萬之範圍之面積之比率為10%以上。 [5] 如上述[1]至[4]中任一項之氫化嵌段共聚物,其中總乙烯基芳香族化合物單體單元之含量為40質量%以上80質量%以下。 [6] 如上述[1]至[5]中任一項之氫化嵌段共聚物,其中上述(a)以乙烯基芳香族化合物單體單元為主體之聚合物嵌段之含量為1質量%以上20質量%以下。 [7] 如上述[1]至[6]中任一項之氫化嵌段共聚物,其含有1質量%以上之(c)以共軛二烯單體單元為主體之氫化聚合物嵌段。 [8] 如上述[1]至[7]中任一項之氫化嵌段共聚物,其中黏彈性測定圖中之tanδ之波峰於0℃以上30℃以下存在至少1個。 [9] 一種氫化嵌段共聚物組合物,其含有如上述[1]至[8]中任一項之氫化嵌段共聚物(一):1質量%以上95質量%以下、及 至少一種烯烴系樹脂(二):5質量%以上99質量%以下。 [10] 如上述[9]之氫化嵌段共聚物組合物,其中上述烯烴系樹脂(二)含有至少一種聚丙烯系樹脂。 [11] 一種成形體,其係如上述[9]或[10]之氫化嵌段共聚物組合物之成形體。 [發明之效果][1] A hydrogenated block copolymer, which is a hydrogenated block copolymer containing vinyl aromatic compound monomer units and conjugated diene monomer units, and Satisfy the necessary conditions of (1) to (7) below; (1): Containing at least one (b) hydrogenated copolymer block comprising vinyl aromatic compound monomer units and conjugated diene monomer units; (2): It has (a) a polymer block mainly composed of vinyl aromatic compound monomer units, and the content of (a) polymer block mainly composed of vinyl aromatic compound monomer units is 40% by mass %the following; (3): The weight average molecular weight (Mw) is less than 200,000; (4): The hydrogenation rate of the double bond of the conjugated diene monomer unit is more than 20%; (5): In the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC), the area with a molecular weight of 10,000 to 150,000 relative to the molecular weight range of 10,000 to 1,000,000 The area ratio exceeds 50%; (6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more; (7): The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) above is 30% by mass or more and 79% by mass or less. [2] The hydrogenated block copolymer according to the above [1], wherein the amount of vinyl bonds in the hydrogenated block copolymer is 30% by mass or more. [3] The hydrogenated block copolymer of the above [1] or [2], wherein the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) is 45% by mass or more and 79% by mass or less. [4] The hydrogenated block copolymer according to any one of the above [1] to [3], wherein in the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC), the molecular weight is 200,000 to 200,000 The ratio of the area of the range of 1 million to the area of the range of the molecular weight of 10,000 to 1,000,000 is 10% or more. [5] The hydrogenated block copolymer according to any one of the above [1] to [4], wherein the content of the total vinyl aromatic compound monomer units is 40% by mass or more and 80% by mass or less. [6] The hydrogenated block copolymer according to any one of the above-mentioned [1] to [5], wherein the content of the above-mentioned (a) polymer block mainly composed of vinyl aromatic compound monomer units is 1% by mass or more and 20% by mass %the following. [7] The hydrogenated block copolymer according to any one of the above [1] to [6], which contains 1% by mass or more of (c) a hydrogenated polymer block mainly composed of conjugated diene monomer units. [8] The hydrogenated block copolymer according to any one of the above-mentioned [1] to [7], wherein at least one peak of tan δ in the viscoelasticity measurement chart exists at 0°C to 30°C. [9] A hydrogenated block copolymer composition comprising the hydrogenated block copolymer (1) according to any one of the above [1] to [8]: 1% by mass to 95% by mass, and At least one olefin-based resin (2): 5% by mass or more and 99% by mass or less. [10] The hydrogenated block copolymer composition according to the above [9], wherein the olefin-based resin (2) contains at least one kind of polypropylene-based resin. [11] A molded article which is a molded article of the hydrogenated block copolymer composition according to the above-mentioned [9] or [10]. [Effect of Invention]
根據本發明,可獲得形成為與聚烯烴之樹脂組合物時,提供優異之耐磨耗性及高MFR之氫化嵌段共聚物。According to the present invention, it is possible to obtain a hydrogenated block copolymer that provides excellent abrasion resistance and high MFR when formed into a resin composition with polyolefin.
以下,詳細說明用以實施本發明之形態(以下,稱為「本實施形態」)。再者,以下本實施形態係用以說明本發明之例示,並未將本發明限定於以下內容,本發明可於其主旨之範圍內進行各種變化而實施。Hereinafter, the mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. In addition, the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited to the following contents, and the present invention can be implemented with various changes within the scope of the gist.
[氫化嵌段共聚物] 本實施形態之氫化嵌段共聚物(以下,有時稱為氫化嵌段共聚物(一))係含有乙烯基芳香族化合物單體單元與共軛二烯單體單元之嵌段共聚物之氫化物,滿足下述(1)~(7)。 (1):含有至少1個(b)包含乙烯基芳香族化合物單體單元與共軛二烯單體單元之氫化共聚物嵌段(以下,有時稱為共聚物嵌段(b))。 (2):具有(a)以乙烯基芳香族化合物單體單元為主體之聚合物嵌段(以下,有時稱為聚合物嵌段(a)),該聚合物嵌段(a)之含量為40質量%以下。 (3):重量平均分子量(Mw)為20萬以下。 (4):共軛二烯單體單元之雙鍵之氫化率為20%以上。 (5):於以凝膠滲透層析(GPC)測定求得之氫化嵌段共聚物之分子量曲線中,分子量為1萬~15萬之範圍之面積相對於分子量為1萬~100萬之範圍之面積之比率超過50%。 (6):氫化嵌段共聚物中之乙烯基鍵結量為20質量%以上。 (7):上述(b)氫化共聚物嵌段中之乙烯基芳香族化合物單體單元之含量為30質量%以上79質量%以下。[Hydrogenated Block Copolymer] The hydrogenated block copolymer of this embodiment (hereinafter sometimes referred to as hydrogenated block copolymer (1)) is a hydrogenated block copolymer containing a vinyl aromatic compound monomer unit and a conjugated diene monomer unit. The material satisfies the following (1) to (7). (1): Contains at least one (b) hydrogenated copolymer block comprising a vinyl aromatic compound monomer unit and a conjugated diene monomer unit (hereinafter, sometimes referred to as copolymer block (b)). (2): Having (a) a polymer block mainly composed of a vinyl aromatic compound monomer unit (hereinafter, sometimes referred to as a polymer block (a)), the content of the polymer block (a) 40% by mass or less. (3): The weight average molecular weight (Mw) is 200,000 or less. (4): The hydrogenation rate of the double bond of the conjugated diene monomer unit is 20% or more. (5): In the molecular weight curve of the hydrogenated block copolymer obtained by gel permeation chromatography (GPC), the area with a molecular weight of 10,000 to 150,000 relative to the molecular weight range of 10,000 to 1,000,000 The area ratio exceeds 50%. (6): The amount of vinyl bonds in the hydrogenated block copolymer is 20% by mass or more. (7): The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) above is 30% by mass or more and 79% by mass or less.
(乙烯基芳香族化合物單體單元) 本實施形態之氫化嵌段共聚物(一)含有乙烯基芳香族單體單元。 作為乙烯基芳香族化合物單體單元,並不限定於以下,例如可列舉:源自苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、二乙烯苯、1,1-二苯基乙烯、N,N-二甲基-對胺基乙基苯乙烯、N,N-二乙基-對胺基乙基苯乙烯等之單體單元。 尤其就價格與機械強度之平衡之觀點而言,較佳為苯乙烯。 該等可單獨使用,亦可併用兩種以上。(vinyl aromatic compound monomer unit) The hydrogenated block copolymer (1) of this embodiment contains vinyl aromatic monomer units. The vinyl aromatic compound monomer unit is not limited to the following, and examples thereof include: derived from styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, and 1,1-diphenylethylene , N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene and other monomer units. In particular, styrene is preferred from the viewpoint of the balance between price and mechanical strength. These may be used alone or in combination of two or more.
(共軛二烯單體單元) 本實施形態之氫化嵌段共聚物(一)含有共軛二烯單體單元。 所謂共軛二烯單體單元係指源自具有1對共軛雙鍵之二烯烴之單體單元。作為此種二烯烴,並不限定於以下,例如可列舉:1,3-丁二烯、2-甲基-1,3-丁二烯(異戊二烯)、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、2-甲基-1,3-戊二烯、1,3-己二烯等。 尤其就良好之成形加工性與機械強度之平衡之觀點而言,較佳為1,3-丁二烯、異戊二烯。 該等可單獨使用,亦可併用兩種以上。(conjugated diene monomer unit) The hydrogenated block copolymer (1) of this embodiment contains a conjugated diene monomer unit. The so-called conjugated diene monomer unit refers to a monomer unit derived from a diene having one pair of conjugated double bonds. Such dienes are not limited to the following, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl -1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc. In particular, 1,3-butadiene and isoprene are preferred from the viewpoint of a balance between good formability and mechanical strength. These may be used alone or in combination of two or more.
本實施形態之氫化嵌段共聚物(一)中,共軛二烯單體單元中之乙烯基鍵結量為20質量%以上,較佳為25質量%以上,更佳為30質量%以上,進而較佳為35質量%以上。 若氫化嵌段共聚物(一)之共軛二烯單體單元中之乙烯基鍵結量為20質量%以上,則於組合氫化嵌段共聚物(一)與下述烯烴系樹脂(二)之本實施形態之氫化嵌段共聚物組合物中,存在硬度、擠出成形性提高之傾向,若為30質量%以上,則存在尤其MFR、耐磨耗性變得良好之傾向。乙烯基鍵結量越高,上述物性越提高。 又,氫化嵌段共聚物(一)之乙烯基鍵結量例如可藉由下述三級胺化合物或醚化合物等調整劑之使用而控制。In the hydrogenated block copolymer (1) of this embodiment, the vinyl bond amount in the conjugated diene monomer unit is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, Furthermore, it is more preferable that it is 35 mass % or more. If the amount of vinyl bonds in the conjugated diene monomer unit of the hydrogenated block copolymer (1) is 20% by mass or more, when combining the hydrogenated block copolymer (1) with the following olefin resin (2) In the hydrogenated block copolymer composition of this embodiment, there exists a tendency for hardness and extrusion formability to improve, and when it is 30 mass % or more, especially MFR and abrasion resistance tend to become favorable. The higher the amount of vinyl bonds, the more the above-mentioned physical properties are improved. In addition, the amount of vinyl bonds in the hydrogenated block copolymer (1) can be controlled, for example, by using regulators such as the following tertiary amine compounds and ether compounds.
本實施形態之氫化嵌段共聚物(一)中,總乙烯基芳香族化合物單體單元之含量較佳為40質量%以上80質量%以下,更佳為45質量%以上80質量%以下,進而較佳為47質量%以上78質量%以下,進而更佳為50質量%以上75質量%以下。 若總乙烯基芳香族化合物單體單元之含量為上述範圍,則存在硬度、擠出成形性、耐磨耗性之平衡變得良好之傾向。 再者,於本實施形態中,氫化嵌段共聚物(一)中之總乙烯基芳香族化合物單體單元之含量可將氫化前之嵌段共聚物或氫化後之氫化嵌段共聚物作為檢體,使用紫外線分光光度計而測定。 又,氫化嵌段共聚物(一)之總乙烯基芳香族化合物單體單元之含量可藉由主要調整添加至反應器中之乙烯基芳香族化合物之量、反應溫度、反應時間,而控制為上述數值範圍。In the hydrogenated block copolymer (1) of this embodiment, the content of the total vinyl aromatic compound monomer units is preferably from 40% by mass to 80% by mass, more preferably from 45% by mass to 80% by mass, and further Preferably it is 47 mass % or more and 78 mass % or less, More preferably, it is 50 mass % or more and 75 mass % or less. When the content of the total vinyl aromatic compound monomer units is within the above range, the balance of hardness, extrusion moldability, and abrasion resistance tends to be favorable. Furthermore, in this embodiment, the content of the total vinyl aromatic compound monomer units in the hydrogenated block copolymer (1) can be detected by using the block copolymer before hydrogenation or the hydrogenated block copolymer after hydrogenation. body, measured using an ultraviolet spectrophotometer. Also, the content of the total vinyl aromatic compound monomer units of the hydrogenated block copolymer (1) can be controlled as above range of values.
再者,本說明書中,氫化嵌段共聚物之構成中,所謂「為主體」係指於特定之嵌段聚合物中或聚合物嵌段中之比率為85質量%以上,較佳為90質量%以上,更佳為95質量%以上。 再者,上述氫化共聚物嵌段(b)中之乙烯基芳香族化合物單體單元之含量為30質量%以上79質量%以下,故而可明確地區別上述聚合物嵌段(a)與氫化聚合物嵌段(b)。Furthermore, in this specification, in the composition of the hydrogenated block copolymer, the term "mainly" means that the ratio in a specific block polymer or in a polymer block is 85% by mass or more, preferably 90% by mass % or more, more preferably more than 95% by mass. Furthermore, since the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is 30% by mass or more and 79% by mass or less, it is possible to clearly distinguish the above polymer block (a) from the hydrogenated polymer block (a) Object block (b).
(以乙烯基芳香族化合物為主體之聚合物嵌段(a)) 作為本實施形態之氫化嵌段共聚物(一),就防止顆粒黏連之觀點而言,含有至少1個以乙烯基芳香族化合物單體單元為主體之聚合物嵌段(a)。 又,本實施形態之氫化嵌段共聚物(一)中,(a)聚合物嵌段之含量為40質量%以下,較佳為1質量%以上40質量%以下,更佳為1質量%以上20質量%以下,進而較佳為5質量%以上15質量%以下。 藉由使本實施形態之氫化嵌段共聚物(一)中之(a)聚合物嵌段之含量為40質量%以下,下述本實施形態之氫化嵌段共聚物組合物成為耐磨耗性與硬度之平衡良好者。(Polymer block (a) mainly composed of vinyl aromatic compounds) The hydrogenated block copolymer (1) of this embodiment contains at least one polymer block (a) mainly composed of vinyl aromatic compound monomer units from the viewpoint of preventing particle blocking. In addition, in the hydrogenated block copolymer (1) of the present embodiment, the content of (a) polymer block is 40 mass % or less, preferably 1 mass % or more and 40 mass % or less, more preferably 1 mass % or more 20 mass % or less, and more preferably 5 mass % or more and 15 mass % or less. By setting the content of (a) polymer block in the hydrogenated block copolymer (1) of this embodiment to be 40% by mass or less, the following hydrogenated block copolymer composition of this embodiment has abrasion resistance Good balance with hardness.
上述聚合物嵌段(a)之含量可將氫化前之嵌段共聚物或氫化後之氫化嵌段共聚物作為檢體,藉由使用有核磁共振裝置(NMR)之方法(Y.Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685(1981)中記載之方法;以下稱為「NMR法」)而測定。 又,氫化嵌段共聚物(一)中之聚合物嵌段(a)之含量可藉由主要調整添加至反應器中之乙烯基芳香族化合物之量、反應溫度、反應時間,而控制為上述數值範圍。The content of the above-mentioned polymer block (a) can be determined by using the block copolymer before hydrogenation or the hydrogenated block copolymer after hydrogenation as a sample by using a method with a nuclear magnetic resonance device (NMR) (Y.Tanaka, et al. al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereinafter referred to as "NMR method"). Also, the content of the polymer block (a) in the hydrogenated block copolymer (1) can be controlled to the above-mentioned range of values.
(氫化共聚物嵌段(b)) 本實施形態之氫化嵌段共聚物(一)含有包含乙烯基芳香族化合物單體單元與共軛二烯單體單元之氫化共聚物嵌段(b)。 氫化共聚物嵌段(b)中之乙烯基芳香族化合物單體單元之含量為30質量%以上79質量%以下,較佳為40質量%以上79質量%以下,更佳為45質量%以上79質量%以下,進而較佳為45質量%以上70質量%以下。(hydrogenated copolymer block (b)) The hydrogenated block copolymer (1) of this embodiment contains a hydrogenated copolymer block (b) comprising a vinyl aromatic compound monomer unit and a conjugated diene monomer unit. The content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is not less than 30% by mass and not more than 79% by mass, preferably not less than 40% by mass and not more than 79% by mass, more preferably not less than 45% by mass79 % by mass or less, more preferably not less than 45% by mass and not more than 70% by mass.
若氫化共聚物嵌段(b)中之乙烯基芳香族化合物單體單元之含量為30質量%以上79質量%以下,則下述本實施形態之氫化嵌段共聚物組合物表現良好之耐磨耗性。進而,若為45質量%以上79質量%以下,則表現更高之耐磨耗性,可用於對耐磨耗性之要求更嚴厲之用途。 又,若氫化共聚物嵌段(b)中之乙烯基芳香族化合物單體單元之含量為79質量%以下,則存在下述本實施形態之氫化嵌段共聚物組合物之擠出成形性提高之傾向,存在硬度下降之傾向。 再者,於本實施形態中,氫化嵌段共聚物(一)中之氫化共聚物嵌段(b)中之乙烯基芳香族化合物單體單元之含量可藉由核磁共振裝置(NMR)等而測定。 又,氫化共聚物嵌段(b)中之乙烯基芳香族化合物單體單元之含量可藉由主要調整添加至反應器中之乙烯基芳香族化合物、共軛二烯之量、反應溫度,而控制為上述數值範圍。If the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is not less than 30% by mass and not more than 79% by mass, the following hydrogenated block copolymer composition of the present embodiment exhibits good wear resistance consumption. Furthermore, if it is 45 mass % or more and 79 mass % or less, higher abrasion resistance will be shown, and it can be used for the use which requires stricter abrasion resistance. In addition, when the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) is 79% by mass or less, the extrusion moldability of the hydrogenated block copolymer composition of the present embodiment is improved as follows There is a tendency for the hardness to decrease. Furthermore, in this embodiment, the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) in the hydrogenated block copolymer (1) can be determined by a nuclear magnetic resonance device (NMR) or the like. Determination. Also, the content of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block (b) can be adjusted mainly by adjusting the amount of the vinyl aromatic compound added to the reactor, the amount of the conjugated diene, and the reaction temperature, and The control is within the above numerical range.
氫化共聚物嵌段(b)之氫化前之共聚物嵌段中之共軛二烯部分之乙烯基鍵結量例如可藉由下述三級胺化合物或醚化合物等調整劑之使用而控制。 於使用1,3-丁二烯作為共軛二烯之情形時,就於下述本實施形態之氫化嵌段共聚物組合物中,獲得耐磨耗性、MFR及硬度之良好之平衡之觀點而言,氫化共聚物嵌段(b)之氫化前之共聚物嵌段中之共軛二烯部分之1,2-乙烯基鍵結量較佳為25質量%以上95質量%以下,更佳為30質量%以上90質量%以下。 於使用異戊二烯作為共軛二烯之情形或併用1,3-丁二烯與異戊二烯作為共軛二烯之情形時,1,2-乙烯基鍵與3,4-乙烯基鍵之總量較佳為3質量%以上75質量%以下,更佳為5質量%以上60質量%以下。 再者,於本實施形態中,將1,2-乙烯基鍵與3,4-乙烯基鍵之總量(其中,於使用1,3-丁二烯作為共軛二烯之情形時為1,2-乙烯基鍵結量)稱為乙烯基鍵結量。 乙烯基鍵結量可藉由以氫化前之共聚物為檢體之利用紅外分光光度計之測定(例如漢普頓(Hampton)法)而測定。The amount of vinyl bonds in the conjugated diene moiety in the copolymer block before hydrogenation of the hydrogenated copolymer block (b) can be controlled, for example, by using an adjuster such as the following tertiary amine compound or ether compound. In the case of using 1,3-butadiene as the conjugated diene, in the hydrogenated block copolymer composition of the present embodiment described below, a good balance of abrasion resistance, MFR and hardness is obtained In other words, the 1,2-vinyl bond amount of the conjugated diene moiety in the copolymer block before hydrogenation of the hydrogenated copolymer block (b) is preferably from 25 mass % to 95 mass %, more preferably It is 30 mass % or more and 90 mass % or less. When isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used together as the conjugated diene, the 1,2-vinyl bond and the 3,4-vinyl bond The total amount of bonds is preferably from 3% by mass to 75% by mass, more preferably from 5% by mass to 60% by mass. Furthermore, in this embodiment, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (here, when 1,3-butadiene is used as the conjugated diene is 1 , 2-vinyl bond amount) is called vinyl bond amount. The amount of vinyl bonds can be measured by measurement with an infrared spectrophotometer (for example, the Hampton method) using the copolymer before hydrogenation as a sample.
