TW201905083A - Master batch composition, method for producing resin composition, and resin composition - Google Patents

Master batch composition, method for producing resin composition, and resin composition

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Publication number
TW201905083A
TW201905083A TW107120146A TW107120146A TW201905083A TW 201905083 A TW201905083 A TW 201905083A TW 107120146 A TW107120146 A TW 107120146A TW 107120146 A TW107120146 A TW 107120146A TW 201905083 A TW201905083 A TW 201905083A
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Taiwan
Prior art keywords
block
group
polymer
vinyl aromatic
mass
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TW107120146A
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Chinese (zh)
Inventor
本山敬子
宮本朗
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日商旭化成股份有限公司
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Publication of TW201905083A publication Critical patent/TW201905083A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Abstract

A masterbatch composition which comprises: a poly(phenylene ether) (A-1) and/or a modified poly(phenylene ether) (A-2) having a carboxyl group or the like; and a block copolymer (B) selected from among a non-hydrogenated block copolymer (B-0) comprising a vinylaromatic compound polymer block (b1) and a conjugated-diene compound polymer block (b2), a product (B-I) of hydrogenation of a block copolymer comprising a vinylaromatic compound polymer block (b1') and a conjugated-diene compound polymer block (b2'), and a product (B-II) of hydrogenation of a block copolymer comprising a vinylaromatic compound polymer block (b1") and a conjugated-diene compound/vinylaromatic compound random copolymer block (b3). The poly(phenylene ether) has an Mw of 10,000-50,000. The components (A-1) and (A-2) and the component (B) are contained in amounts of 10-90 parts by mass and 10-90 parts by mass, respectively, per 100 parts by mass of the sum of the components (A-1), (A-2), and (B).

Description

母料組合物、樹脂組合物之製造方法、及樹脂組合物Master batch composition, method for producing resin composition, and resin composition

本發明係關於一種母料組合物、樹脂組合物之製造方法、及樹脂組合物。The present invention relates to a master batch composition, a method for producing a resin composition, and a resin composition.

已知聚苯醚一般於200℃附近具有玻璃轉移溫度，且具有較高之耐熱性，故而藉由混合至熱塑性彈性體中，可獲得耐熱性較高之熱塑性彈性體組合物。 例如，於專利文獻1中揭示有一種包含瀝青、熱塑性彈性體、聚苯醚之瀝青組合物及其製造方法，且報告有由聚苯醚引起之瀝青組合物之軟化點之上升。 於專利文獻2中揭示有一種含有乙烯基芳香族二烯彈性體、補強用填充劑、交聯繫即交聯劑、及包含聚苯醚單元之熱塑性樹脂之橡膠組合物，且報告有由聚苯醚所引起之玻璃轉移溫度之上升。 [先前技術文獻] [專利文獻]It is known that polyphenylene ether generally has a glass transition temperature around 200 ° C. and has high heat resistance. Therefore, by mixing into a thermoplastic elastomer, a thermoplastic elastomer composition having high heat resistance can be obtained. For example, Patent Document 1 discloses an asphalt composition containing asphalt, a thermoplastic elastomer, and a polyphenylene ether and a method for producing the same, and reports an increase in the softening point of the asphalt composition caused by polyphenylene ether. Patent Document 2 discloses a rubber composition containing a vinyl aromatic diene elastomer, a reinforcing filler, a cross-linking or cross-linking agent, and a thermoplastic resin containing a polyphenylene ether unit. Elevation of glass transition temperature caused by ether. [Prior Art Literature] [Patent Literature]

[專利文獻1]國際公開第2002/42377號 [專利文獻2]日本專利特表2017-502145號公報[Patent Document 1] International Publication No. 2002/42377 [Patent Document 2] Japanese Patent Publication No. 2017-502145

[發明所欲解決之問題][Problems to be solved by the invention]

然而，專利文獻1中所記載之瀝青組合物具有如下問題：於使聚苯醚混合分散至瀝青組合物中時需要高溫、高剪切力、及較長之攪拌時間，就易製造性之觀點而言存在改善之餘地。又，由於瀝青組合物中之聚苯醚之分散穩定性並不充分，故而亦有儲存穩定性較差之問題。 專利文獻2中所記載之橡膠組合物由於為了提高乙烯基芳香族二烯彈性體與聚苯醚之相溶性而使用有數量平均分子量未達6,000之低分子量聚苯醚，故而具有如下問題，即由聚苯醚所引起之玻璃轉移溫度之上升效果方面存在改善之餘地。又，由於聚苯醚為粉體，故而亦具有如下問題，即處理性較差，就易製造性之觀點而言存在改善之餘地。However, the asphalt composition described in Patent Document 1 has problems in that when polyphenylene ether is mixed and dispersed in the asphalt composition, a high temperature, a high shear force, and a long stirring time are required, from the viewpoint of ease of manufacturability. There is room for improvement. In addition, since the dispersion stability of the polyphenylene ether in the asphalt composition is not sufficient, there is also a problem of poor storage stability. Since the rubber composition described in Patent Document 2 uses a low molecular weight polyphenylene ether having a number average molecular weight of less than 6,000 in order to improve the compatibility between the vinyl aromatic diene elastomer and the polyphenylene ether, it has the following problems: There is room for improvement in the effect of increasing the glass transition temperature caused by polyphenylene ether. In addition, since polyphenylene ether is a powder, there is also a problem that the handling property is poor, and there is room for improvement from the viewpoint of easy manufacturability.

因此，本發明之目的在於：鑒於上述先前技術之問題點而提供一種可以簡便之步驟且於溫和之混練條件下使具有充分之分子量之聚苯醚均一分散及相溶於熱塑性彈性體等媒體中，可獲得耐熱老化性優異之樹脂組合物之母料組合物。 [解決問題之技術手段]Therefore, an object of the present invention is to provide a simple procedure in which the polyphenylene ether having a sufficient molecular weight is uniformly dispersed and dissolved in a medium such as a thermoplastic elastomer under mild kneading conditions in view of the problems of the foregoing prior art. A master batch composition of a resin composition excellent in heat aging resistance can be obtained. [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進行了努力研究，結果發現，以特定之比率包含具有特定範圍之重量平均分子量之聚苯醚與嵌段共聚物之母料組合物可解決上述先前技術之課題，從而完成本發明。 即，本發明如下所述。The present inventors have conducted diligent research in order to solve the problems of the prior art described above, and as a result, have found that a masterbatch composition containing a polyphenylene ether and a block copolymer having a specific range of weight average molecular weight in a specific ratio can solve the above problems. The subject of the prior art has thus completed the present invention. That is, the present invention is as follows.

[1] 一種母料組合物，其係包含如下成分者： 聚苯醚(A-1)、及/或具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基之官能基改性聚苯醚(A-2)；與 嵌段共聚物(B)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段(b1)與至少1個共軛二烯化合物聚合物嵌段(b2)之嵌段共聚物之非氫化物(B-0)；包含至少1個乙烯基芳香族化合物聚合物嵌段(b1')與至少1個共軛二烯化合物聚合物嵌段(b2')之嵌段共聚物之氫化物(B-I)；及包含至少1個乙烯基芳香族化合物聚合物嵌段(b1'')及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)之嵌段共聚物之氫化物(B-II)所組成