(以共軛二烯單體單元為主體之氫化聚合物嵌段(c)) 本實施形態之氫化嵌段共聚物(一)較佳為含有以共軛二烯單體單元為主體之氫化聚合物嵌段(c)。 於本實施形態之氫化嵌段共聚物(一)中,氫化聚合物嵌段(c)之含量就氫化嵌段共聚物(一)之MFR、硬度及下述本實施形態之氫化嵌段共聚物組合物之MFR、耐磨耗性、硬度之平衡之觀點而言,較佳為1質量%以上,更佳為2質量%以上20質量%以下,進而較佳為2質量%以上15質量%以下,進而更佳為2質量%以上8質量%以下。 又,氫化嵌段共聚物(一)中之氫化聚合物嵌段(c)之含量可藉由主要控制添加至反應器中之共軛二烯之量、反應溫度,而控制為上述數值範圍。(Hydrogenated polymer block (c) mainly composed of conjugated diene monomer units) The hydrogenated block copolymer (1) of this embodiment preferably contains a hydrogenated polymer block (c) mainly composed of conjugated diene monomer units. In the hydrogenated block copolymer (1) of this embodiment, the content of the hydrogenated polymer block (c) depends on the MFR and hardness of the hydrogenated block copolymer (1) and the following hydrogenated block copolymer of this embodiment From the viewpoint of the balance of MFR, abrasion resistance, and hardness of the composition, it is preferably at least 1% by mass, more preferably at least 2% by mass and not more than 20% by mass, and still more preferably at least 2% by mass and not more than 15% by mass , and more preferably at least 2% by mass and not more than 8% by mass. Also, the content of the hydrogenated polymer block (c) in the hydrogenated block copolymer (1) can be controlled within the above numerical range by mainly controlling the amount of conjugated diene added to the reactor and the reaction temperature.
氫化聚合物嵌段(c)中之氫化後之共軛二烯單體單元之乙烯基鍵具有與下述烯烴系樹脂(二)類似之化學結構。故而,氫化聚合物嵌段(c)中之氫化前之共軛二烯單體單元之乙烯基鍵結量對氫化嵌段共聚物(一)與烯烴系樹脂(二)之相溶性產生影響,就提高該相溶性,使下述本實施形態之氫化嵌段共聚物組合物之耐磨耗性、MFR、硬度變得良好之觀點而言,較佳為50質量%以上,更佳為55質量%以上,進而較佳為60質量%以上。The vinyl bond of the hydrogenated conjugated diene monomer unit in the hydrogenated polymer block (c) has a chemical structure similar to that of the following olefin resin (2). Therefore, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation in the hydrogenated polymer block (c) affects the compatibility between the hydrogenated block copolymer (1) and the olefin resin (2), From the viewpoint of improving the compatibility and improving the wear resistance, MFR, and hardness of the hydrogenated block copolymer composition of the present embodiment described below, it is preferably 50% by mass or more, more preferably 55% by mass % or more, and more preferably 60% by mass or more.
(氫化嵌段共聚物(一)之黏彈性測定圖中之tanδ(損耗正切)) 本實施形態之氫化嵌段共聚物(一)於黏彈性測定圖中,tanδ(損耗正切)之波峰較佳為於-25℃以上40℃以下存在至少1個。更佳為於-15℃以上35℃以下,進而較佳為於-10℃以上30℃以下,進而更佳為於0℃以上30℃以下存在至少1個。 該tanδ之波峰係起因於氫化嵌段共聚物(一)中之氫化共聚物嵌段(b)之波峰。為了保持氫化嵌段共聚物之硬度、及下述實施形態之氫化嵌段共聚物組合物中之耐磨耗性及良好之觸感,重要的為該波峰於-25℃以上40℃以下之範圍內存在至少1個。 如上所述,氫化共聚物嵌段(b)係將包含共軛二烯單體單元與乙烯基芳香族單體單元之共聚物嵌段進行氫化而獲得。 為了使tanδ(損耗正切)之波峰於-25℃以上40℃以下之範圍內存在至少1個,有效的為控制共軛二烯單體單元/乙烯基芳香族單體單元(質量比),共軛二烯單體單元/乙烯基芳香族單體單元(質量比)較佳為75/25~16/84,更佳為70/30~18/82,進而較佳為60/40~25/75。 為了使tanδ(損耗正切)之波峰於0℃以上30℃以下之範圍內存在至少1個,有效的為控制共軛二烯單體單元/乙烯基芳香族單體單元(質量比),共軛二烯單體單元/乙烯基芳香族單體單元(質量比)較佳為65/35~16/84,更佳為60/40~25/75,進而較佳為55/45~30/70。 再者,tanδ可使用黏彈性測定裝置(TA Instruments股份有限公司製造,ARES),於應變0.5%、頻率1 Hz、升溫速度3℃/分鐘之條件下進行測定。具體而言,可藉由下述實施例中記載之方法而測定。(tanδ (loss tangent) in the viscoelasticity measurement chart of hydrogenated block copolymer (1)) In the hydrogenated block copolymer (1) of this embodiment, in the viscoelasticity measurement graph, it is preferable that at least one peak of tan δ (loss tangent) exists at -25°C or higher and 40°C or lower. More preferably, at least one is present at -15°C to 35°C, more preferably -10°C to 30°C, still more preferably 0°C to 30°C. This peak of tan δ originates from the peak of the hydrogenated copolymer block (b) in the hydrogenated block copolymer (1). In order to maintain the hardness of the hydrogenated block copolymer, and the wear resistance and good touch of the hydrogenated block copolymer composition of the following embodiments, it is important that the peak is in the range of -25°C to 40°C There is at least 1 in memory. As described above, the hydrogenated copolymer block (b) is obtained by hydrogenating a copolymer block including a conjugated diene monomer unit and a vinyl aromatic monomer unit. In order to have at least one peak of tanδ (loss tangent) in the range of -25°C to 40°C, it is effective to control the conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio). Conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio) is preferably 75/25 to 16/84, more preferably 70/30 to 18/82, further preferably 60/40 to 25/ 75. In order to have at least one peak of tanδ (loss tangent) in the range of 0°C to 30°C, it is effective to control the conjugated diene monomer unit/vinyl aromatic monomer unit (mass ratio), conjugated Diene monomer unit/vinyl aromatic monomer unit (mass ratio) is preferably 65/35 to 16/84, more preferably 60/40 to 25/75, further preferably 55/45 to 30/70 . In addition, tan δ can be measured using a viscoelasticity measuring device (manufactured by TA Instruments Co., Ltd., ARES) under the conditions of a strain of 0.5%, a frequency of 1 Hz, and a heating rate of 3° C./min. Specifically, it can be measured by the method described in the following examples.
(氫化嵌段共聚物(一)之重量平均分子量) 本實施形態之氫化嵌段共聚物(一)之重量平均分子量(Mw)為20萬以下,就於下述本實施形態之氫化嵌段共聚物組合物中獲得良好之耐磨耗性、MFR、硬度、顆粒黏連性之平衡之觀點而言,較佳為5萬以上19萬以下,更佳為6萬以上18萬以下,進而較佳為7萬以上17萬以下。 再者,於本實施形態中,氫化嵌段共聚物(一)之重量平均分子量係進行藉由凝膠滲透層析法(GPC)之測定,使用自市售之標準聚苯乙烯之測定求出之校準曲線(使用標準聚苯乙烯之波峰分子量而製作)而求得。(weight average molecular weight of hydrogenated block copolymer (1)) The weight-average molecular weight (Mw) of the hydrogenated block copolymer (1) of this embodiment is 200,000 or less, in order to obtain good abrasion resistance, MFR, From the viewpoint of the balance between hardness and particle cohesion, it is preferably from 50,000 to 190,000, more preferably from 60,000 to 180,000, and still more preferably from 70,000 to 170,000. Furthermore, in this embodiment, the weight average molecular weight of the hydrogenated block copolymer (1) is measured by gel permeation chromatography (GPC), and obtained from the measurement of commercially available standard polystyrene The calibration curve (made using the peak molecular weight of standard polystyrene) was obtained.
(氫化嵌段共聚物(一)之分子量曲線之分佈) 本實施形態之氫化嵌段共聚物(一)之GPC曲線中,分子量為1萬~15萬之範圍之面積相對於分子量為1萬~100萬之範圍之面積之比率(%)超過50%。 就獲得良好之耐磨耗性、MFR、硬度、顆粒黏連性之平衡之觀點而言,設為超過50%,較佳為60~99%,更佳為70~95%。 分子量1萬~15萬之範圍之面積之比率越多,則越可提高MFR,降低硬度,越少則越可提高耐磨耗性,降低顆粒黏連性。 再者,本實施形態之氫化嵌段共聚物(一)之GPC曲線中之分子量為1萬~15萬之面積之比率可藉由聚合起始劑、偶合劑之量之控制,或具有適宜之分子量分佈之兩種以上之聚合物之混合,而控制為上述數值範圍。(Distribution of Molecular Weight Curve of Hydrogenated Block Copolymer (1)) In the GPC curve of the hydrogenated block copolymer (1) of this embodiment, the ratio (%) of the area of the molecular weight range of 10,000 to 150,000 to the area of the molecular weight range of 10,000 to 1,000,000 exceeds 50%. From the viewpoint of obtaining a good balance between wear resistance, MFR, hardness, and particle adhesion, the content is more than 50%, preferably 60-99%, and more preferably 70-95%. The more the area ratio in the range of molecular weight 10,000 to 150,000, the more the MFR can be increased and the hardness can be lowered, and the lower the ratio, the more the wear resistance can be improved and the particle adhesion can be reduced. Furthermore, the area ratio of the molecular weight of the hydrogenated block copolymer (1) in the GPC curve of the present embodiment is 10,000 to 150,000 can be controlled by the amount of polymerization initiator and coupling agent, or have an appropriate The mixture of two or more polymers with molecular weight distribution is controlled within the above numerical range.
又,本實施形態之氫化嵌段共聚物(一)之GPC曲線中,分子量為20萬~100萬之範圍之面積相對於分子量為1萬~100萬之範圍之面積之比率(%)就獲得耐磨耗性、顆粒黏連性之平衡之觀點而言,較佳為10%以上,更佳為20%以上。 分子量20萬~100萬之範圍之面積之比率越多,則越可提高耐磨耗性,降低顆粒黏連性。 尤其為了提高耐磨耗性、顆粒黏連,較佳為氫化嵌段共聚物(一)之分子量為20萬以上之範圍之面積之比率為上述數值範圍,更佳為22萬以上之範圍之面積之比率為上述數值範圍,進而較佳為24萬以上之範圍之面積之比率為上述數值範圍。 為了提高MFR,較佳為氫化嵌段共聚物(一)之分子量為100萬以下之範圍之面積之比率為上述數值範圍,更佳為70萬以下之範圍之面積為上述數值範圍,進而較佳為50萬以下之範圍之面積為上述數值範圍,進而更佳為30萬以下之範圍之面積為上述數值範圍。 再者,本實施形態之氫化嵌段共聚物(一)之GPC曲線中之分子量為20萬~100萬之面積之比率可藉由聚合起始劑、偶合劑之量之調整,或具有適宜之分子量分佈之兩種以上之聚合物之混合,而控制為上述數值範圍。Also, in the GPC curve of the hydrogenated block copolymer (1) of the present embodiment, the ratio (%) of the area of the molecular weight range of 200,000 to 1,000,000 to the area of the molecular weight of 10,000 to 1,000,000 is obtained From the viewpoint of the balance between abrasion resistance and particle adhesion, it is preferably at least 10%, more preferably at least 20%. The more the ratio of the area of the molecular weight range of 200,000 to 1 million, the more the wear resistance can be improved and the particle adhesion can be reduced. In particular, in order to improve abrasion resistance and particle adhesion, it is preferable that the ratio of the area of the hydrogenated block copolymer (1) with a molecular weight of 200,000 or more is in the above numerical range, more preferably the area of the range of 220,000 or more The ratio is in the above numerical range, and more preferably the ratio of the area in the range above 240,000 is in the above numerical range. In order to increase the MFR, it is preferable that the ratio of the area of the hydrogenated block copolymer (1) with a molecular weight of 1 million or less is in the above numerical range, more preferably the area of the range of 700,000 or less is in the above numerical range, and even more preferably The area within the range of 500,000 or less is the above numerical range, and more preferably the area within the range of 300,000 or less is the above numerical range. Furthermore, the area ratio of the molecular weight of the hydrogenated block copolymer (1) in the GPC curve of the present embodiment is 200,000 to 1,000,000 can be adjusted by the amount of polymerization initiator and coupling agent, or have a suitable The mixture of two or more polymers with molecular weight distribution is controlled within the above numerical range.
(氫化嵌段共聚物(一)中之共軛二烯單體單元之雙鍵之氫化率) 作為本實施形態之氫化嵌段共聚物(一)中之共軛二烯單體單元之雙鍵之氫化率,就於下述本實施形態之氫化嵌段共聚物組合物中獲得良好之硬度、MFR之觀點而言,設為20%以上,較佳為50%以上,更佳為85%以上,進而較佳為92%以上。 氫化嵌段共聚物(一)中之共軛二烯單體單元之雙鍵之氫化率可藉由氫化量之調整,而控制上述數值範圍。(Hydrogenation rate of double bond of conjugated diene monomer unit in hydrogenated block copolymer (1)) As the hydrogenation rate of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (1) of this embodiment, good hardness is obtained in the following hydrogenated block copolymer composition of this embodiment, In view of MFR, it is 20% or more, Preferably it is 50% or more, More preferably, it is 85% or more, More preferably, it is 92% or more. The hydrogenation rate of the double bond of the conjugated diene monomer unit in the hydrogenated block copolymer (1) can be controlled by adjusting the amount of hydrogenation to control the above numerical range.
(氫化嵌段共聚物(一)中之乙烯基芳香族化合物單元之芳香族雙鍵之氫化率) 關於本實施形態之氫化嵌段共聚物(一)中之乙烯基芳香族化合物單元之芳香族雙鍵之氫化率,並無特別限制,較佳為50%以下,更佳為30%以下,進而較佳為20%以下。 此處,氫化嵌段共聚物(一)之氫化率可使用核磁共振裝置(NMR)等而測定。(Hydrogenation rate of aromatic double bond of vinyl aromatic compound unit in hydrogenated block copolymer (1)) There is no particular limitation on the hydrogenation rate of the aromatic double bond of the vinyl aromatic compound unit in the hydrogenated block copolymer (1) of this embodiment, but it is preferably 50% or less, more preferably 30% or less, and further Preferably it is 20% or less. Here, the hydrogenation rate of the hydrogenated block copolymer (1) can be measured using a nuclear magnetic resonance apparatus (NMR) etc.
(氫化嵌段共聚物(一)之結晶化波峰) 本實施形態之氫化嵌段共聚物(一)較佳為於示差掃描熱量測定(DSC)圖中,於-25~80℃之範圍內,實質不存在起因於氫化共聚物嵌段(b)之結晶化波峰之氫化物。 此處,所謂「於-25~80℃之範圍內實質不存在起因於氫化共聚物嵌段(b)之結晶化波峰」係指於該溫度範圍內,未出現起因於氫化共聚物嵌段(b)部分之結晶化之波峰,或即使於確認有起因於結晶化之波峰之情形時,該結晶化所引起之結晶化波峰熱量亦未達3 J/g,較佳為未達2 J/g,更佳為未達1 J/g,進而較佳為無結晶化波峰熱量。(Crystalization peak of hydrogenated block copolymer (1)) The hydrogenated block copolymer (1) of this embodiment is preferably in a differential scanning calorimetry (DSC) chart, within the range of -25 to 80°C, there is substantially no hydrogenated copolymer block (b) The hydride of the crystallization peak. Here, "there is substantially no crystallization peak due to the hydrogenated copolymer block (b) in the range of -25 to 80°C" means that within this temperature range, no crystallization peak due to the hydrogenated copolymer block (b) appears. b) Part of the crystallization peak, or even when it is confirmed that there is a peak caused by crystallization, the crystallization peak calorific value caused by the crystallization does not reach 3 J/g, preferably it does not reach 2 J/g g, more preferably less than 1 J/g, and still more preferably no crystallization peak calorific value.
如上所述,若於-25~80℃之範圍內實質不存在起因於氫化共聚物嵌段(b)之結晶化波峰,則於本實施形態之氫化嵌段共聚物(一)中獲得良好之柔軟性,從而可謀求下述本實施形態之氫化嵌段共聚物組合物之軟質化,故而較佳。 為了獲得於-25~80℃之範圍內實質不存在起因於氫化共聚物嵌段(b)之結晶化波峰之氫化嵌段共聚物(一),只要使用進行乙烯基鍵結量之調整或乙烯基芳香族化合物與共軛二烯之共聚性之調整之特定之調整劑,於下述條件下進行聚合反應,將藉此獲得之共聚物進行氫化反應即可。As described above, if there is substantially no crystallization peak attributable to the hydrogenated copolymer block (b) in the range of -25 to 80°C, a favorable hydrogenated block copolymer (1) according to the present embodiment can be obtained. Flexibility is preferable because it can achieve softening of the hydrogenated block copolymer composition of the present embodiment described below. In order to obtain a hydrogenated block copolymer (1) in which there is substantially no crystallization peak attributable to the hydrogenated copolymer block (b) in the range of -25 to 80°C, it is only necessary to use vinyl bonded amount adjustment or ethylene As a specific regulator for adjusting the copolymerizability of an aromatic compound and a conjugated diene, the polymerization reaction is carried out under the following conditions, and the copolymer thus obtained is subjected to a hydrogenation reaction.
(氫化嵌段共聚物(一)之結構) 關於本實施形態之氫化嵌段共聚物(一)之結構,並無特別限制,例如可列舉具有下述通式所表示之結構者。 (b-c)n 、c-(b-c)n 、b-(c-b)n 、(b-c)m -X、(c-b)m -X、c-(b-a)n 、c-(a-b)n 、c-(a-b-a)n 、c-(b-a-b)n 、c-(b-c-a)n 、a-(c-b-c-a)n 、a-c-(b-a)n 、a-c-(a-b)n 、a-c-(b-a)n -b、[(a-b-c)n ]m -X、[a-(b-c)n ]m -X、[(a-b)n -c]m -X、[(a-b-a)n -c]m -X、[(b-a-b)n -c]m -X、[(c-b-a)n ]m -X、[c-(b-a)n ]m -X、[c-(a-b-a)n ]m -X、[c-(b-a-b)n ]m -X 再者,於上述各通式中,a表示以乙烯基芳香族化合物單體單元為主體之聚合物嵌段(a),b表示包含乙烯基芳香族化合物單體單元與共軛二烯單體單元之氫化共聚物嵌段(b),c表示以共軛二烯單體單元為主體之氫化聚合物嵌段(c)。 n為1以上之整數,較佳為1~5之整數。 m為2以上之整數,較佳為2~11之整數。 X表示偶合劑之殘基或多官能起始劑之殘基。(Structure of Hydrogenated Block Copolymer (1)) The structure of the hydrogenated block copolymer (1) of this embodiment is not particularly limited, and examples thereof include structures represented by the following general formula. (bc) n , c-(bc) n , b-(cb) n , (bc) m -X, (cb) m -X, c-(ba) n , c-(ab) n , c-( aba) n , c-(bab) n , c-(bca) n , a-(cbca) n , ac-(ba) n , ac-(ab) n , ac-(ba) n -b, [( abc) n ] m -X, [a-(bc) n ] m -X, [(ab) n -c] m -X, [(aba) n -c] m -X, [(bab) n - c] m -X, [(cba) n ] m -X, [c-(ba) n ] m -X, [c-(aba) n ] m -X, [c-(bab) n ] m - X In addition, in each of the above general formulas, a represents a polymer block (a) mainly composed of vinyl aromatic compound monomer units, and b represents a polymer block (a) composed of vinyl aromatic compound monomer units and conjugated diene monomers. The hydrogenated copolymer block (b) of the monomer unit, c represents the hydrogenated polymer block (c) mainly composed of the conjugated diene monomer unit. n is an integer of 1 or more, preferably an integer of 1-5. m is an integer of 2 or more, preferably an integer of 2-11. X represents the residue of a coupler or the residue of a polyfunctional initiator.
(氫化嵌段共聚物(一)之結構之其他例) 本實施形態之氫化嵌段共聚物(一)可為鍵結有具有特定官能基之原子團之改性嵌段共聚物。 又,改性嵌段共聚物可為二次改性嵌段共聚物。(Other examples of the structure of the hydrogenated block copolymer (1)) The hydrogenated block copolymer (1) of this embodiment may be a modified block copolymer bonded with atomic groups having specific functional groups. Also, the modified block copolymer may be a secondary modified block copolymer.
[氫化嵌段共聚物(一)之製造方法] 本實施形態之氫化嵌段共聚物(一)之氫化前之狀態之嵌段共聚物例如係藉由如下方式獲得:於烴溶劑中使用有機鹼金屬化合物等聚合起始劑,使乙烯基芳香族化合物與共軛二烯化合物進行活性陰離子聚合。[Manufacturing method of hydrogenated block copolymer (1)] The block copolymer in the state before hydrogenation of the hydrogenated block copolymer (1) of this embodiment is obtained, for example, by using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent to make a vinyl aromatic The compound is subjected to living anionic polymerization with a conjugated diene compound.
(溶劑) 作為烴溶劑,並不限定於以下,例如可列舉:正丁烷、異丁烷、正戊烷、正己烷、正庚烷、正辛烷等脂肪族烴類;環己烷、環庚烷、甲基環庚烷等脂環式烴類;苯、甲苯、二甲苯、乙苯等芳香族烴。(solvent) The hydrocarbon solvent is not limited to the following, and examples include: aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane, cycloheptane, Alicyclic hydrocarbons such as methyl cycloheptane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.
(聚合起始劑) 作為聚合起始劑,並無特別限定,例如通常可應用已知對乙烯基芳香族化合物及共軛二烯具有陰離子聚合活性之脂肪族烴鹼金屬化合物、芳香族烴鹼金屬化合物、有機胺基鹼金屬化合物等有機鹼金屬化合物。 作為有機鹼金屬化合物,並不限定於以下,例如較佳為碳數1~20之脂肪族及芳香族烴鋰化合物,可應用於1分子中含有1個鋰之化合物、於1分子中含有複數個鋰之二鋰化合物、三鋰化合物、四鋰化合物。 具體可列舉:正丙基鋰、正丁基鋰、第二丁基鋰、第三丁基鋰、正戊基鋰、正己基鋰、苄基鋰、苯基鋰、甲苯基鋰、二異丙烯基苯與第二丁基鋰之反應產物、二乙烯苯與第二丁基鋰與少量1,3-丁二烯之反應產物等。 進而,亦可應用例如美國專利第5,708,092號說明書、英國專利第2,241,239號說明書、美國專利第5,527,753號說明書中揭示之有機鹼金屬化合物。(polymerization initiator) The polymerization initiator is not particularly limited. For example, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amine groups known to have anionic polymerization activity for vinyl aromatic compounds and conjugated dienes are generally applicable. Organic alkali metal compounds such as alkali metal compounds. The organoalkali metal compound is not limited to the following. For example, aliphatic and aromatic hydrocarbon lithium compounds with 1 to 20 carbon atoms are preferred. Compounds containing one lithium in one molecule and multiple lithium in one molecule can be applied. Lithium dilithium compounds, trilithium compounds, and tetralithium compounds. Specifically, n-propyllithium, n-butyllithium, second-butyllithium, third-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropene The reaction product of phenylbenzene and second butyl lithium, the reaction product of divinylbenzene and second butyl lithium and a small amount of 1,3-butadiene, etc. Furthermore, organic alkali metal compounds disclosed in, for example, US Patent No. 5,708,092, UK Patent No. 2,241,239, and US Patent No. 5,527,753 can also be used.
(調整劑) 例如於使用有機鹼金屬化合物作為聚合起始劑,將乙烯基芳香族化合物與共軛二烯共聚時,藉由使用特定之調整劑,可調整組入聚合物之起因於共軛二烯之乙烯基鍵(1,2鍵或3,4鍵)之含量或乙烯基芳香族化合物與共軛二烯之無規共聚性。 作為此種調整劑,並不限定於以下,例如可列舉:三級胺化合物、醚化合物、金屬醇鹽化物等。 調整劑可僅單獨使用一種,亦可組合兩種以上使用。(Adjuster) For example, when using an organic alkali metal compound as a polymerization initiator to copolymerize a vinyl aromatic compound with a conjugated diene, by using a specific modifier, the ethylene originating from the conjugated diene incorporated into the polymer can be adjusted. The content of radical bonds (1,2 bonds or 3,4 bonds) or the random copolymerization of vinyl aromatic compounds and conjugated dienes. Such an adjuster is not limited to the following, and examples thereof include tertiary amine compounds, ether compounds, metal alkoxides, and the like. The regulator may be used alone or in combination of two or more.
作為三級胺化合物,並不限定於以下,例如可應用通式R1R2R3N(此處,R1、R2,R3表示碳數1~20之烴基或具有三級胺基之烴基)所表示之化合物。 具體可列舉:三甲胺、三乙胺、三丁胺、N,N-二甲基苯胺、N-乙基哌啶、N-甲基吡咯啶、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四乙基乙二胺、1,2-二哌啶基乙烷、三甲胺基乙基哌𠯤、N,N,N',N'',N''-五甲基乙三胺、N,N'-二辛基-對苯二胺等。The tertiary amine compound is not limited to the following, for example, a compound represented by the general formula R1R2R3N (where R1, R2, and R3 represent a hydrocarbon group having 1 to 20 carbons or a hydrocarbon group having a tertiary amine group) can be used. Specific examples include: trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethyl ethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylaminoethylpiperone, N,N,N',N' ',N''-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, etc.
作為醚化合物,並不限定於以下,例如可應用:直鏈狀醚化合物及環狀醚化合物等。 作為直鏈狀醚化合物,並不限定於以下,例如可列舉:二甲醚、二乙醚、二苯醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚等乙二醇之二烷基醚化合物類、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丁醚等二乙二醇之二烷基醚化合物類。 作為環狀醚化合物,並不限定於以下,例如可列舉:四氫呋喃、二㗁烷、2,5-二甲基氧雜環戊烷、2,2,5,5-四甲基氧雜環戊烷、2,2-雙(2-氧雜環戊烷基)丙烷、呋喃甲醇之烷基醚等。As an ether compound, it is not limited to the following, For example, a linear ether compound, a cyclic ether compound, etc. are applicable. The linear ether compound is not limited to the following, and examples thereof include ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Dialkyl ether compounds of alcohols, dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. The cyclic ether compound is not limited to the following, for example, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane Alkanes, 2,2-bis(2-oxolane)propane, alkyl ethers of furanmethanol, etc.
作為金屬醇鹽化物,並不限定於以下,例如可列舉:第三戊醇鈉、第三丁醇鈉、第三戊醇鉀、第三丁醇鉀等。The metal alkoxide is not limited to the following, and examples thereof include sodium tert-pentoxide, sodium tert-butoxide, potassium tert-pentoxide, potassium tert-butoxide, and the like.
(聚合方法) 又,例如作為使用有機鹼金屬化合物作為聚合起始劑,將乙烯基芳香族化合物及共軛二烯聚合物聚合之方法,可應用先前公知之方法。 並不限定於以下,例如可為分批聚合、連續聚合、或該等之組合之任一者。尤其,為了獲得耐熱性優異之共聚物,較佳為分批聚合。 聚合溫度較佳為0℃~180℃,更佳為30℃~150℃。聚合時間根據條件而有所不同,通常為48小時以內,較佳為0.1~10小時。 又,作為聚合系統之環境,較佳為氮氣等惰性氣體環境。 聚合壓力設定為於上述溫度範圍中可將單體及溶劑維持為液相之壓力範圍即可,並無特別限定。 進而,較佳為留意使聚合系統內不會混入使觸媒及活性聚合物失活之雜質,例如水、氧、二氧化碳等。(aggregation method) Also, for example, as a method of polymerizing a vinyl aromatic compound and a conjugated diene polymer using an organic alkali metal compound as a polymerization initiator, a conventionally known method can be applied. It is not limited to the following, For example, any one of batch polymerization, continuous polymerization, or a combination thereof may be used. In particular, batch polymerization is preferred in order to obtain a copolymer excellent in heat resistance. The polymerization temperature is preferably from 0°C to 180°C, more preferably from 30°C to 150°C. The polymerization time varies depending on conditions, but is usually within 48 hours, preferably 0.1 to 10 hours. Also, as the environment of the polymerization system, an inert gas environment such as nitrogen is preferable. The polymerization pressure may be set to a pressure range in which the monomer and the solvent can be maintained in the liquid phase in the above temperature range, and is not particularly limited. Furthermore, it is preferable to prevent impurities such as water, oxygen, and carbon dioxide, which deactivate the catalyst and the active polymer, from being mixed into the polymerization system.
又,上述聚合步驟結束時,可添加必需量之雙官能以上之偶合劑,進行偶合反應。 作為雙官能偶合劑,可應用公知者,並無特別限定。例如可列舉:三甲氧基矽烷、三乙氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、二甲基二甲氧基矽烷、二乙基二甲氧基矽烷、二氯二甲氧基矽烷、二氯二乙氧基矽烷、三氯甲氧基矽烷、三氯乙氧基矽烷等烷氧基矽烷化合物、二氯乙烷、二溴乙烷、二甲基二氯矽烷、二甲基二溴矽烷等二鹵化合物、苯甲酸甲酯、苯甲酸乙酯、苯甲酸苯酯、鄰苯二甲酸酯類等酸酯類等。 又,作為三官能以上之多官能偶合劑,可應用先前公知者,並無特別限定。例如可列舉:三元以上之多元醇類、環氧化大豆油、二縮水甘油基雙酚A、1,3-雙(N-N'-二縮水甘油胺基甲基)環己烷等多元環氧化合物、通式R4 -nSiXn (此處,R表示碳數1~20之烴基,X表示鹵素,n表示3~4之整數)所表示之鹵化矽化合物,例如甲基三氯化矽烷、第三丁基三氯化矽烷、四氯化矽及該等之溴化物等、通式R4 -nSnXn (此處,R表示碳數1~20之烴基,X表示鹵素,n表示3~4之整數)所表示之鹵化錫化合物,例如甲基三氯化錫、第三丁基三氯化錫、四氯化錫等多鹵化合物。又,亦可使用碳酸二甲酯或碳酸二乙酯等。Also, at the end of the above-mentioned polymerization step, a necessary amount of a bifunctional or higher-functional coupling agent may be added to carry out a coupling reaction. Known ones can be used as the bifunctional coupling agent, and it is not particularly limited. Examples include: trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane Alkoxysilane compounds such as dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyl Dihalide compounds such as dibromosilane, esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. In addition, conventionally known ones can be used as the trifunctional or higher multifunctional coupling agent, and are not particularly limited. Examples include polyhydric alcohols with three or more valences, epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane and other polycyclic rings. Oxygen compounds, silicon halide compounds represented by the general formula R 4 -nSiX n (here, R represents a hydrocarbon group with 1 to 20 carbons, X represents a halogen, and n represents an integer of 3 to 4), such as methyl trichlorosilane , tertiary butyl trichlorosilane, silicon tetrachloride and their bromides, etc., general formula R 4 -nSnX n (here, R represents a hydrocarbon group with 1 to 20 carbons, X represents a halogen, and n represents 3 The tin halide compound represented by an integer of ~4), for example, polyhalogen compounds such as methyl tin trichloride, tertiary butyl tin trichloride, and tin tetrachloride. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used.
(改性步驟) 如上所述,本實施形態之氫化嵌段共聚物(一)可為鍵結有具有官能基之原子團之改性嵌段共聚物。具有官能基之原子團較佳為作為下述氫化步驟之前步驟而鍵結。 作為上述「具有官能基之原子團」,並無特別限定,例如可列舉:含有至少一種選自羥基、羧基、羰基、硫羰基、醯鹵化物基、酸酐基、羧酸基、硫羧酸基、醛基、硫醛基、羧酸酯基、醯胺基、磺酸基、磺酸酯基、磷酸基、磷酸酯基、胺基、亞胺基、腈基、吡啶基、喹啉基、環氧基、硫代環氧基、硫基、異氰酸酯基、異硫氰酸酯基、鹵化矽基、矽烷醇基、烷氧基矽基、鹵化錫基、硼酸基、含硼之基、硼酸鹽基、烷氧基錫基、苯基錫基等中之官能基之原子團。尤佳為具有至少一個選自羥基、環氧基、胺基、矽烷醇基、烷氧基矽烷基中之官能基之原子團。 上述「具有官能基之原子團」係藉由改性劑而鍵結。 作為改性劑,並無特別限定,例如可列舉:四縮水甘油基間苯二甲胺、四縮水甘油基-1,3-雙胺基甲基環己烷、ε-己內酯、δ-戊內酯、4-甲氧基二苯甲酮、γ-縮水甘油氧基乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基二甲基苯氧基矽烷、雙(γ-縮水甘油氧基丙基)甲基丙氧基矽烷、1,3-二甲基-2-咪唑啶酮、1,3-二乙基-2-咪唑啶酮、N,N'-二甲基伸丙基脲、N-甲基吡咯啶酮等。(modification step) As mentioned above, the hydrogenated block copolymer (1) of this embodiment may be a modified block copolymer bonded with an atomic group having a functional group. The atomic group having a functional group is preferably bonded as a step preceding the hydrogenation step described below. The above-mentioned "atomic group having a functional group" is not particularly limited, and examples include: containing at least one selected from the group consisting of hydroxyl, carboxyl, carbonyl, thiocarbonyl, acyl halide, acid anhydride, carboxylic acid, thiocarboxylic acid, Aldehyde, Thialdehyde, Carboxylate, Amide, Sulfonate, Sulfonate, Phosphate, Phosphate, Amino, Imino, Nitrile, Pyridyl, Quinolinyl, Cyclic Oxygen, thioepoxy, thio, isocyanate, isothiocyanate, silicon halide, silanol, alkoxy silicon, tin halide, boronic acid, boron-containing, borate The atomic group of the functional group in the group, the alkoxytin group, the phenyl tin group, etc. Especially preferably, it is an atomic group having at least one functional group selected from hydroxyl group, epoxy group, amino group, silanol group, and alkoxysilyl group. The above-mentioned "atomic group having a functional group" is bonded by a modifier. The modifier is not particularly limited, and examples thereof include tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ- Valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl dimethyl phenylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidine Ketone, N,N'-dimethylpropylidene urea, N-methylpyrrolidone, etc.
改性嵌段共聚物並無特別限定,例如可藉由如下方式獲得:藉由陰離子活性聚合,使用具有官能基之聚合起始劑或具有官能基之不飽和單體進行聚合,或於活性末端形成官能基,或使含有官能基之改性劑進行加成反應。 作為其他方法,可藉由如下方式獲得:使有機鋰化合物等有機鹼金屬化合物與嵌段共聚物反應(金屬化反應),使具有官能基之改性劑與加成了有機鹼金屬之嵌段聚合物進行加成反應。 其中,於後者之方法之情形時,亦可藉由於獲得氫化嵌段共聚物(一)後進行金屬化反應,其後使改性劑反應,而製作改性氫化嵌段共聚物。 進行改性反應之溫度較佳為0~150℃,更佳為20~120℃。改性反應所需之時間根據其他條件而有所不同,較佳為24小時以內,更佳為0.1~10小時。 根據所使用之改性劑之種類,亦存在於使改性劑反應之階段通常胺基等變為有機金屬鹽之情形,於該情形時,可藉由以水或醇等具有活性氫之化合物進行處理,而轉換為胺基等。再者,於此種改性共聚物中,改性共聚物中可混合存在一部分未改性之共聚物。The modified block copolymer is not particularly limited, and it can be obtained, for example, by anionic living polymerization, using a polymerization initiator with a functional group or an unsaturated monomer with a functional group to carry out polymerization, or at an active terminal Form a functional group, or make an addition reaction of a modifier containing a functional group. As another method, it can be obtained by reacting an organoalkali metal compound such as an organolithium compound with a block copolymer (metallation reaction), and making a modifier having a functional group react with a block copolymer to which an organoalkali metal has been added. The polymer undergoes an addition reaction. However, in the case of the latter method, a modified hydrogenated block copolymer can also be produced by performing a metallization reaction after obtaining the hydrogenated block copolymer (1), and then reacting a modifying agent. The temperature for the modification reaction is preferably 0-150°C, more preferably 20-120°C. The time required for the modification reaction varies depending on other conditions, but is preferably within 24 hours, more preferably 0.1 to 10 hours. Depending on the type of modifying agent used, there is also the case where the amino group etc. are converted into an organic metal salt at the stage of reacting the modifying agent. For processing, and conversion to amine groups, etc. In addition, in such a modified copolymer, a part of unmodified copolymer may be mixed in the modified copolymer.
又,上述改性嵌段共聚物可為二次改性嵌段共聚物。二次改性嵌段共聚物可藉由使與該改性嵌段共聚物之官能基具有反應性之二次改性劑與改性嵌段共聚物反應而獲得。 作為二次改性劑,並無特別限定,例如可列舉:具有選自羧基、酸酐基、異氰酸酯基、環氧基、矽烷醇基、烷氧基矽烷基中之官能基之改性劑,為具有至少2個選自該等官能基中之官能基者。 其中,於官能基為酸酐基之情形時,可為具備1個酸酐基者。In addition, the above-mentioned modified block copolymer may be a secondary modified block copolymer. The secondary modified block copolymer can be obtained by reacting a secondary modifier reactive with the functional group of the modified block copolymer with the modified block copolymer. The secondary modifier is not particularly limited, and examples include: modifiers having functional groups selected from carboxyl groups, acid anhydride groups, isocyanate groups, epoxy groups, silanol groups, and alkoxysilyl groups. Those having at least 2 functional groups selected from these functional groups. Among them, when the functional group is an acid anhydride group, one having one acid anhydride group may be used.
如上所述,於使二次改性劑與改性嵌段共聚物反應之情形時,相對於鍵結於改性嵌段共聚物之官能基每1當量,二次改性劑之使用量較佳為0.3~10莫耳,更佳為0.4~5莫耳,進而較佳為0.5~4莫耳。 關於使改性嵌段共聚物與二次改性劑反應之方法,可應用公知之方法,並無特別限定。例如可列舉:下述熔融混練方法、或者使各成分溶解或分散混合於溶劑等中並使之反應之方法等。再者,該等二次改性較佳為於氫化步驟後進行。As described above, when the secondary modifier is reacted with the modified block copolymer, the amount of the secondary modifier used is relatively small relative to 1 equivalent of the functional group bonded to the modified block copolymer. Preferably, it is 0.3-10 mol, More preferably, it is 0.4-5 mol, More preferably, it is 0.5-4 mol. A known method can be applied to the method of reacting the modified block copolymer with the secondary modifier, and it is not particularly limited. For example, the following melt-kneading method, or the method of dissolving or dispersing-mixing each component in a solvent etc., and making it react, etc. are mentioned. Furthermore, the secondary modification is preferably performed after the hydrogenation step.
作為二次改性劑,具體而言,較佳為順丁烯二酸酐、均苯四甲酸酐、1,2,4,5-苯四羧酸二酐、甲苯基二異氰酸酯、四縮水甘油基-1,3-雙胺基甲基環己烷、雙-(3-三乙氧基矽烷基丙基)-四硫化物等。As the secondary modifier, specifically, maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, tolyl diisocyanate, tetraglycidyl -1,3-bisaminomethylcyclohexane, bis-(3-triethoxysilylpropyl)-tetrasulfide, etc.
又,本實施形態之氫化嵌段共聚物(一)可為以α,β-不飽和羧酸或其衍生物,例如其酸酐、酯化物、醯胺化物、醯亞胺化物進行接枝改性之改性嵌段共聚物。 作為α,β-不飽和羧酸或其衍生物之具體例,並無特別限定,例如可列舉:順丁烯二酸酐、順丁烯二酸酐醯亞胺、丙烯酸或其酯、甲基丙烯酸或其酯、內-順-雙環[2,2,1]-5-庚烯-2,3-二羧酸或其酸酐等。 α,β-不飽和羧酸或其衍生物之加成量相對於氫化嵌段共聚物(一)每100質量份,較佳為0.01~20質量份,更佳為0.1~10質量份。 接枝改性之情形時之反應溫度較佳為100~300℃,更佳為120~280℃。 作為接枝改性之具體方法,並無特別限定,例如可應用日本專利特開昭62-79211號公報中記載之方法。In addition, the hydrogenated block copolymer (1) of this embodiment can be graft-modified with α,β-unsaturated carboxylic acid or its derivatives, such as its anhydride, esterified product, amidated product, and amidated product modified block copolymers. Specific examples of α,β-unsaturated carboxylic acids or derivatives thereof are not particularly limited, for example, maleic anhydride, maleic anhydride imide, acrylic acid or its esters, methacrylic acid or Its ester, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or its anhydride, etc. The added amount of the α,β-unsaturated carboxylic acid or its derivative is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass per 100 parts by mass of the hydrogenated block copolymer (1). In the case of graft modification, the reaction temperature is preferably from 100 to 300°C, more preferably from 120 to 280°C. The specific method of graft modification is not particularly limited, and for example, the method described in JP-A-62-79211 can be applied.
(氫化反應步驟) 本實施形態之氫化嵌段共聚物(一)係藉由使用特定之氫化觸媒將如上述之非氫化之非改性或改性嵌段共聚物供至氫化反應而獲得。 作為氫化觸媒,並無特別限定,例如可使用公知之觸媒,即(1)將Ni、Pt、Pd、Ru等金屬擔載於碳、二氧化矽、氧化鋁、矽藻土等而成之擔載型非均質氫化觸媒,(2)使用Ni、Co、Fe、Cr等之有機酸鹽或乙醯丙酮鹽等過渡金屬鹽與有機鋁等還原劑之所謂齊格勒型氫化觸媒,(3)Ti、Ru、Rh、Zr等之有機金屬化合物等所謂有機金屬錯合物等均質氫化觸媒。 具體而言,並不限定於以下,例如可使用:日本專利特公昭42-8704號公報、日本專利特公昭43-6636號公報、日本專利特公昭63-4841號公報、日本專利特公平1-37970號公報、日本專利特公平1-53851號公報、日本專利特公平2-9041號公報中記載之氫化觸媒。 作為較佳之氫化觸媒,可列舉:二茂鈦化合物、還原性有機金屬化合物、或該等之混合物。 作為二茂鈦化合物,並不限定於以下,例如可列舉日本專利特開平8-109219號公報中記載之化合物。具體可列舉:雙環戊二烯基二氯化鈦、單五甲基環戊二烯基三氯化鈦等具有至少1個以上具有(取代)環戊二烯基骨架、茚基骨架或茀基骨架之配位基之化合物。 作為還原性有機金屬化合物,並不限定於以下,例如可列舉:有機鋰等有機鹼金屬化合物、有機鎂化合物、有機鋁化合物、有機硼化合物或有機鋅化合物等。(hydrogenation reaction step) The hydrogenated block copolymer (1) of this embodiment is obtained by subjecting the above-mentioned non-hydrogenated non-modified or modified block copolymer to a hydrogenation reaction using a specific hydrogenation catalyst. The hydrogenation catalyst is not particularly limited, and for example, known catalysts can be used, that is, (1) metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc. (2) The so-called Ziegler type hydrogenation catalyst using organic acid salts such as Ni, Co, Fe, Cr or transition metal salts such as acetylacetonate and reducing agents such as organoaluminum , (3) Homogeneous hydrogenation catalysts such as organometallic compounds of Ti, Ru, Rh, Zr, etc., such as so-called organometallic complexes. Specifically, it is not limited to the following, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1- Hydrogenation catalysts described in Publication No. 37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041. As a preferable hydrogenation catalyst, a titanocene compound, a reducing organometallic compound, or a mixture thereof may be mentioned. The titanocene compound is not limited to the following, and examples thereof include compounds described in JP-A-8-109219. Specifically, dicyclopentadienyl titanium dichloride, monopentamethylcyclopentadienyl titanium trichloride, etc. have at least one (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fenene group. The compound of the ligand of the skeleton. The reducing organometallic compound is not limited to the following, and examples thereof include organoalkali metal compounds such as organolithium compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
對氫化反應進行說明。 反應溫度通常較佳為0~200℃之溫度範圍,更佳為30~150℃之溫度範圍。 氫化反應中所使用之氫之壓力較佳為0.1~15 MPa,更佳為0.2~10 MPa,進而較佳為0.3~5 MPa。 氫化反應時間通常較佳為3分鐘~10小時,更佳為10分鐘~5小時。 氫化反應可為分批製程、連續製程、或該等之組合之任一者。 較佳為視需要自經過氫化反應而獲得之氫化嵌段共聚物之溶液去除觸媒殘渣,將氫化嵌段共聚物自溶液分離。 作為分離方法,並不限定於以下,例如可列舉:於氫化後之反應液中添加丙酮或醇等對氫化改性共聚物而言為不良溶劑之極性溶劑而使聚合物沈澱並回收的方法;將反應液於攪拌下投入熱水中,藉由蒸汽汽提而去除溶劑並回收的方法;直接加熱聚合物溶液而蒸餾去除溶劑之方法等。 再者,本實施形態之氫化嵌段共聚物(一)中可添加各種酚系穩定劑、磷系穩定劑、硫系穩定劑、胺系穩定劑等穩定劑。The hydrogenation reaction will be described. The reaction temperature is generally preferably in the temperature range of 0-200°C, more preferably in the temperature range of 30-150°C. The pressure of hydrogen used in the hydrogenation reaction is preferably from 0.1 to 15 MPa, more preferably from 0.2 to 10 MPa, and still more preferably from 0.3 to 5 MPa. The hydrogenation reaction time is usually preferably from 3 minutes to 10 hours, more preferably from 10 minutes to 5 hours. The hydrogenation reaction can be any one of a batch process, a continuous process, or a combination thereof. It is preferable to remove catalyst residue from the solution of the hydrogenated block copolymer obtained through the hydrogenation reaction as necessary, and to separate the hydrogenated block copolymer from the solution. The separation method is not limited to the following, and examples include: adding a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated modified copolymer, to the reaction liquid after hydrogenation to precipitate and recover the polymer; The method of putting the reaction liquid into hot water under stirring, removing the solvent by steam stripping and recovering it; the method of directly heating the polymer solution to distill and remove the solvent, etc. Furthermore, various stabilizers such as phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers can be added to the hydrogenated block copolymer (1) of this embodiment.
[氫化嵌段共聚物組合物] 本實施形態之氫化嵌段共聚物組合物含有上述(一)氫化嵌段共聚物:1質量%以上95質量%以下、及(二)至少一種烯烴系樹脂:5質量%以上99質量%以下。[Hydrogenated block copolymer composition] The hydrogenated block copolymer composition of the present embodiment contains the above-mentioned (1) hydrogenated block copolymer: 1 mass % to 95 mass %, and (2) at least one olefin resin: 5 mass % to 99 mass %.
((二)烯烴系樹脂) 以下對構成本實施形態之氫化嵌段共聚物組合物之烯烴系樹脂(二)加以說明。 作為烯烴系樹脂(二),並不限定於以下,例如可列舉:聚乙烯(PE)、聚丙烯(PP)、1-丁烯、1-戊烯、1-己烯、3-甲基-1-丁烯、4-甲基-1-戊烯、1-辛烯等α-烯烴類之均聚物。又可列舉:包含選自乙烯、丙烯、丁烯、戊烯、己烯、辛烯等中之烯烴之組合之無規共聚物或嵌段共聚物。 具體可列舉:乙烯-丙烯共聚物、乙烯-1-丁烯共聚物、乙烯-3-甲基-1-丁烯共聚物、乙烯-4-甲基-1-戊烯共聚物、乙烯-1-己烯共聚物、乙烯-1-辛烯共聚物、乙烯-1-癸烯共聚物、丙烯-1-丁烯共聚物、丙烯-1-己烯共聚物、丙烯-1-辛烯共聚物、丙烯-4-甲基-1-戊烯共聚物、乙烯-丙烯-1-丁烯共聚物、丙烯-1-己烯-乙烯共聚物、丙烯-1-辛烯-乙烯共聚物等乙烯及/或丙烯-α-烯烴共聚物。 又,作為與乙烯及/或丙烯之共聚物,亦包含與其他不飽和單體之共聚物。 作為上述與其他不飽和單體之共聚物,並不限定於以下,例如可列舉:乙烯及/或丙烯與丙烯酸、甲基丙烯酸、順丁烯二酸、伊康酸、丙烯酸甲酯、甲基丙烯酸甲酯、順丁烯二酸酐、芳基順丁烯二醯亞胺、烷基順丁烯二醯亞胺等不飽和有機酸或其衍生物之共聚物;乙烯及/或丙烯與乙酸乙烯酯等乙烯酯類之共聚物;進而乙烯及/或丙烯與二環戊二烯、4-亞乙基-2-降𦯉烯、4-甲基-1,4-己二烯、5-甲基-1,4-己二烯等非共軛二烯等之共聚物。 作為(二)烯烴系樹脂,就經濟性或使本實施形態之氫化嵌段共聚物組合物中之相溶性變得良好,獲得高透明性之觀點而言,較佳為含有至少一種聚丙烯系樹脂。((2) Olefin resin) The olefin-based resin (2) constituting the hydrogenated block copolymer composition of this embodiment will be described below. The olefin-based resin (2) is not limited to the following, for example, polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl- Homopolymers of α-olefins such as 1-butene, 4-methyl-1-pentene, and 1-octene. Further examples include: random copolymers or block copolymers containing combinations of olefins selected from ethylene, propylene, butene, pentene, hexene, octene, and the like. Specifically, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1 -hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer , propylene-4-methyl-1-pentene copolymer, ethylene-propylene-1-butene copolymer, propylene-1-hexene-ethylene copolymer, propylene-1-octene-ethylene copolymer and other ethylene and /or propylene-α-olefin copolymers. In addition, copolymers with ethylene and/or propylene also include copolymers with other unsaturated monomers. The above-mentioned copolymers with other unsaturated monomers are not limited to the following, for example, ethylene and/or propylene and acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl Copolymers of methyl acrylate, maleic anhydride, arylmaleimide, alkylmaleimide and other unsaturated organic acids or their derivatives; ethylene and/or propylene and vinyl acetate Copolymers of vinyl esters such as esters; furthermore, ethylene and/or propylene with dicyclopentadiene, 4-ethylidene-2-northene, 4-methyl-1,4-hexadiene, 5-methanol Copolymers of non-conjugated dienes such as 1,4-hexadiene, etc. The (2) olefin-based resin preferably contains at least one polypropylene-based resin.
又,烯烴系樹脂(二)可為藉由特定之官能基而改性者。 作為官能基,並無特別限定,例如可列舉:環氧基、羧基、酸酐、羥基等。 作為用以使烯烴系樹脂(二)改性之含官能基之化合物或改性劑,並無特別限定,例如可列舉下述化合物。 例如可列舉:甲基丙烯酸縮水甘油酯、丙烯酸縮水甘油酯、乙烯基縮水甘油醚、烯丙基縮水甘油醚等不飽和環氧化物、或順丁烯二酸、反丁烯二酸、伊康酸、甲基順丁烯二酸、烯丙基琥珀酸、順丁烯二酸酐、反丁烯二酸酐、伊康酸酐等不飽和有機酸等。 其他並無特別限定,例如可列舉:離子聚合物、氯化聚烯烴等。Also, the olefin-based resin (2) may be modified with a specific functional group. It does not specifically limit as a functional group, For example, an epoxy group, a carboxyl group, an acid anhydride, a hydroxyl group etc. are mentioned. Although it does not specifically limit as a functional group containing compound or modifier used for modifying olefin resin (2), For example, the following compounds are mentioned. For example, unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether, or maleic acid, fumaric acid, icon acid, unsaturated organic acids such as methylmaleic acid, allylsuccinic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, etc. Others are not particularly limited, and examples thereof include ionomers, chlorinated polyolefins, and the like.
作為烯烴系樹脂(二),就經濟性、或使本實施形態之氫化嵌段共聚物組合物中之相容性變得良好,獲得高透明性之觀點而言,較佳為聚丙烯均聚物、乙烯-丙烯無規或嵌段共聚物等聚丙烯系樹脂。 尤其,就透明性、柔軟性之觀點而言,更佳為乙烯-丙烯無規共聚物。 烯烴系樹脂(二)可包含僅一種之單獨之材料,亦可併用兩種以上。The olefin-based resin (2) is preferably a polypropylene homopolymer from the standpoint of economical efficiency, improved compatibility in the hydrogenated block copolymer composition of the present embodiment, and high transparency. Polypropylene-based resins such as ethylene-propylene random or block copolymers. In particular, an ethylene-propylene random copolymer is more preferable from the viewpoint of transparency and flexibility. The olefin-based resin (2) may contain only one kind of material alone, or two or more kinds may be used in combination.
本實施形態之氫化嵌段共聚物組合物係含有氫化嵌段共聚物(一)及至少一種烯烴系樹脂(二)者,氫化嵌段共聚物(一)之含量為1質量%以上95質量%以下,更佳為1質量%以上90質量%以下,進而較佳為1質量%以上85質量%以下。 若氫化嵌段共聚物(一)之含量為1質量%以上,則存在氫化嵌段共聚物組合物之耐磨耗性提高,硬度下降之傾向。另一方面,若氫化嵌段共聚物(一)之含量為95質量%以下,則存在氫化嵌段共聚物組合物之耐磨耗性提高之傾向。The hydrogenated block copolymer composition of this embodiment is a hydrogenated block copolymer (1) and at least one olefin-based resin (2), and the content of the hydrogenated block copolymer (1) is 1% by mass to 95% by mass Below, more preferably 1 mass % or more and 90 mass % or less, More preferably, it is 1 mass % or more and 85 mass % or less. When the content of the hydrogenated block copolymer (1) is 1% by mass or more, the abrasion resistance of the hydrogenated block copolymer composition tends to increase and the hardness tends to decrease. On the other hand, when the content of the hydrogenated block copolymer (1) is 95% by mass or less, the abrasion resistance of the hydrogenated block copolymer composition tends to improve.
本實施形態之氫化嵌段共聚物組合物除上述氫化嵌段共聚物(一)、聚烯烴系樹脂(二)以外,亦可調配任意之橡膠用軟化劑或改質劑、添加劑等。 橡膠用軟化劑使本實施形態之氫化嵌段共聚物組合物柔軟化,且賦予流動性(成形加工性)。 作為橡膠用軟化劑,並不限定於以下,例如可應用礦物油或者液狀或低分子量之合成軟化劑,尤佳為環烷系及/或石蠟系之加工處理油或增量油。 礦物油系橡膠用軟化劑為芳香族環、環烷環及石蠟鏈之混合物,石蠟鏈之碳數占全部碳之50%以上者被稱為石蠟系,環烷環之碳數為30~45%者被稱為環烷系,又芳香族碳數超過30%者被稱為芳香族系。 作為合成軟化劑,例如可使用聚丁烯、低分子量聚丁二烯、液態石蠟等,更佳為上述礦物油系橡膠用軟化劑。 於要求本實施形態之氫化嵌段共聚物組合物具有高耐熱性、機械物性之情形時,較佳為所應用之礦物油系橡膠用軟化劑之40℃之動黏度為60 cst以上,較佳為120 cst以上。 橡膠用軟化劑可僅單獨一種使用,亦可併用兩種以上。 改質劑係具有提高本實施形態之氫化嵌段共聚物組合物之表面之耐損傷性或改良黏著性之功能者。 作為改質劑,並不限定於以下,例如可應用有機聚矽氧烷。其發揮氫化嵌段共聚物組合物之表面改質效果,且作為耐磨耗性改善助劑而發揮功能。 作為改質劑之形態,可為低黏度之液狀~高黏度之液狀物、固體狀之任一者,就確保於本實施形態之氫化嵌段共聚物組合物中之良好之分散性之觀點而言,較佳為液狀物,即矽油。進而關於動黏度,就抑制聚矽氧烷自身之滲出之觀點而言,較佳為90 cst以上,更佳為1000 cst以上。作為聚矽氧烷之具體例,並不限定於以下,例如可列舉:二甲基聚矽氧烷、甲基苯基聚矽氧烷等通用矽油或烷基改性、聚醚改性、氟改性、醇改性、胺基改性、環氧改性等各種改性矽油。就作為耐磨耗性改善助劑之效果較高之方面而言,較佳為二甲基聚矽氧烷,但無特別限制。該等有機聚矽氧烷可僅單獨使用一種,亦可併用兩種以上。 作為添加劑,為填充劑、潤滑劑、脫模劑、塑化劑、抗氧化劑、熱穩定劑、光穩定劑、紫外線吸收劑、阻燃劑、抗靜電劑、補強劑、著色劑,只要為熱塑性樹脂或橡膠狀聚合物之調配中通常所使用者,則並無特別限制。 作為填充劑,並不限定於以下,例如可列舉:二氧化矽、滑石、雲母、矽酸鈣、鋁碳酸鎂、高嶺土、矽藻土、石墨、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、硫酸鈣、硫酸鋇等無機填充劑、碳黑等有機填充劑。 作為潤滑劑,並不限定於以下,例如可列舉:硬脂酸、山萮酸、硬脂酸鋅、硬脂酸鈣、硬脂酸鎂、伸乙基雙硬脂醯胺等。 作為塑化劑,並不限定於以下,例如可列舉:有機聚矽氧烷、礦物油等。 作為抗氧化劑,並不限定於以下,例如可列舉:受阻酚系抗氧化劑。 作為熱穩定劑,並不限定於以下,例如可列舉:磷系、硫系及胺系熱穩定劑等。 作為光穩定劑,並不限定於以下,例如可列舉:受阻胺系光穩定劑。 作為紫外線吸收劑,並不限定於以下,例如可列舉:苯并三唑系紫外線吸收劑。 作為補強劑,並不限定於以下,例如可列舉:有機纖維、玻璃纖維、碳纖維、金屬晶鬚等。 作為著色劑,並不限定於以下,例如可列舉:氧化鈦、氧化鐵、碳黑等。 其他可列舉:「橡膠-塑膠調配藥品」(Rubber Digest公司編著)等中記載者。In addition to the hydrogenated block copolymer (1) and polyolefin resin (2) mentioned above, the hydrogenated block copolymer composition of this embodiment may also contain any rubber softener or modifier, additives, and the like. The softener for rubber softens the hydrogenated block copolymer composition of this embodiment and imparts fluidity (moldability). The softener for rubber is not limited to the following, for example, mineral oil or liquid or low molecular weight synthetic softener can be used, especially naphthenic and/or paraffinic processing oil or extender oil. Mineral oil-based softener for rubber is a mixture of aromatic rings, naphthenic rings and paraffin chains. Those whose carbon number in the paraffin chain accounts for more than 50% of the total carbons are called paraffin-based, and the carbon number of the naphthene ring is 30-45. % are called naphthenic series, and those with more than 30% aromatic carbons are called aromatic series. As the synthetic softener, for example, polybutene, low-molecular-weight polybutadiene, liquid paraffin, etc. can be used, and the above-mentioned softener for mineral oil-based rubber is more preferable. When the hydrogenated block copolymer composition of this embodiment is required to have high heat resistance and mechanical properties, it is preferable that the applied mineral oil-based rubber softener has a dynamic viscosity of 60 cst or more at 40°C, preferably It is above 120 cst. The rubber softener may be used alone or in combination of two or more. The modifier has the function of improving the damage resistance of the surface of the hydrogenated block copolymer composition of this embodiment or improving the adhesion. The modifying agent is not limited to the following, for example, organopolysiloxane can be used. It exerts the surface modification effect of the hydrogenated block copolymer composition and functions as an abrasion resistance improving auxiliary agent. As the form of the modifying agent, it can be any of low-viscosity liquid to high-viscosity liquid or solid, and it is necessary to ensure good dispersibility in the hydrogenated block copolymer composition of this embodiment. From the point of view, it is preferably a liquid, that is, silicone oil. Furthermore, the kinematic viscosity is preferably 90 cst or more, more preferably 1000 cst or more, from the viewpoint of suppressing exudation of polysiloxane itself. The specific examples of polysiloxane are not limited to the following. Modified, alcohol modified, amino modified, epoxy modified and other modified silicone oils. In terms of its high effect as an abrasion resistance improving auxiliary agent, dimethylpolysiloxane is preferred, but not particularly limited. These organopolysiloxanes may be used alone or in combination of two or more. As additives, fillers, lubricants, mold release agents, plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, reinforcing agents, colorants, as long as they are thermoplastic There are no particular restrictions on the usual use in the formulation of resins or rubbery polymers. The filler is not limited to the following, for example, silicon dioxide, talc, mica, calcium silicate, aluminum magnesium carbonate, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, hydroxide Aluminum, calcium sulfate, barium sulfate and other inorganic fillers, carbon black and other organic fillers. The lubricant is not limited to the following, and examples thereof include stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylidenebisstearamide, and the like. It is not limited to the following as a plasticizer, For example, organopolysiloxane, mineral oil, etc. are mentioned. It is not limited to the following as an antioxidant, For example, a hindered phenol type antioxidant is mentioned. The heat stabilizer is not limited to the following, and examples thereof include phosphorus-based, sulfur-based, and amine-based heat stabilizers. It is not limited to the following as a light stabilizer, For example, a hindered amine light stabilizer is mentioned. The ultraviolet absorber is not limited to the following, and examples thereof include benzotriazole-based ultraviolet absorbers. The reinforcing agent is not limited to the following, and examples thereof include organic fibers, glass fibers, carbon fibers, metal whiskers, and the like. It is not limited to the following as a coloring agent, For example, titanium oxide, iron oxide, carbon black, etc. are mentioned. Other examples include those described in "Rubber-Plastic Compounded Drugs" (edited by Rubber Digest Co., Ltd.).
本實施形態之氫化嵌段共聚物組合物可藉由先前公知之方法而製造。 本實施形態之氫化嵌段共聚物組合物之製造方法並不限定於以下,例如可使用:使用班布里混合機、單螺桿擠出機、雙螺桿擠出機、雙向捏合機、多螺桿擠出機等混合機,將各成分(上述氫化嵌段共聚物(一)與聚烯烴系樹脂(二)、其他添加劑)熔融混練的方法;將各成分溶解或分散混合後,加熱去除溶劑的方法等。 尤其,藉由擠出機之熔融混練法就生產性、優良混練性之觀點而言較佳。 關於本實施形態之氫化嵌段共聚物組合物之形狀,並不限定於以下,例如可為顆粒狀、片狀、股線狀、小片狀等任意形狀。又,可於熔融混練後,直接製作成形品。The hydrogenated block copolymer composition of the present embodiment can be produced by a previously known method. The production method of the hydrogenated block copolymer composition of this embodiment is not limited to the following, for example, it can be used: using a Banbury mixer, a single-screw extruder, a twin-screw extruder, a two-way kneader, a multi-screw extruder A mixer such as a discharge machine, a method of melting and kneading each component (the above-mentioned hydrogenated block copolymer (1), polyolefin resin (2), and other additives); a method of removing the solvent by heating after dissolving or dispersing and mixing each component wait. In particular, the melt-kneading method with an extruder is preferable from the viewpoint of productivity and excellent kneading properties. The shape of the hydrogenated block copolymer composition of the present embodiment is not limited to the following, and may be in any shape such as granular, sheet, strand, or small sheet, for example. Also, molded products can be produced directly after melting and kneading.
[使用有氫化嵌段共聚物組合物之成形體] 本實施形態之成形體係上述本實施形態之氫化嵌段共聚物組合物之成形體。 本實施形態之氫化嵌段共聚物組合物並無特別限定,例如可藉由擠出成形、射出成形、雙色射出成形、三明治成形、中空成形、壓縮成形、真空成形、旋轉成形、粉末凝塑成形、發泡成形、積層成形、壓延成形、吹塑成形等,加工為實用上有用之成形體。 作為本實施形態之成形體,並無特別限定,例如可列舉片材、膜、各種形狀之射出成形體、中空成形體、壓空成形體、真空成形體、擠出成形體、發泡成形體、不織布或纖維狀之成形體、合成皮革等多種多樣之成形體。 該等成形體例如可用於汽車用零件、食品包裝材料、醫療器具、家電製品構件、電子裝置構件、建築材料、工業零件、家庭用品、玩具素材、鞋類用素材、纖維素材等。[Molded article using hydrogenated block copolymer composition] Molding system of this embodiment is a molded body of the hydrogenated block copolymer composition of this embodiment. The hydrogenated block copolymer composition of this embodiment is not particularly limited, for example, it can be formed by extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder gel molding , foam molding, lamination molding, calender molding, blow molding, etc., and process them into practically useful moldings. The molded article of this embodiment is not particularly limited, and examples thereof include sheets, films, injection molded articles of various shapes, hollow molded articles, pressure molded articles, vacuum formed articles, extrusion molded articles, and foam molded articles. , non-woven fabric or fibrous shaped body, synthetic leather and other various shaped bodies. Such molded articles can be used, for example, in automotive parts, food packaging materials, medical devices, home appliance components, electronic device components, construction materials, industrial parts, household goods, toy materials, shoe materials, fiber materials, and the like.
作為汽車用零件,並不限定於以下,例如可列舉:側飾條、密封墊、排檔頭、防風雨襯條、窗框與其密封材、扶手、輔助握把、車門拉手、手柄、控制台盒、頭枕、儀錶板、保險杠、擾流板、安全氣囊蓋板等。 作為醫療器具,並不限定於以下,例如可列舉:醫療用管(tube)、醫療用軟管(hose)、導管、採血袋、輸液袋、血小板保存袋、人工透析用袋等。 作為建築材料,並不限定於以下,例如可列舉:壁材、地板材等。 其他並無特別限定,例如可列舉:工業用軟管、食品用軟管、吸塵器軟管、電冷密封件、電線及其他各種被覆材、握把用被覆材、軟質人偶等。 可對本實施形態之成形體適宜施加發泡、粉末、延伸、接著、印刷、塗裝、鍍覆等加工。 本實施形態之氫化嵌段共聚物組合物表現出柔軟性、低反跳彈性、透明性、耐扭結性優異之效果,故而作為軟管、管等中空狀之成形體之材料極其有用。The automotive parts are not limited to the following, and examples include: side moldings, gaskets, gear knobs, weather strips, window frames and their sealants, armrests, auxiliary grips, door handles, handles, and console boxes , Headrests, dashboards, bumpers, spoilers, airbag covers, etc. The medical equipment is not limited to the following, and examples include medical tubes, medical hoses, catheters, blood collection bags, transfusion bags, platelet storage bags, artificial dialysis bags, and the like. It is not limited to the following as a building material, For example, a wall material, a floor material, etc. are mentioned. Others are not particularly limited, and examples thereof include industrial hoses, food hoses, vacuum cleaner hoses, electric cooling seals, electric wires, and other various covering materials, covering materials for grips, soft dolls, and the like. Processes such as foaming, powdering, stretching, bonding, printing, painting, and plating can be appropriately applied to the molded body of this embodiment. The hydrogenated block copolymer composition of this embodiment exhibits excellent effects of flexibility, low rebound elasticity, transparency, and kink resistance, so it is extremely useful as a material for hollow molded objects such as hoses and tubes.
(補強性填充劑調配物) 可於本實施形態之氫化嵌段共聚物或氫化嵌段共聚物組合物(以下,有時記為成分(A))中調配選自二氧化矽系無機填充劑、金屬氧化物、金屬氫氧化物、金屬碳酸化物、碳黑中之至少一種補強性填充劑(以下,有時記為成分(C)),從而製備補強性填充劑調配物。 補強性填充劑調配物中之成分(C)之調配量相對於氫化嵌段共聚物或氫化嵌段共聚物組合物100質量份較佳為0.5~100質量份,更佳為5~100質量份,進而較佳為20~80質量份。 於使用本實施形態之氫化嵌段共聚物或氫化嵌段共聚物組合物(成分(A))製備上述補強性填充劑調配物之情形時,較佳為進而包含相對於成分(A)100質量份為0~500質量份,較佳為5~300質量份,更佳為10~200質量份之與上述本實施形態之氫化嵌段共聚物及上述烯烴系樹脂(二)不同之熱塑性樹脂及/或橡膠狀聚合物(以下,有時記為成分(B))。(reinforcing filler formulation) In the hydrogenated block copolymer or the hydrogenated block copolymer composition (hereinafter, sometimes referred to as component (A)) of this embodiment, a filler selected from silica-based inorganic fillers, metal oxides, and metal hydroxides can be formulated. At least one reinforcing filler (hereinafter, sometimes referred to as component (C)) among compound, metal carbonate, and carbon black to prepare a reinforcing filler formulation. The compounded amount of the component (C) in the reinforcing filler formulation is preferably 0.5-100 parts by mass, more preferably 5-100 parts by mass relative to 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition , and more preferably 20 to 80 parts by mass. In the case of using the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)) of this embodiment to prepare the aforementioned reinforcing filler formulation, it is preferable to further include 100 mass of component (A) The parts are 0 to 500 parts by mass, preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass of a thermoplastic resin different from the hydrogenated block copolymer of the present embodiment and the olefin-based resin (2) above and /or a rubbery polymer (hereinafter, may be referred to as component (B)).
作為上述熱塑性樹脂及/或橡膠狀聚合物(成分(B)),例如可列舉:乙烯基芳香族單體單元含量超過60質量%之共軛二烯單體與乙烯基芳香族單體之嵌段共聚樹脂及其氫化物(但與本實施形態之氫化嵌段共聚物(A)不同);上述乙烯基芳香族單體之聚合物;上述乙烯基芳香族單體與其他乙烯基單體(例如乙烯、丙烯、丁烯、氯乙烯、偏二氯乙烯、乙酸乙烯酯、丙烯酸及丙烯酸甲酯等丙烯酸酯、甲基丙烯酸及甲基丙烯酸甲酯等甲基丙烯酸酯、丙烯腈、甲基丙烯腈等)之共聚樹脂;橡膠改性苯乙烯系樹脂(HIPS);丙烯腈-丁二烯-苯乙烯共聚樹脂(ABS);甲基丙烯酸酯-丁二烯-苯乙烯共聚樹脂(MBS);聚乙烯;乙烯-丙烯共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、乙烯-辛烯共聚物、乙烯-乙酸乙烯酯共聚物及其水解物等包含乙烯與其他可共聚之單體之乙烯含量為50質量%以上之共聚物;乙烯-丙烯酸離子聚合物或氯化聚乙烯等聚乙烯系樹脂;聚丙烯;丙烯-乙烯共聚物、丙烯-丙烯酸乙酯共聚物或氯化聚丙烯等聚丙烯系樹脂、乙烯-降𦯉烯樹脂等環狀烯烴系樹脂、聚丁烯系樹脂、聚氯乙烯系樹脂、聚乙酸乙烯酯系樹脂及其水解物等包含丙烯與其他可共聚之單體之丙烯含量為50質量%以上之共聚物;丙烯酸及其酯或醯胺之聚合物;聚丙烯酸酯系樹脂;丙烯腈及/或甲基丙烯腈之聚合物;包含丙烯腈系單體與其他可共聚之單體之丙烯腈系單體含量為50質量%以上之共聚物,即腈樹脂;尼龍-46、尼龍-6、尼龍-66、尼龍-610、尼龍-11、尼龍-12、尼龍-6、尼龍-12共聚物等聚醯胺系樹脂;聚酯系樹脂;熱塑性聚胺基甲酸酯系樹脂;聚-4,4'-二氧基二苯基-2,2'-丙烷碳酸酯等聚碳酸酯系聚合物;聚醚碸或聚芳碸等熱塑性聚碸;聚甲醛系樹脂;聚(2,6-二甲基-1,4-伸苯基)醚等聚苯醚系樹脂;聚苯硫醚、聚4,4'-二伸苯基硫醚等聚苯硫醚系樹脂;聚芳酯系樹脂;聚醚酮聚合物或共聚物;聚酮系樹脂;氟系樹脂;聚氧基苯甲醯基系聚合物;聚醯亞胺系樹脂;1,2-聚丁二烯、反式聚丁二烯等聚丁二烯系樹脂等。 該等成分(B)可為鍵結有含羥基、環氧基、胺基、羧酸基、酸酐基等極性基之原子團者。Examples of the above-mentioned thermoplastic resin and/or rubber-like polymer (component (B)) include a combination of a conjugated diene monomer and a vinyl aromatic monomer having a vinyl aromatic monomer unit content of more than 60% by mass. Segment copolymer resin and its hydrogenated product (but different from the hydrogenated block copolymer (A) of this embodiment); the polymer of the above-mentioned vinyl aromatic monomer; the above-mentioned vinyl aromatic monomer and other vinyl monomers ( For example, ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and methyl acrylate and other acrylates, methacrylic acid and methyl methacrylate and other methacrylates, acrylonitrile, methacrylic Nitrile, etc.) copolymer resin; rubber modified styrene resin (HIPS); acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene-styrene copolymer resin (MBS); Polyethylene; ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer and its hydrolyzate, etc., containing ethylene and other copolymerizable monomers Copolymers with an ethylene content of more than 50% by mass; polyethylene-based resins such as ethylene-acrylic acid ionomers or chlorinated polyethylene; polypropylene; propylene-ethylene copolymers, propylene-ethyl acrylate copolymers or chlorinated poly Polypropylene-based resins such as propylene, cyclic olefin-based resins such as ethylene-northene resins, polybutene-based resins, polyvinyl chloride-based resins, polyvinyl acetate-based resins and their hydrolyzates, etc., including propylene and other copolymerizable resins Copolymers with a propylene content of 50 mass% or more of the monomers; polymers of acrylic acid and its esters or amides; polyacrylate resins; polymers of acrylonitrile and/or methacrylonitrile; containing acrylonitrile monomers Copolymers containing more than 50% by mass of acrylonitrile monomers with other copolymerizable monomers, i.e. nitrile resins; Nylon-46, Nylon-6, Nylon-66, Nylon-610, Nylon-11, Nylon-12 , nylon-6, nylon-12 copolymers and other polyamide resins; polyester resins; thermoplastic polyurethane resins; poly-4,4'-dioxydiphenyl-2,2' -Polycarbonate-based polymers such as propane carbonate; thermoplastic polymers such as polyether or polyarylene; polyoxymethylene-based resins; poly(2,6-dimethyl-1,4-phenylene) ether and other polycarbonates Phenyl ether resins; polyphenylene sulfide, polyphenylene sulfide, poly4,4'-diphenylene sulfide and other polyphenylene sulfide resins; polyarylate resins; polyetherketone polymers or copolymers; polyketone resins; Fluorine-based resins; polyoxybenzoyl-based polymers; polyimide-based resins; polybutadiene-based resins such as 1,2-polybutadiene and trans-polybutadiene, etc. These components (B) may be bonded with atomic groups containing polar groups such as hydroxyl groups, epoxy groups, amine groups, carboxylic acid groups, and acid anhydride groups.
用作補強性填充劑(成分(C))之二氧化矽系無機填充劑係以化學式SiO2 為結構單元之主成分之固體粒子,例如可列舉:二氧化矽、黏土、滑石、高嶺土、雲母、矽灰石、蒙脫石、沸石、玻璃纖維等無機纖維狀物質等。又,亦可使用將表面疏水化之二氧化矽系無機填充劑或二氧化矽系無機填充劑與二氧化矽系以外之無機填充劑之混合物。作為二氧化矽系無機填充劑,較佳為二氧化矽及玻璃纖維。作為二氧化矽,可使用稱為乾式法白碳、濕式法白碳、合成矽酸鹽系白碳,膠體二氧化矽者等。 二氧化矽系無機填充劑較佳為平均粒徑為0.01~150 μm者,為使二氧化矽系無機填充劑分散於補強性填充劑調配物中,充分發揮其添加效果,平均分散粒徑較佳為0.05~1 μm,更佳為0.05~0.5 μm。The silica-based inorganic filler used as a reinforcing filler (ingredient (C)) is a solid particle with the chemical formula SiO2 as the main component of the structural unit, for example: silica, clay, talc, kaolin, mica , Wollastonite, montmorillonite, zeolite, glass fiber and other inorganic fibrous substances. In addition, a silica-based inorganic filler that hydrophobizes the surface, or a mixture of a silica-based inorganic filler and an inorganic filler other than silica-based fillers may also be used. As the silica-based inorganic filler, silica and glass fiber are preferred. As silica, what is called dry-process white carbon, wet-process white carbon, synthetic silicate white carbon, colloidal silica, etc. can be used. The silica-based inorganic filler is preferably one with an average particle size of 0.01-150 μm. In order to disperse the silica-based inorganic filler in the reinforcing filler formulation and fully exert its addition effect, the average dispersed particle diameter is Preferably it is 0.05-1 μm, more preferably 0.05-0.5 μm.
用作補強性填充劑(成分(C))之金屬氧化物係以化學式MxOy(M為金屬原子,x、y分別為1~6之整數)為結構單元之主成分之固體粒子,例如氧化鋁、氧化鈦、氧化鎂、氧化鋅等。又,可使用金屬氧化物與金屬氧化物以外之無機填充劑之混合物。 用作補強性填充劑之金屬氫氧化物係氫氧化鋁、氫氧化鎂、氫氧化鋯、水合矽酸鋁、水合矽酸鎂、鹼性碳酸鎂、水滑石、氫氧化鈣、氫氧化鋇、氧化錫之水合物、硼砂等無機金屬化合物之水合物等水合系無機填充材,其中較佳為氫氧化鎂與氫氧化鋁。 作為用作補強性填充劑之金屬碳酸化物,可列舉:碳酸鈣、碳酸鎂等。 又,作為補強性填充劑,可使用FT(Fine thermal,細粒子熱裂法爐黑)、SRF(semi-reinforcing furnace,半補強爐黑)、FEF(fast extrusion furnace,快壓出爐黑)、HAF(high abrasion furnace,高耐磨爐黑)、ISAF(Intermediate super abrasion furnace,中超耐磨爐黑)、SAF(super abrasion furnace,超耐磨爐黑)等各等級之碳黑,較佳為氮吸附比表面積為50 mg/g以上,DBP(鄰苯二甲酸二丁酯)吸油量為80 mL/100 g之碳黑。The metal oxide used as a reinforcing filler (ingredient (C)) is a solid particle with the chemical formula MxOy (M is a metal atom, and x and y are integers from 1 to 6) as the main component of the structural unit, such as alumina , titanium oxide, magnesium oxide, zinc oxide, etc. In addition, a mixture of a metal oxide and an inorganic filler other than the metal oxide can be used. Metal hydroxide aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, Hydrated inorganic fillers such as hydrates of tin oxide and hydrates of inorganic metal compounds such as borax, among which magnesium hydroxide and aluminum hydroxide are preferred. Calcium carbonate, magnesium carbonate, etc. are mentioned as a metal carbonate used as a reinforcing filler. Also, as a reinforcing filler, FT (Fine thermal, fine particle thermal cracking furnace black), SRF (semi-reinforcing furnace, semi-reinforcing furnace black), FEF (fast extrusion furnace, fast extrusion furnace black), HAF (high abrasion furnace, high wear-resistant furnace black), ISAF (Intermediate super abrasion furnace, super wear-resistant furnace black), SAF (super abrasion furnace, super wear-resistant furnace black) and other grades of carbon black, preferably nitrogen adsorption Carbon black with a specific surface area of 50 mg/g or more and a DBP (dibutyl phthalate) oil absorption of 80 mL/100 g.
於使用有本實施形態之氫化嵌段共聚物或氫化嵌段共聚物組合物之補強性填充劑調配物中,可使用矽烷偶合劑(以下,有時記為成分(D))。 矽烷偶合劑係用以使氫化嵌段共聚物與補強性填充劑之相互作用變得緊密者,係具有對氫化嵌段共聚物與補強性填充劑之一者或兩者為親和性或鍵結性之基之化合物。 作為較佳之矽烷偶合劑,可列舉:2個以上之巰基及/或硫與矽烷醇基或烷氧基矽烷一同連結而成之具有多硫鍵者,具體可列舉:雙-[3-(三乙氧基矽烷基)-丙基]-四硫化物、雙-[3-(三乙氧基矽烷基)-丙基]-二硫化物、雙-[2-(三乙氧基矽烷基)-乙基]-四硫化物、3-巰基丙基-三甲氧基矽烷、3-三乙氧基矽烷基丙基-N,N-二甲基硫代胺甲醯基四硫化物、3-三乙氧基矽烷基丙基苯并噻唑四硫化物等。 就獲得目標之作用效果之觀點而言,矽烷偶合劑之調配量相對於補強性填充劑調配物較佳為0.1~30質量%,更佳為0.5~20質量%,進而較佳為1~15質量%。A silane coupling agent (hereinafter sometimes referred to as component (D)) can be used in a reinforcing filler formulation using the hydrogenated block copolymer or the hydrogenated block copolymer composition of this embodiment. The silane coupling agent is used to make the interaction between the hydrogenated block copolymer and the reinforcing filler close, and it has affinity or bonding to one or both of the hydrogenated block copolymer and the reinforcing filler Compounds that are the basis of sex. As a preferred silane coupling agent, it can be listed: two or more mercapto groups and/or sulfur are linked together with silanol groups or alkoxysilanes and have polysulfide bonds. Specifically, bis-[3-(three Ethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, bis-[2-(triethoxysilyl) -Ethyl]-tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3-triethoxysilylpropyl-N,N-dimethylthioamidoformyl tetrasulfide, 3- Triethoxysilylpropylbenzothiazole tetrasulfide, etc. From the viewpoint of obtaining the desired effect, the blending amount of the silane coupling agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 15% by mass relative to the reinforcing filler formulation. quality%.
含有本實施形態之氫化嵌段共聚物或氫化嵌段共聚物組合物與補強性填充劑之補強性填充劑調配物可利用硫化劑進行硫化,即進行交聯而形成為硫化組合物。 作為硫化劑,可使用:有機過氧化物及偶氮化合物等自由基產生劑、肟化合物、亞硝基化合物、多胺化合物、硫、硫化合物(一氯化硫、二氯化硫、二硫醚化合物、高分子多硫化合物等)。 硫化劑之使用量通常為相對於氫化嵌段共聚物或氫化嵌段共聚物組合物100質量份為0.01~20質量份,較佳為0.1~15質量份之比率。 作為用作硫化劑之有機過氧化物(以下,有時記為成分(E)),就臭氣性或焦化穩定性(各成分之混合時之條件下不交聯,但設為交聯反應條件時迅速交聯之特性)之觀點而言,較佳為2,5-二甲基-2,5-二-(第三丁基過氧基)己烷、2,5-二甲基-2,5-二-(第三丁基過氧基)己炔-3、1,3-雙(第三丁基過氧基異丙基)苯、1,1-雙(第三丁基過氧基)-3,3,5-三甲基環己烷、4,4-雙(第三丁基過氧基)戊酸正丁酯、過氧化二第三丁基。 上述以外,亦可使用:過氧化二異丙苯、過氧化苯甲醯、對氯過氧化苯甲醯、2,4-二氯過氧化苯甲醯、過氧化苯甲酸第三丁酯、過氧化苯甲酸第三丁酯、第三丁基過氧基異丙基碳酸酯、過氧化二乙醯、過氧化月桂醯、第三丁基異丙苯基過氧化物等。The reinforcing filler formulation containing the hydrogenated block copolymer or the hydrogenated block copolymer composition of this embodiment and the reinforcing filler can be vulcanized with a vulcanizing agent, that is, cross-linked to form a vulcanized composition. As the vulcanizing agent, free radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, sulfur compounds (sulfur monochloride, sulfur dichloride, disulfide ether compounds, polymer polysulfide compounds, etc.). The usage-amount of a vulcanizing agent is 0.01-20 mass parts normally with respect to 100 mass parts of hydrogenated block copolymers or a hydrogenated block copolymer composition, Preferably it is the ratio of 0.1-15 mass parts. As an organic peroxide used as a vulcanizing agent (hereinafter sometimes referred to as component (E)), in terms of odor or coking stability (it does not cross-link under the conditions when the components are mixed, but it is a cross-linking reaction From the point of view of rapid cross-linking characteristics under certain conditions), 2,5-dimethyl-2,5-bis-(tert-butylperoxy)hexane, 2,5-dimethyl- 2,5-bis-(tertiary butylperoxy)hexyne-3, 1,3-bis(tertiary butylperoxyisopropyl)benzene, 1,1-bis(tertiary butylperoxy Oxy)-3,3,5-trimethylcyclohexane, 4,4-bis(tert-butylperoxy)-n-butyl valerate, di-tert-butyl peroxide. In addition to the above, you can also use: dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, peroxide Oxidized tert-butyl benzoate, tert-butyl peroxy isopropyl carbonate, diacetyl peroxide, lauryl peroxide, tert-butyl cumyl peroxide, etc.
又,硫化時,作為硫化加速劑(以下,有時記為成分(F)),可以視需要之量使用亞磺醯胺系、胍系、秋蘭姆系、醛-胺系、醛-氨系、噻唑系、硫脲系、二硫代胺基甲酸鹽系之化合物等。 又,作為硫化助劑,亦可以視需要之量使用鋅白、硬脂酸等。 又,於使用上述有機過氧化物對補強性填充劑調配物進行交聯時,尤其亦可與有機過氧化物併用作為硫化加速劑之硫;對醌二肟、p,p'-二苯甲醯基醌二肟、N-甲基-N-4-二亞硝基苯胺、亞硝基苯、二苯基胍、三羥甲基丙烷-N,N'-間伸苯基二順丁烯二醯亞胺等過氧交聯用助劑(以下,有時記為成分(G));二乙烯苯、氰尿酸三烯丙酯、乙二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、甲基丙烯酸烯丙酯等多官能性甲基丙烯酸酯單體;丁酸乙烯酯、硬脂酸乙烯酯等多官能性乙烯基單體(以下,有時記為成分(H))等。 此種硫化加速劑通常以相對於氫化嵌段共聚物或氫化嵌段共聚物組合物100質量份較佳為0.01~20質量份,更佳為0.1~15質量份之比率使用。 作為利用硫化劑將補強性填充劑調配物硫化之方法,可應用先前實施之方法,例如於120~200℃,較佳為140~180℃之溫度下硫化。硫化之補強性填充劑調配物於硫化物之狀態下發揮耐熱性、耐彎曲性或耐油性。Also, during vulcanization, as a vulcanization accelerator (hereinafter, sometimes referred to as component (F)), sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based series, thiazole series, thiourea series, dithiocarbamate series compounds, etc. Moreover, zinc white, stearic acid, etc. can also be used as a vulcanization auxiliary agent in an optional amount. In addition, when using the above-mentioned organic peroxides to crosslink the reinforcing filler formulations, especially sulfur that can also be used as a vulcanization accelerator together with organic peroxides; p-quinonedioxime, p,p'-benzo Acyl quinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N,N'-m-phenylene butene Auxiliaries for peroxygen crosslinking such as diimide (hereinafter, sometimes referred to as component (G)); divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol di Multifunctional methacrylate monomers such as methacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate; vinyl butyrate, stearin Polyfunctional vinyl monomers such as vinyl acid esters (hereinafter, may be referred to as component (H)) and the like. Such a vulcanization accelerator is usually used in a ratio of preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the hydrogenated block copolymer or hydrogenated block copolymer composition. As a method of vulcanizing the reinforcing filler formulation using a vulcanizing agent, the previously implemented method can be applied, for example, vulcanizing at a temperature of 120-200°C, preferably 140-180°C. Vulcanized reinforcing filler formulations exhibit heat resistance, flex resistance, or oil resistance in the vulcanized state.
為了改良補強性填充劑調配物之加工性,可調配橡膠用軟化劑(以下,有時記為成分(I))。 橡膠用軟化劑中適合的為礦物油、或者液狀或低分子量之合成軟化劑。其中,較佳為通常於橡膠之軟化、增容、加工性提昇中所使用之環烷系及/或石蠟系之加工處理油或增量油。 礦物油系橡膠用軟化劑為芳香族環、環烷環及石蠟鏈之混合物,石蠟鏈之碳數占全部碳之50%以上者被稱為石蠟系,環烷環之碳數為30~45%者被稱為環烷系,又芳香族碳數超過30%者被稱為芳香族系。於補強性填充劑調配物中可使用合成軟化劑,可使用聚丁烯、低分子量聚丁二烯、液態石蠟等。但較佳為上述礦物油系橡膠用軟化劑。 補強性填充劑調配物中之橡膠用軟化劑(成分(I))之調配量相對於氫化嵌段共聚物或氫化嵌段共聚物組合物(成分(A))100質量份較佳為0~100質量份,更佳為1~90質量份,進而較佳為30~90質量份。若橡膠用軟化劑之量超過100質量份,則易於產生滲出,存在於組合物表面產生黏膩之虞。In order to improve the processability of the reinforcing filler formulation, a rubber softener (hereinafter sometimes referred to as component (I)) may be formulated. Mineral oil, or liquid or low-molecular-weight synthetic softeners are suitable among rubber softeners. Among them, naphthenic and/or paraffinic processing oils or extender oils generally used for softening, compatibilizing, and improving processability of rubber are preferred. Mineral oil-based softener for rubber is a mixture of aromatic rings, naphthenic rings and paraffin chains. Those whose carbon number in the paraffin chain accounts for more than 50% of the total carbons are called paraffin-based, and the carbon number of the naphthene ring is 30-45. % are called naphthenic series, and those with more than 30% aromatic carbons are called aromatic series. Synthetic softeners may be used in the reinforcing filler formulations, polybutene, low molecular weight polybutadiene, liquid paraffin, etc. may be used. However, the above-mentioned softener for mineral oil-based rubber is preferable. The compounding amount of the rubber softener (component (I)) in the reinforcing filler formulation is preferably 0 to 100 parts by mass of the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)). 100 mass parts, More preferably, it is 1-90 mass parts, More preferably, it is 30-90 mass parts. When the amount of the softener for rubber exceeds 100 parts by mass, bleeding is likely to occur, and there is a possibility of stickiness on the surface of the composition.
含有本實施形態之氫化嵌段共聚物或氫化嵌段共聚物組合物之補強性填充劑調配物可較佳地用作建築材料、電線被覆材或制振材料等。又,其硫化組合物可發揮其特徵,適用於輪胎用途或抗振橡膠、皮帶、工業用品、鞋類、發泡體等之材料。The reinforcing filler formulation containing the hydrogenated block copolymer or the hydrogenated block copolymer composition of this embodiment can be suitably used as a building material, an electric wire covering material, a vibration damping material, and the like. Moreover, its vulcanized composition can exhibit its characteristics and is suitable for materials such as tires, anti-vibration rubber, belts, industrial products, shoes, and foams.
(交聯物) 本實施形態之氫化嵌段共聚物或氫化嵌段共聚物組合物可於硫化劑之存在下交聯,形成為交聯物,即交聯氫化嵌段共聚物或交聯氫化嵌段共聚物組合物。 藉由使本實施形態之氫化嵌段共聚物或氫化嵌段共聚物組合物交聯,可提高耐熱性[高溫C-Set(compression set,壓縮永久變形)]或耐彎曲性。 於製備含有本實施形態之氫化嵌段共聚物組合物之上述補強性填充劑調配物之交聯物之情形時,尤其氫化嵌段共聚物或氫化嵌段共聚物組合物(成分(A))與熱塑性樹脂及/或橡膠狀聚合物(成分(B))之調配比率以成分(A)/成分(B)之質量比率計,較佳為10/90~100/0,更佳為20/80~90/10,進而較佳為30/70~80/20。(cross-linked) The hydrogenated block copolymer or hydrogenated block copolymer composition of this embodiment can be cross-linked in the presence of a vulcanizing agent to form a cross-linked product, that is, a cross-linked hydrogenated block copolymer or a combination of cross-linked hydrogenated block copolymers thing. By crosslinking the hydrogenated block copolymer or the hydrogenated block copolymer composition of this embodiment, heat resistance [high temperature C-Set (compression set, compression set)] and bending resistance can be improved. In the case of preparing a cross-linked product of the above-mentioned reinforcing filler formulation containing the hydrogenated block copolymer composition of this embodiment, especially the hydrogenated block copolymer or the hydrogenated block copolymer composition (component (A)) The compounding ratio of thermoplastic resin and/or rubber-like polymer (component (B)) is based on the mass ratio of component (A)/component (B), preferably 10/90 to 100/0, more preferably 20/ 80-90/10, more preferably 30/70-80/20.
於本實施形態中,交聯之方法並無特別限定,較佳為進行所謂「動態交聯」。 所謂動態交聯係指於熔融狀態下將各種調配物於硫化劑反應之溫度條件下混練,藉此使分散與交聯同時發生之方法,於A.Y. Coran等人之文獻(Rub. Chem. and Technol. vol. 53. 141-(1980))中詳細記載。動態交聯通常係使用如班布里混合機或加壓式捏合機之密閉式混練機、或者單軸或雙軸擠出機等而進行。混練溫度通常為130~300℃,較佳為150~250℃,混練時間通常為1~30分鐘。 作為於動態交聯中使用之硫化劑,可使用有機過氧化物或酚樹脂交聯劑,其使用量通常相對於氫化嵌段共聚物或氫化嵌段共聚物組合物(成分(A))100質量份為0.01~15質量份,較佳為0.04~10質量份。 作為用作硫化劑之有機過氧化物,可使用上述成分(E)。使用有機過氧化物進行交聯時,可使用上述成分(F)作為硫化加速劑,又亦可併用上述成分(G)或上述成分(H)等。該等硫化加速劑之使用量通常相對於氫化嵌段共聚物或氫化嵌段共聚物組合物(成分(A))100質量份為0.01~20質量份,較佳為0.1~15質量份。In this embodiment, the method of cross-linking is not particularly limited, but it is preferable to perform so-called "dynamic cross-linking". The so-called dynamic crosslinking refers to the method of mixing various formulations under the temperature conditions of the vulcanizing agent reaction in the molten state, thereby causing dispersion and crosslinking to occur simultaneously. In the literature of A.Y. Coran et al. (Rub. Chem. and Technol. vol. 53. 141-(1980)) is described in detail. Dynamic crosslinking is usually carried out using a closed kneader such as a Banbury mixer or a pressurized kneader, or a single-screw or twin-screw extruder. The kneading temperature is usually 130-300°C, preferably 150-250°C, and the kneading time is usually 1-30 minutes. As a vulcanizing agent used in dynamic crosslinking, an organic peroxide or phenolic resin crosslinking agent can be used, and its usage is usually relative to the hydrogenated block copolymer or the hydrogenated block copolymer composition (ingredient (A)) 100 The mass parts are 0.01 to 15 mass parts, preferably 0.04 to 10 mass parts. As the organic peroxide used as a vulcanizing agent, the above-mentioned component (E) can be used. When performing crosslinking using an organic peroxide, the above-mentioned component (F) may be used as a vulcanization accelerator, and the above-mentioned component (G) or the above-mentioned component (H) may be used in combination. The usage-amount of these vulcanization accelerators is 0.01-20 mass parts normally with respect to 100 mass parts of hydrogenated block copolymers or a hydrogenated block copolymer composition (component (A)), Preferably it is 0.1-15 mass parts.
可於使用有本實施形態之氫化嵌段共聚物或氫化嵌段共聚物組合物(成分(A))之交聯物中,於不損害其目的之範圍內視需要調配軟化劑、耐熱穩定劑、抗靜電劑、耐候穩定劑、抗老化劑、填充劑、著色劑、潤滑劑等添加物。作為為了調節最終製品之硬度或流動性而調配之軟化劑,可使用上述成分(I)。 軟化劑可於混練各成分時添加,亦可於氫化嵌段共聚物之製造時預先使其含有於該共聚物中,即,可製備充油橡膠。 軟化劑之添加量相對於氫化嵌段共聚物或氫化嵌段共聚物組合物(成分(A))100質量份,通常為0~200質量份,較佳為10~150質量份,更佳為20~100質量份。 又,作為填充劑,可使用上述作為補強性填充材之成分(C)。填充劑之添加量相對於氫化嵌段共聚物或氫化嵌段共聚物組合物(成分(A))100質量份,通常為0~200質量份,較佳為10~150質量份,更佳為20~100質量份。 推薦上述交聯物以凝膠含量(其中,不含無機填充材等不溶物等不溶成分)成為較佳為5~80質量%,更佳為10~70質量%,進而較佳為20~60質量%之方式進行動態交聯。關於凝膠含量,使用沸騰二甲苯以索氏萃取器將交聯物1 g回流10小時,將殘留物以80網目之金屬絲網過濾,測定篩網上殘留之不溶物之乾燥質量(g)而求得不溶物相對於試樣1 g之比率(質量%),將該比率作為凝膠含量。凝膠含量可藉由調整硫化劑之種類或量、硫化時之條件(溫度、滯留時間、剪切等)而控制。 上述交聯物與補強性填充劑調配物之硫化組合物同樣地,可適用於輪胎用途或抗振橡膠、皮帶、工業用品、鞋類、發泡體等,進而亦可用作醫療用器具材料或食品包裝材料。 [實施例]In the cross-linked product using the hydrogenated block copolymer of this embodiment or the hydrogenated block copolymer composition (component (A)), a softener and a heat-resistant stabilizer can be formulated as needed within the range that does not impair the purpose , antistatic agent, weather stabilizer, antiaging agent, filler, colorant, lubricant and other additives. The above-mentioned component (I) can be used as a softener formulated to adjust the hardness or fluidity of the final product. The softener may be added when kneading the components, or it may be contained in the copolymer in advance when the hydrogenated block copolymer is produced, that is, an oil-extended rubber can be prepared. The amount of the softener to be added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass. Moreover, as a filler, the above-mentioned component (C) which is a reinforcing filler can be used. The amount of the filler to be added is usually 0 to 200 parts by mass, preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass. It is recommended that the above-mentioned cross-linked product has a gel content (excluding insoluble components such as inorganic fillers, etc.) of preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass. The dynamic cross-linking is carried out by mass %. Regarding the gel content, reflux 1 g of the cross-linked product with a Soxhlet extractor for 10 hours using boiling xylene, filter the residue with an 80-mesh wire mesh, and measure the dry mass (g) of the insoluble matter remaining on the mesh Then, the ratio (mass %) of the insoluble matter to 1 g of the sample was obtained, and this ratio was defined as the gel content. The gel content can be controlled by adjusting the type or amount of vulcanizing agent, and the conditions during vulcanization (temperature, residence time, shear, etc.). The above-mentioned cross-linked product can be applied to tires, anti-vibration rubber, belts, industrial products, footwear, foam, etc. like the vulcanized composition of the reinforcing filler formulation, and can also be used as a material for medical devices or food packaging materials. [Example]
以下,列舉具體之實施例及比較例,詳細說明本實施形態,但本實施形態不受以下實施例及比較例之任何限定。 各種物性係藉由下述所示之方法而測定。Hereinafter, specific examples and comparative examples will be given to describe this embodiment in detail, but this embodiment is not limited to the following examples and comparative examples. Various physical properties were measured by the methods shown below.
[共聚物之結構之特定方法、物性之測定方法] ((1)氫化嵌段共聚物(一)中之總乙烯基芳香族化合物(苯乙烯)單體單元之含量) 使用氫化前之嵌段共聚物,藉由紫外分光光度計(島津製作所製造,UV-2450)測定總乙烯基芳香族化合物(苯乙烯)單體單元之含量。[Specific methods for the structure of copolymers, and methods for measuring physical properties] ((1) Content of total vinyl aromatic compound (styrene) monomer units in hydrogenated block copolymer (1)) Using the block copolymer before hydrogenation, the content of the total vinyl aromatic compound (styrene) monomer unit was measured by an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450).
((2)氫化嵌段共聚物(一)中之以乙烯基芳香族化合物單體單元為主體之聚合物嵌段(聚苯乙烯嵌段)之含量) 使用氫化前之嵌段共聚物,使用核磁共振裝置(NMR)(Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685(1981)中記載之方法;以下稱為「NMR法」)測定。((2) Content of polymer block (polystyrene block) mainly composed of vinyl aromatic compound monomer unit in hydrogenated block copolymer (1)) Using a block copolymer before hydrogenation, it was measured using a nuclear magnetic resonance apparatus (NMR) (the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereinafter referred to as "NMR method").
((3-1)氫化嵌段共聚物(一)中之乙烯基鍵結量) 使用氫化前之嵌段共聚物,使用紅外分光光度計(日本分光公司製造,FT/IR-4100)進行測定。共聚物中之乙烯基鍵結量係藉由漢普頓法而算出。((3-1) Vinyl bond amount in hydrogenated block copolymer (1)) Using the block copolymer before hydrogenation, it measured using the infrared spectrophotometer (manufactured by JASCO Corporation, FT/IR-4100). The amount of vinyl bonds in the copolymer was calculated by the Hampton method.
((3-2)共聚物嵌段(b)中之乙烯基鍵結量) 使用即將使聚合物嵌段(c)聚合前進行採樣之氫化前之嵌段共聚物,使用紅外分光光度計(日本分光公司製造,FT/IR-4100)進行測定。共聚物嵌段(b)中之乙烯基鍵結量係藉由漢普頓法而算出。((3-2) Amount of vinyl bonds in copolymer block (b)) Measurement was performed using an infrared spectrophotometer (manufactured by JASCO Corporation, FT/IR-4100) using a block copolymer before hydrogenation which was sampled immediately before polymerizing the polymer block (c). The amount of vinyl bonds in the copolymer block (b) was calculated by the Hampton method.
((3-3)聚合物嵌段(c)中之乙烯基鍵結量) 根據上述(3-1)、(3-2)之乙烯基鍵結量之值算出。((3-3) Vinyl bond amount in polymer block (c)) Calculated from the value of the amount of vinyl bonds in (3-1) and (3-2) above.
((4)氫化嵌段共聚物(一)之重量平均分子量) 藉由GPC[裝置:HLC-82209PC(Tosoh公司製造),管柱:TSKgeguard colum SuperHZ-L(4.6 mm×20 cm)×3根]測定氫化嵌段共聚物(一)之重量平均分子量。 溶劑係使用四氫呋喃。測定係於溫度35℃下進行。 重量平均分子量係使用根據市售之標準聚苯乙烯之測定求出之校準曲線(使用標準聚苯乙烯之波峰分子量而製作),求出層析圖之波峰之分子量。 再者,於層析圖中具有複數個波峰之情形時,將根據各波峰之分子量與各波峰之組成比(根據層析圖之各個波峰之面積比求得)求出之平均分子量作為重量平均分子量。 又,亦對即將添加苯甲酸乙酯前之重量平均分子量進行測定。作為測定方法,關於未添加苯甲酸乙酯者,自以甲醇使即將添加苯甲酸乙酯前進行採樣之聚合物失活而獲得之聚合物之GPC算出,關於添加有苯甲酸乙酯者,使用製作之氫化嵌段共聚物(一)以GPC進行測定。 關於分子量分佈,亦同樣地以GPC進行測定。((4) Weight average molecular weight of hydrogenated block copolymer (1)) The weight average molecular weight of the hydrogenated block copolymer (1) was measured by GPC [device: HLC-82209PC (manufactured by Tosoh Corporation), column: TSKgeguard column SuperHZ-L (4.6 mm×20 cm)×3 pieces]. As the solvent, tetrahydrofuran was used. The measurement is carried out at a temperature of 35°C. The weight-average molecular weight was determined by using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene to obtain the molecular weight of the peak of the chromatogram. Furthermore, when there are multiple peaks in the chromatogram, the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in the chromatogram) is taken as the weight average molecular weight. Moreover, the weight average molecular weight immediately before adding ethyl benzoate was also measured. As a measurement method, for those without ethyl benzoate, it is calculated from the GPC of the polymer obtained by inactivating the polymer sampled immediately before the addition of ethyl benzoate with methanol, and for those with ethyl benzoate added, use The produced hydrogenated block copolymer (1) was measured by GPC. The molecular weight distribution was also measured by GPC in the same manner.
((5)氫化嵌段共聚物(一)之GPC曲線中之分子量1萬以上15萬以下之範圍之面積相對於分子量1萬~100萬之範圍之面積之比率(%)、20萬以上100以下之範圍之面積相對於分子量1萬~100萬之範圍之面積之比率(%)) 藉由GPC[裝置:HLC-82209PC(Tosoh公司製造),管柱:TSKgeguard colum SuperHZ-L(4.6 mm×20 cm)×3根]進行測定。 溶劑係使用四氫呋喃。 測定係於溫度35℃下進行。 所謂氫化嵌段共聚物(一)之1萬以上15萬以下之範圍之分子量之面積值(%)係指自GPC曲線中之氫化嵌段共聚物(一)之分子量1萬以上15萬以下之範圍之面積值與分子量1萬~100萬之範圍之面積值之比求得之值。 所謂氫化嵌段共聚物(一)之20萬以上100萬以下之範圍之分子量之面積值(%)係指自GPC曲線中氫化嵌段共聚物(一)之分子量20萬以上100萬以下之範圍之面積值與分子量1萬~100萬之範圍之面積值之比求得之值。(5) The ratio (%) of the area of the molecular weight range of 10,000 to 150,000 to the area of the molecular weight range of 10,000 to 1 million in the GPC curve of the hydrogenated block copolymer (1), 200,000 to 100 The ratio of the area of the following range to the area of the range of molecular weight 10,000 to 1,000,000 (%)) Measurement was carried out by GPC [device: HLC-82209PC (manufactured by Tosoh), column: TSKgeguard column SuperHZ-L (4.6 mm×20 cm)×3]. As the solvent, tetrahydrofuran was used. The measurement is carried out at a temperature of 35°C. The area value (%) of the molecular weight of the hydrogenated block copolymer (1) in the range of 10,000 to 150,000 is the area value (%) of the hydrogenated block copolymer (1) with a molecular weight of 10,000 to 150,000 in the GPC curve. The value obtained from the ratio of the area value of the range to the area value of the range of molecular weight from 10,000 to 1,000,000. The area value (%) of the molecular weight in the range of 200,000 to 1 million of the hydrogenated block copolymer (1) refers to the range of the molecular weight of the hydrogenated block copolymer (1) from 200,000 to 1 million in the GPC curve The value obtained from the ratio of the area value of the molecular weight to the area value of the molecular weight range of 10,000 to 1,000,000.
((6)氫化嵌段共聚物(一)之共軛二烯單體單元之雙鍵之氫化率) 使用氫化嵌段共聚物,使用核磁共振裝置(JEOL RESONANCE公司製造,ECS400),測定共軛二烯單體單元之雙鍵之氫化率。((6) Hydrogenation rate of the double bond of the conjugated diene monomer unit of the hydrogenated block copolymer (1)) Using the hydrogenated block copolymer, the hydrogenation rate of the double bond of the conjugated diene monomer unit was measured using a nuclear magnetic resonance apparatus (manufactured by JEOL RESONANCE, ECS400).
((7)共聚物嵌段(b)中之乙烯基芳香族化合物單體單元之含量) 將氫化前之嵌段共聚物作為檢體,自使用核磁共振裝置(NMR)(Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981)中記載之方法;以下稱為「NMR法」)測定的氫化嵌段共聚物(一)中之總乙烯基芳香族化合物(苯乙烯)單體單元之含量與氫化嵌段共聚物(一)中之以乙烯基芳香族化合物單體單元為主體之聚合物嵌段之含量之差算出。((7) Content of vinyl aromatic compound monomer unit in copolymer block (b)) Using the block copolymer before hydrogenation as a sample, the method described in using a nuclear magnetic resonance apparatus (NMR) (Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereinafter referred to as "NMR method ") measured hydrogenated block copolymer (one) in the total vinyl aromatic compound (styrene) monomer unit content and hydrogenated block copolymer (one) in the vinyl aromatic compound monomer unit The difference in the content of the polymer block in the main body was calculated.
[特性之測定方法] ((1)tanδ波峰溫度) 首先,將如下述方式製造之「加壓成形片材」切割為寬12.5 mm、長40 mm之尺寸,作為測定用樣品。 其次,將該測定用樣品設置於裝置ARES(TA Instruments股份有限公司製造,商品名)之扭轉型之幾何佈局,於有效測定長度25 mm、應變0.5%、頻率1 Hz、升溫速度3℃/分鐘之條件下求得。 tanδ波峰溫度係自藉由RSI Orchestrator(TA Instruments股份有限公司製造,商品名)之自動測定而檢測出之波峰求得之值。[Measurement method of characteristics] ((1) tanδ peak temperature) First, the "press-molded sheet" manufactured as follows was cut into a size of 12.5 mm in width and 40 mm in length, and used as a sample for measurement. Next, set the sample for measurement in the torsional geometry of the device ARES (manufactured by TA Instruments Co., Ltd., trade name), at an effective measurement length of 25 mm, a strain of 0.5%, a frequency of 1 Hz, and a heating rate of 3°C/min. Obtained under the conditions. The tan δ peak temperature is a value obtained from the peak detected by automatic measurement by RSI Orchestrator (manufactured by TA Instruments Co., Ltd., trade name).
((2)硬度) 依據JIS K6253,以A型硬度計測定瞬間之值與10秒後之值。 測定降下硬度測定器之探針至樣品上之瞬間之硬度值、及降下後10秒後之硬度值。 於下述表1、2中分別記為硬度(JIS-A,瞬間)、硬度(JIS-A,10 s)。 硬度之值較佳為96以下。((2) Hardness) According to JIS K6253, the instant value and the value after 10 seconds were measured with a type A hardness tester. Measure the hardness value at the moment when the probe of the hardness tester is lowered onto the sample, and the hardness value 10 seconds after it is lowered. In the following Tables 1 and 2, they are described as hardness (JIS-A, instant) and hardness (JIS-A, 10 s), respectively. The hardness value is preferably 96 or less.
((3)熔體流動速率(MFR,單位:g/10 分鐘)) 依據JIS K7210,於溫度230℃、負載2.16 kg之條件下進行測定。 又,以如下方式記載分數:MFR值未達25(g/10分鐘)設為0分,未達25~35(g/10分鐘)設為1分,未達35~45(g/10分鐘)設為2分,45(g/10分鐘以上)設為3分。((3) Melt flow rate (MFR, unit: g/10 minutes)) According to JIS K7210, the measurement was carried out under the conditions of a temperature of 230°C and a load of 2.16 kg. In addition, the score is described as follows: MFR value less than 25 (g/10 minutes) is set as 0 point, less than 25-35 (g/10 minutes) is set as 1 point, less than 35-45 (g/10 minutes) ) was set as 2 points, and 45 (g/10 minutes or more) was set as 3 points.
((4)耐磨耗性) 使用學振型摩擦試驗器(TESTER SANGYO股份有限公司製造,AB-301型),以摩擦布細白布3號(canequim No.3)棉,以負載500 g對藉由下述[射出成形片材之製作]而製作之成形片材表面(皮紋加工面)進行摩擦,根據摩擦後之體積減少量,依據以下基準進行判定。 ◎(3分):摩擦次數10,000次後,體積減少量為0.01 ml以下 ○(2分):摩擦次數10,000次後,體積減少量為超過0.01 ml且0.1 ml以下 △(1分):摩擦次數10,000次後,體積減少量為超過0.1 ml且0.2 ml以下 ×(0分):摩擦次數10,000次後,體積減少量為超過0.2 ml((4) Abrasion resistance) Using a Gakushin-type friction tester (manufactured by TESTER SANGYO Co., Ltd., AB-301 type), rubbing cloth No. 3 (canequim No. 3) cotton with a load of 500 g is applied to the sheet formed by the following [injection molding] Production] and the surface of the formed sheet (textured surface) is rubbed, and the volume reduction after rubbing is judged according to the following criteria. ◎(3 points): After rubbing 10,000 times, the volume loss is 0.01 ml or less ○ (2 points): After rubbing 10,000 times, the amount of volume loss is more than 0.01 ml and less than 0.1 ml △(1 point): After rubbing 10,000 times, the volume loss is more than 0.1 ml and less than 0.2 ml × (0 points): After rubbing 10,000 times, the volume reduction is more than 0.2 ml
((5)股線之拉線容易度(擠出成形性)) 使用下述氫化嵌段共聚物組合物,利用目視以3個等級評價經由日本製鋼所股份有限公司製造之單軸擠出機TEX-30型排氣孔之模噴嘴擠出之股線之拉線容易度。 將可以高速拉伸股線者評價為「3」,將若以高速拉伸股線則輕易地斷裂,但若以低速拉伸則不斷裂者評價為「2」,將即使以低速拉伸股線亦輕易地斷裂者評價為「1」。 3個等級評價之數字越大,擠出成形性越優異。((5) Ease of drawing strands (extrusion formability)) Using the following hydrogenated block copolymer composition, the draw wire of the strand extruded through the die nozzle of the single-screw extruder TEX-30 type vent hole manufactured by Nippon Steel Works Co., Ltd. was visually evaluated on a 3-point scale ease. Those who can stretch the strands at a high speed are evaluated as "3", those who are easily broken when stretched at a high speed but not broken when stretched at a low speed are rated as "2", and those who stretch the strands at a low speed are rated as "3". The case where the thread was easily broken was rated as "1". The larger the number of the three grade evaluations, the better the extrusion formability.
((6)顆粒之耐黏連性) 耐黏連性係藉由以下方法測定。 於直徑5 cm之金屬圓筒中裝入包含氫化嵌段共聚物之相同形狀(直徑約3 mm×3 mm之圓筒狀)之樣品顆粒60 g,於其上放置1160 g之重物。 於該狀態下,於加溫至42℃之吉爾烘箱中加溫20小時後,觀察圓筒中之顆粒之附著狀態。 具體而言,因自圓筒取出之顆粒塊崩散(其中,耐黏連性較差者維持塊狀,未崩散),故而測定包含3粒以上之顆粒之塊之重量,求出顆粒塊之重量相對於顆粒之總重量(60 g)之比(%)。 耐黏連性之優良與否係依據下述基準進行評價。 再者,於各樣品顆粒中添加相當於1500 ppm之硬脂酸鈣後進行評價。 3:崩散,包含3粒以上之顆粒之塊未達總質量之50% 2:崩散,包含3粒以上之顆粒之塊為總質量之50%以上 1:緊固,完全未崩散((6) Blocking resistance of particles) Blocking resistance was measured by the following method. Put 60 g of sample particles of the same shape (cylindrical shape with a diameter of about 3 mm×3 mm) containing hydrogenated block copolymer into a metal cylinder with a diameter of 5 cm, and place a weight of 1160 g on it. In this state, after heating for 20 hours in a Gell oven heated to 42° C., the adhesion state of the particles in the cylinder was observed. Specifically, since the pellets taken out from the cylinder disintegrated (among them, those with poor blocking resistance remained in the form of pellets and did not collapse), so the weight of the pellets containing more than three pellets was measured to obtain the weight of the pellets. The ratio (%) of the weight relative to the total weight of the pellet (60 g). Whether the blocking resistance is excellent or not is evaluated based on the following criteria. In addition, the evaluation was performed after adding calcium stearate equivalent to 1500 ppm to each sample granule. 3: Disintegration, the block containing more than 3 particles does not reach 50% of the total mass 2: Disintegration, the block containing more than 3 particles is more than 50% of the total mass 1: Tightened, not collapsed at all
[氫化嵌段共聚物之製造] (氫化觸媒之製備) 藉由下述方法製備下述實施例及比較例中,製作氫化嵌段共聚物時所使用之氫化觸媒。 預先將具備攪拌裝置之反應容器進行氮氣置換,於其中添加乾燥、精製之環己烷1升。 其次,添加雙(η5-環戊二烯基)二氯化鈦100毫莫耳。 一面將其充分攪拌一面添加含有三甲基鋁200毫莫耳之正己烷溶液,於室溫下使之反應約3日。藉此獲得氫化觸媒。[Manufacture of hydrogenated block copolymer] (Preparation of hydrogenation catalyst) The hydrogenation catalyst used in the production of the hydrogenated block copolymer in the following Examples and Comparative Examples was prepared by the following method. The reaction vessel equipped with a stirring device was replaced with nitrogen in advance, and 1 liter of dry and purified cyclohexane was added thereto. Next, 100 millimoles of bis(η5-cyclopentadienyl)titanium dichloride was added. While fully stirring it, a n-hexane solution containing 200 mmoles of trimethylaluminum was added, and the reaction was allowed to take place at room temperature for about 3 days. Thereby a hydrogenation catalyst is obtained.
<氫化嵌段共聚物> 如下述方式製備構成氫化嵌段共聚物組合物之氫化嵌段共聚物(一)-1~(一)-30、(一)-A~(一)-G。<Hydrogenated block copolymer> The hydrogenated block copolymers (1)-1 to (1)-30, (1)-A to (1)-G constituting the hydrogenated block copolymer composition were prepared in the following manner.
[實施例1] (氫化嵌段共聚物(一)-1) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.096質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-1。 所得氫化嵌段共聚物(一)-1之氫化率為98%。其他特性示於表1。[Example 1] (Hydrogenated block copolymer (1)-1) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.096 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-1. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-1 was 98%. Other properties are shown in Table 1.
[實施例2] (氫化嵌段共聚物(一)-2) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.097質量份之正丁基鋰、相對於正丁基鋰1莫耳為0.9莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」),於70℃下聚合20分鐘。 其次,添加含有丁二烯33質量份與苯乙烯47質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.048莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量67質量%,聚苯乙烯嵌段含量20質量%,乙烯基鍵結量21質量%,重量平均分子量13.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-2。 所得氫化嵌段共聚物(一)-2之氫化率為96%。其他特性示於表1。[Example 2] (Hydrogenated block copolymer (1)-2) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, 0.097 parts by mass of n-butyllithium per 100 parts by mass of all monomers, and 0.9 moles of N,N,N',N'-tetramethylethylenedioxide per 1 mole of n-butyllithium were added. Amine (hereinafter referred to as "TMEDA") was polymerized at 70°C for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.048 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 21% by mass, and a weight average molecular weight of 131,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-2. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-2 was 96%. Other properties are shown in Table 1.
[實施例3] (氫化嵌段共聚物(一)-3) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯20質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.097質量份之正丁基鋰、相對於正丁基鋰1莫耳為0.9莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」),於70℃下聚合20分鐘。 其次,添加含有丁二烯33質量份與苯乙烯47質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量67質量%,聚苯乙烯嵌段含量20質量%,乙烯基鍵結量21質量%,重量平均分子量12萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-3。 所得氫化嵌段共聚物(一)-3之氫化率為98%。其他特性示於表1。[Example 3] (Hydrogenated block copolymer (1)-3) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was charged. Next, add 0.097 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 0.9 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was polymerized at 70°C for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 21% by mass, and a weight average molecular weight of 120,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-3. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-3 was 98%. Other properties are shown in Table 1.
[實施例4] (氫化嵌段共聚物(一)-4) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯20質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.095質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯33質量份與苯乙烯47質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量67質量%,聚苯乙烯嵌段含量20質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-4。 所得氫化嵌段共聚物(一)-4之氫化率為97%。其他特性示於表1。[Example 4] (Hydrogenated block copolymer (1)-4) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was charged. Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide were added to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-4. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-4 was 97%. Other properties are shown in Table 1.
[實施例5] (氫化嵌段共聚物(一)-5) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯4質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.097質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯39質量份與苯乙烯57質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量61質量%,聚苯乙烯嵌段含量4質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-5。 所得氫化嵌段共聚物(一)-5之氫化率為97%。其他特性示於表1。[Example 5] (Hydrogenated block copolymer (1)-5) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 4 parts by mass of styrene was charged. Next, add 0.097 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 39 parts by mass of butadiene and 57 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 61% by mass, a polystyrene block content of 4% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-5. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-5 was 97%. Other properties are shown in Table 1.
[實施例6] (氫化嵌段共聚物(一)-6) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有丁二烯41質量份與苯乙烯59質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.097質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量59質量%,聚苯乙烯嵌段含量0質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-6。 所得氫化嵌段共聚物(一)-6之氫化率為97%。其他特性示於表1。[Example 6] (Hydrogenated block copolymer (1)-6) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 41 parts by mass of butadiene and 59 parts by mass of styrene was charged. Next, add 0.097 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 59% by mass, a polystyrene block content of 0% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-6. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-6 was 97%. Other properties are shown in Table 1.
[實施例7] (氫化嵌段共聚物(一)-7) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.097質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯36質量份與苯乙烯51質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加含有丁二烯3質量份之環己烷溶液(濃度20質量%),於60℃下聚合10分鐘。添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量61質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量52質量%(共聚物嵌段(b)之乙烯基鍵結量51質量%,聚合物嵌段(c)之乙烯基鍵結量70質量%),重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-7。 所得氫化嵌段共聚物(一)-7之氫化率為95%。其他特性示於表1。[Example 7] (Hydrogenated block copolymer (1)-7) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.097 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 36 parts by mass of butadiene and 51 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of butadiene was added, and polymerization was carried out at 60° C. for 10 minutes. 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. Regarding the block copolymer obtained as described above, the styrene content is 61% by mass, the polystyrene block content is 10% by mass, and the vinyl bond amount is 52% by mass (the vinyl group of the copolymer block (b) The bonding amount is 51% by mass, the vinyl bonding amount of the polymer block (c) is 70% by mass), and the weight average molecular weight is 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-7. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-7 was 95%. Other properties are shown in Table 1.
[實施例8] (氫化嵌段共聚物(一)-8) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.099質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯33質量份與苯乙烯47質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加含有丁二烯10質量份之環己烷溶液(濃度20質量%),於60℃下聚合2小時。添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量57質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量53質量%(共聚物嵌段(b)之乙烯基鍵結量51質量%,聚合物嵌段(c)之乙烯基鍵結量70質量%),重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-8。 所得氫化嵌段共聚物(一)-8之氫化率為98%。其他特性示於表1。[Example 8] (Hydrogenated block copolymer (1)-8) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.099 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 47 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of butadiene was added and polymerized at 60° C. for 2 hours. 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. Regarding the block copolymer obtained as described above, the styrene content is 57% by mass, the polystyrene block content is 10% by mass, and the vinyl bond amount is 53% by mass (the vinyl group of the copolymer block (b) The bonding amount is 51% by mass, the vinyl bonding amount of the polymer block (c) is 70% by mass), and the weight average molecular weight is 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the copolymer to obtain a hydrogenated block copolymer Object (1)-8. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-8 was 98%. Other properties are shown in Table 1.
[實施例9] (氫化嵌段共聚物(一)-9) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.101質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯29質量份與苯乙烯41質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加含有丁二烯20質量份之環己烷溶液(濃度20質量%),於60℃下聚合2小時。添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量51質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量55質量%(共聚物嵌段(b)之乙烯基鍵結量51質量%,聚合物嵌段(c)之乙烯基鍵結量70質量%),重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-9。 所得氫化嵌段共聚物(一)-9之氫化率為97%。其他特性示於表1。[Example 9] (Hydrogenated block copolymer (1)-9) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.101 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 29 parts by mass of butadiene and 41 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of butadiene was added and polymerized at 60° C. for 2 hours. 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. Regarding the block copolymer obtained as described above, the styrene content is 51% by mass, the polystyrene block content is 10% by mass, and the vinyl bond amount is 55% by mass (the vinyl group of the copolymer block (b) The bonding amount is 51% by mass, the vinyl bonding amount of the polymer block (c) is 70% by mass), and the weight average molecular weight is 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-9. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-9 was 97%. Other properties are shown in Table 1.
[實施例10] (氫化嵌段共聚物(一)-10) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.095質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量12.6萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-10。 所得氫化嵌段共聚物(一)-10之氫化率為96%。其他特性示於表1。[Example 10] (Hydrogenated block copolymer (1)-10) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide were added to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 126,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-10. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-10 was 96%. Other properties are shown in Table 1.
[實施例11] (氫化嵌段共聚物(一)-11) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.095質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.225莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.2萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-11。 所得氫化嵌段共聚物(一)-11之氫化率為98%。其他特性示於表2。[Example 11] (Hydrogenated block copolymer (1)-11) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, 0.095 parts by mass of n-butyllithium per 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide were added to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.225 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 152,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-11. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-11 was 98%. Other properties are shown in Table 2.
[實施例12] (氫化嵌段共聚物(一)-12) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.108質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.2莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.02莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量29質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-12。 所得氫化嵌段共聚物(一)-12之氫化率為95%。其他特性示於表2。[Example 12] (Hydrogenated block copolymer (1)-12) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.2 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.02 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 29% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-12. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-12 was 95%. Other properties are shown in Table 2.
[實施例13] (氫化嵌段共聚物(一)-13) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.108質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.5莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.06莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量40質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-13。 所得氫化嵌段共聚物(一)-13之氫化率為95%。其他特性示於表2。[Example 13] (Hydrogenated block copolymer (1)-13) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.5 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.06 mol of sodium pentapentoxide relative to 1 mol of n-butyl lithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 40% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-13. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-13 was 95%. Other properties are shown in Table 2.
[實施例14] (氫化嵌段共聚物(一)-14) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.108質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-14。 所得氫化嵌段共聚物(一)-14之氫化率為86%。其他特性示於表2。[Example 14] (Hydrogenated block copolymer (1)-14) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-14. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-14 was 86%. Other properties are shown in Table 2.
[實施例15] (氫化嵌段共聚物(一)-15) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.108質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-15。 所得氫化嵌段共聚物(一)-15之氫化率為90%。其他特性示於表2。[Example 15] (Hydrogenated block copolymer (1)-15) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-15. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-15 was 90%. Other properties are shown in Table 2.
[實施例16] (氫化嵌段共聚物(一)-16) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.108質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-16。 所得氫化嵌段共聚物(一)-16之氫化率為60%。其他特性示於表2。[Example 16] (Hydrogenated block copolymer (1)-16) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-16. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-16 was 60%. Other properties are shown in Table 2.
[實施例17] (氫化嵌段共聚物(一)-17) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.108質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-17。 所得氫化嵌段共聚物(一)-17之氫化率為40%。其他特性示於表2。[Example 17] (Hydrogenated block copolymer (1)-17) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.108 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-17. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-17 was 40%. Other properties are shown in Table 2.
[實施例18] (氫化嵌段共聚物(一)-18) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.102質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯52質量份與苯乙烯38質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量48質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量60質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-18。 所得氫化嵌段共聚物(一)-18之氫化率為97%。其他特性示於表2。[Example 18] (Hydrogenated block copolymer (1)-18) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.102 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 52 parts by mass of butadiene and 38 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 48% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 60% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-18. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-18 was 97%. Other properties are shown in Table 2.
[實施例19] (氫化嵌段共聚物(一)-19) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.090質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯19質量份與苯乙烯71質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量81質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量40質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-19。 所得氫化嵌段共聚物(一)-19之氫化率為96%。其他特性示於表2。[Example 19] (Hydrogenated block copolymer (1)-19) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 19 parts by mass of butadiene and 71 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 81% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 40% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-19. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-19 was 96%. Other properties are shown in Table 2.
[實施例20] (氫化嵌段共聚物(一)-20) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.090質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯39.6質量份與苯乙烯50.4質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量50質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量55質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-20。 所得氫化嵌段共聚物(一)-20之氫化率為96%。其他特性示於表2。[Example 20] (Hydrogenated block copolymer (1)-20) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 39.6 parts by mass of butadiene and 50.4 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 50% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 55% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-20. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-20 was 96%. Other properties are shown in Table 2.
[實施例21] (氫化嵌段共聚物(一)-21) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.090質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯42.3質量份與苯乙烯47.7質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量52質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-21。 所得氫化嵌段共聚物(一)-21之氫化率為96%。其他特性示於表3。[Example 21] (Hydrogenated block copolymer (1)-21) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 42.3 parts by mass of butadiene and 47.7 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 52% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-21. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-21 was 96%. Other properties are shown in Table 3.
[實施例22] (氫化嵌段共聚物(一)-22) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.090質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.045莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量13.6萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-22。 所得氫化嵌段共聚物(一)-22之氫化率為96%。其他特性示於表3。[Example 22] (Hydrogenated block copolymer (1)-22) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.045 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 136,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-22. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-22 was 96%. Other properties are shown in Table 3.
[實施例23] (氫化嵌段共聚物(一)-23) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.090質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.06莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量14.0萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-23。 所得氫化嵌段共聚物(一)-23之氫化率為96%。其他特性示於表3。[Example 23] (Hydrogenated block copolymer (1)-23) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.06 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 140,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-23. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-23 was 96%. Other properties are shown in Table 3.
[實施例24] (氫化嵌段共聚物(一)-24) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.090質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量33質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-24。 所得氫化嵌段共聚物(一)-24之氫化率為96%。其他特性示於表3。[Example 24] (Hydrogenated block copolymer (1)-24) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 33% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-24. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-24 was 96%. Other properties are shown in Table 3.
[實施例25] (氫化嵌段共聚物(一)-25) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯30質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.102質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯29質量份與苯乙烯41質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量71質量%,聚苯乙烯嵌段含量30質量%,乙烯基鍵結量51質量%,重量平均分子量13.3萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-25。 所得氫化嵌段共聚物(一)-25之氫化率為96%。其他特性示於表3。[Example 25] (Hydrogenated block copolymer (1)-25) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 30 parts by mass of styrene was charged. Next, add 0.102 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 29 parts by mass of butadiene and 41 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 71% by mass, a polystyrene block content of 30% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 133,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-25. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-25 was 96%. Other properties are shown in Table 3.
[實施例26] (氫化嵌段共聚物(一)-26) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.090質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯33質量份與苯乙烯57質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量67質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-26。 所得氫化嵌段共聚物(一)-26之氫化率為96%。其他特性示於表3。[Example 26] (Hydrogenated block copolymer (1)-26) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 57 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 67% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-26. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-26 was 96%. Other properties are shown in Table 3.
[實施例27] (氫化嵌段共聚物(一)-27) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯3質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.090質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯36質量份與苯乙烯42質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量39質量%,聚苯乙烯嵌段含量3質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-27。 所得氫化嵌段共聚物(一)-27之氫化率為96%。其他特性示於表3。[Example 27] (Hydrogenated block copolymer (1)-27) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of styrene was charged. Next, add 0.090 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 36 parts by mass of butadiene and 42 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 39% by mass, a polystyrene block content of 3% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-27. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-27 was 96%. Other properties are shown in Table 3.
[實施例28] (氫化嵌段共聚物(一)-28) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.112質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯32質量份與苯乙烯58質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量42質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量60質量%,重量平均分子量13.5萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-28。 所得氫化嵌段共聚物(一)-28之氫化率為97%。其他特性示於表3。[Example 28] (Hydrogenated block copolymer (1)-28) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.112 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 32 parts by mass of butadiene and 58 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 42% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 60% by mass, and a weight average molecular weight of 135,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-28. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-28 was 97%. Other properties are shown in Table 3.
[實施例29] (氫化嵌段共聚物(一)-29) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯16.7質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.112質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯33質量份與苯乙烯50質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量50質量%,聚苯乙烯嵌段含量13.7質量%,乙烯基鍵結量75質量%,重量平均分子量13.7萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-29。 所得氫化嵌段共聚物(一)-29之氫化率為97%。其他特性示於表3。[Example 29] (Hydrogenated block copolymer (1)-29) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 16.7 parts by mass of styrene was charged. Next, add 0.112 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 33 parts by mass of butadiene and 50 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 50% by mass, a polystyrene block content of 13.7% by mass, a vinyl bond amount of 75% by mass, and a weight average molecular weight of 137,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (1)-29. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-29 was 97%. Other properties are shown in Table 3.
[實施例30] (氫化嵌段共聚物(一)-30) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯15質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.075質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」),於70℃下聚合20分鐘。 其次,添加含有丁二烯35質量份與苯乙烯50質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量65質量%,聚苯乙烯嵌段含量15質量%,乙烯基鍵結量23質量%,重量平均分子量15.0萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-30。 所得氫化嵌段共聚物(一)-30之氫化率為97%。其他特性示於表3。[Example 30] (Hydrogenated block copolymer (1)-30) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was charged. Next, add 0.075 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was polymerized at 70°C for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 35 parts by mass of butadiene and 50 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 65% by mass, a polystyrene block content of 15% by mass, a vinyl bond amount of 23% by mass, and a weight average molecular weight of 150,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment Copolymer (I)-30. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-30 was 97%. Other properties are shown in Table 3.
[比較例1] (氫化嵌段共聚物(一)-A) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯45質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.092質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯23質量份與苯乙烯32質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量77質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-A。 所得氫化嵌段共聚物(一)-A之氫化率為98%。其他特性示於表4。[Comparative example 1] (Hydrogenated block copolymer (1)-A) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 45 parts by mass of styrene was charged. Next, add 0.092 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 23 parts by mass of butadiene and 32 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 77% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-A. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-A was 98%. Other properties are shown in Table 4.
[比較例2] (氫化嵌段共聚物(一)-B) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.116質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.15莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量16.2萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-B。 所得氫化嵌段共聚物(一)-B之氫化率為96%。其他特性示於表4。[Comparative example 2] (Hydrogenated block copolymer (1)-B) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.116 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.15 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 162,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-B. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-B was 96%. Other properties are shown in Table 4.
[比較例3] (氫化嵌段共聚物(一)-C) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.080質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.25莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量21.0萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-C。 所得氫化嵌段共聚物(一)-C之氫化率為95%。其他特性示於表4。[Comparative example 3] (Hydrogenated block copolymer (1)-C) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.080 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.25 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 210,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-C. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-C was 95%. Other properties are shown in Table 4.
[比較例4] (氫化嵌段共聚物(一)-D) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.096質量份之正丁基鋰、相對於正丁基鋰1莫耳為0.2莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」),於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量10質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-D。 所得氫化嵌段共聚物(一)-D之氫化率為98%。其他特性示於表4。[Comparative example 4] (Hydrogenated block copolymer (1)-D) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.096 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 0.2 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was polymerized at 70°C for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 10% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-D. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-D was 98%. Other properties are shown in Table 4.
[比較例5] (氫化嵌段共聚物(一)-E) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.096質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯37質量份與苯乙烯53質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量63質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量51質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-E。 所得氫化嵌段共聚物(一)-E之氫化率為15%。其他特性示於表4。[Comparative Example 5] (Hydrogenated block copolymer (1)-E) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.096 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 37 parts by mass of butadiene and 53 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 63% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 51% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-E. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-E was 15%. Other properties are shown in Table 4.
[比較例6] (氫化嵌段共聚物(一)-F) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.096質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯72質量份與苯乙烯18質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其次,添加相對於正丁基鋰1莫耳為0.105莫耳之苯甲酸乙酯,於70℃下反應10分鐘。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量28質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量66質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-F。 所得氫化嵌段共聚物(一)-F之氫化率為97%。其他特性示於表4。[Comparative Example 6] (Hydrogenated block copolymer (1)-F) Batch polymerization was carried out using a tank reactor (with an inner volume of 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.096 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 72 parts by mass of butadiene and 18 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Next, 0.105 mol of ethyl benzoate was added with respect to 1 mol of n-butyllithium, and it was made to react at 70 degreeC for 10 minutes. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 28% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 66% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on a Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-F. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-F was 97%. Other properties are shown in Table 4.
[比較例7] (氫化嵌段共聚物(一)-G) 使用具備攪拌裝置及夾套之槽型反應器(內容積10 L)進行分批聚合。 首先,投入含有苯乙烯10質量份之環己烷溶液(濃度20質量%)。 其次,添加相對於全部單體100質量份為0.09質量份之正丁基鋰、相對於正丁基鋰1莫耳為1.8莫耳之N,N,N',N'-四甲基乙二胺(以下稱為「TMEDA」)、進而添加相對於正丁基鋰1莫耳為0.08莫耳之第三戊醇鈉,於70℃下聚合20分鐘。 其次,添加含有丁二烯17質量份與苯乙烯73質量份之環己烷溶液(濃度20質量%)於60℃下聚合2小時。其後,添加甲醇,停止聚合反應。 關於以如上所述之方式獲得之嵌段共聚物,苯乙烯含量83質量%,聚苯乙烯嵌段含量10質量%,乙烯基鍵結量36質量%,重量平均分子量15.1萬。 進而,於所得嵌段共聚物中,相對於嵌段共聚物每100質量份添加以Ti基準計為100 ppm之以如上所述之方式製備之氫化觸媒,於氫壓0.7 MPa、溫度65℃下進行氫化反應。 其次,相對於嵌段共聚物100質量份添加0.3質量份之作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯,獲得氫化嵌段共聚物(一)-G。 所得氫化嵌段共聚物(一)-G之氫化率為97%。其他特性示於表4。[Comparative Example 7] (Hydrogenated block copolymer (1)-G) Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was charged. Next, add 0.09 parts by mass of n-butyllithium to 100 parts by mass of all monomers, and 1.8 moles of N,N,N',N'-tetramethylethylenedioxide to 1 mole of n-butyllithium. Amine (hereinafter referred to as "TMEDA") was further added with 0.08 mol of sodium pentapentoxide relative to 1 mol of n-butyllithium, and polymerized at 70° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 17 parts by mass of butadiene and 73 parts by mass of styrene was added and polymerized at 60° C. for 2 hours. Thereafter, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 83% by mass, a polystyrene block content of 10% by mass, a vinyl bond amount of 36% by mass, and a weight average molecular weight of 151,000. Furthermore, to the obtained block copolymer, 100 ppm of the hydrogenation catalyst prepared as described above was added on the Ti basis per 100 parts by mass of the block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. under hydrogenation reaction. Next, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain a hydrogenated block copolymer. Segment copolymer (1)-G. The hydrogenation rate of the obtained hydrogenated block copolymer (1)-G was 97%. Other properties are shown in Table 4.
[加壓成形片材之製作] 使用4英吋之輥分別單獨對以如上所述之方式製作之氫化嵌段共聚物(一)-1~(一)-30及(一)-A~(一)-G於160℃下進行輥壓出,其後藉由油壓加壓,於200℃、100 kg/cm2 下進行加壓成形,製作2 mm厚之加壓成形片材。[Preparation of press-formed sheet] Use a 4-inch roll to separate the hydrogenated block copolymers (1)-1~(1)-30 and (1)-A~( 1)-G is rolled out at 160°C, and then pressurized by hydraulic pressure at 200°C and 100 kg/cm 2 to make a 2 mm thick press-formed sheet.
對上述[實施例1~30]、[比較例1~7]之氫化嵌段共聚物(一)-1~30及(一)-A~G測定下述項目之數值。 (物性值) ・總乙烯基芳香族化合物單體單元之含量(質量%) ・(a)以乙烯基芳香族化合物單體單元為主體之聚合物嵌段之含量(質量%) ・(b)包含乙烯基芳香族化合物單體單元與共軛二烯單體單元之氫化共聚物嵌段之含量(質量%) ・(c)以共軛二烯單體單元為主體之氫化聚合物嵌段之含量(質量%) ・上述(b)氫化共聚物嵌段之乙烯基鍵結量(質量%) ・上述(c)氫化聚合物嵌段之乙烯基鍵結量(質量%) ・即將添加苯甲酸乙酯前之重量平均分子量(萬) ・分子量分佈 (苯甲酸乙酯添加品即將添加前之分子量分佈) ・(一)之重量平均分子量(萬) ・GPC圖中之相對於分子量1萬~100萬之範圍之面積的分子量1萬~15萬之範圍之面積值(%) ・GPC圖中之相對於分子量1萬~100萬之範圍之面積的分子量20萬~100萬之範圍之面積值(%) ・共軛二烯單體單元中之乙烯基鍵結量(質量%) ・共軛二烯單體單元之雙鍵之氫化率(%) ・上述(b)之氫化共聚物嵌段中之乙烯基芳香族化合物單體單元之含量(質量%) ・上述(b)之氫化共聚物嵌段中之共軛二烯單體單元之含量(質量%) (特性) ・熔體流動速率(230℃,2.16 kg) ・黏彈性測定圖中之tanδ(損耗正切)之波峰溫度 ・A硬度(瞬間、10 s) ・顆粒之黏連性The values of the following items were measured for the hydrogenated block copolymers (1)-1-30 and (1)-A-G of the above-mentioned [Examples 1-30] and [Comparative Examples 1-7]. (physical value) ・Content of total vinyl aromatic compound monomer units (mass%) ・(a) Content of polymer block mainly composed of vinyl aromatic compound monomer units (mass%) ・(b) Content of hydrogenated copolymer block containing vinyl aromatic compound monomer unit and conjugated diene monomer unit (mass%) ・(c) Content of hydrogenated polymer block mainly composed of conjugated diene monomer units (mass%) ・Vinyl bond amount (mass %) of the above (b) hydrogenated copolymer block ・Vinyl bond amount (mass %) of hydrogenated polymer block (c) above ・Weight average molecular weight immediately before adding ethyl benzoate (10,000) ·The molecular weight distribution (Molecular weight distribution immediately before addition of ethyl benzoate) ・(1) Weight average molecular weight (10,000) ・The value of the area of the molecular weight range of 10,000 to 150,000 relative to the area of the molecular weight range of 10,000 to 1,000,000 in the GPC chart (%) ・The value of the area of the molecular weight range of 200,000 to 1 million relative to the area of the molecular weight range of 10,000 to 1,000,000 in the GPC chart (%) ・Vinyl bond amount in conjugated diene monomer unit (mass%) ・Hydrogenation rate of double bond of conjugated diene monomer unit (%) ・Content (% by mass) of the vinyl aromatic compound monomer unit in the hydrogenated copolymer block of (b) above ・The content of the conjugated diene monomer unit in the hydrogenated copolymer block of (b) above (mass %) (characteristic) ・Melt flow rate (230°C, 2.16 kg) ・The peak temperature of tanδ (loss tangent) in the viscoelasticity measurement chart ・A hardness (momentary, 10 s) ・Particle adhesion
再者,聚合物嵌段(a)~(c)分別表示以下之聚合物嵌段。 聚合物嵌段(a):以乙烯基芳香族化合物單體單元為主體之聚合物嵌段 共聚物嵌段(b):包含乙烯基芳香族化合物單體單元與共軛二烯單體單元之氫化共聚物嵌段 聚合物嵌段(c):以共軛二烯單體單元為主體之氫化聚合物嵌段In addition, the polymer blocks (a) to (c) respectively represent the following polymer blocks. Polymer block (a): a polymer block mainly composed of vinyl aromatic compound monomer units Copolymer block (b): a hydrogenated copolymer block comprising vinyl aromatic compound monomer units and conjugated diene monomer units Polymer block (c): a hydrogenated polymer block mainly composed of conjugated diene monomer units
[氫化嵌段共聚物組合物之製造] 使用上述氫化嵌段共聚物(一)-1~30、(一)-A~G與下述烯烴系樹脂(二)製造氫化嵌段共聚物組合物。[Manufacture of Hydrogenated Block Copolymer Composition] A hydrogenated block copolymer composition was produced using the above-mentioned hydrogenated block copolymers (1)-1 to 30, (1)-A to G and the following olefin resin (2).
(烯烴系樹脂(二)) 作為烯烴系樹脂(二),使用PM900C(PP/SunAllomer製造;MFR=30)。(Olefin resin (2)) As the olefin-based resin (2), PM900C (manufactured by PP/SunAllomer; MFR=30) was used.
[射出成形片材之製作] [實施例31] 以下述表5所示之比率(質量%)調配製為顆粒狀之氫化嵌段共聚物(一)-1與烯烴系樹脂(二),以雙軸擠出機(TEX-30)混練,進行顆粒化,藉此獲得氫化嵌段共聚物組合物。 擠出條件為缸體溫度230℃,螺桿轉速300 rpm。使用所得組合物,於210℃下進行射出成形,製作2 mm厚之片材,獲得物性測定片。物性測定之結果示於表中。[Manufacturing of Injection Molded Sheet] [Example 31] Prepare the granular hydrogenated block copolymer (1)-1 and olefin resin (2) according to the ratio (mass %) shown in the following Table 5, and knead with a twin-screw extruder (TEX-30). Pelletization, whereby a hydrogenated block copolymer composition is obtained. The extrusion conditions are cylinder temperature 230°C and screw speed 300 rpm. Using the obtained composition, injection molding was carried out at 210° C. to produce a sheet with a thickness of 2 mm to obtain a physical property measurement sheet. The results of physical property measurement are shown in the table.
[實施例31~62、比較例8~14] 除將各成分如表5~表8所示進行變更以外,以與上述實施例31相同之方式製造氫化嵌段共聚物組合物,測定其物性。 物性測定之結果示於表5~表8。[Examples 31-62, Comparative Examples 8-14] Except that each component was changed as shown in Table 5 to Table 8, a hydrogenated block copolymer composition was produced in the same manner as in Example 31 above, and its physical properties were measured. The results of the physical property measurement are shown in Tables 5 to 8.
[表1]
[表2]
[表3]
[表4]
[表5]
[表6]
[表7]
[表8]
實施例1~30之氫化嵌段共聚物及實施例31~62之氫化嵌段共聚物組合物之耐磨耗性與MFR之平衡優異,硬度、成形性良好。 [產業上之可利用性]The hydrogenated block copolymers of Examples 1 to 30 and the hydrogenated block copolymer compositions of Examples 31 to 62 had an excellent balance between wear resistance and MFR, and had good hardness and formability. [Industrial availability]
本發明之氫化嵌段共聚物及其組合物於汽車零件(汽車內裝材料、汽車外裝材料)、醫療用具材料、食品包裝容器等各種容器、家電用品、工業零件、玩具等領域中具有產業上之可利用性。The hydrogenated block copolymer of the present invention and its composition have industrial potential in the fields of automobile parts (automobile interior materials, automobile exterior materials), medical equipment materials, various containers such as food packaging containers, home appliances, industrial parts, toys, etc. above availability.
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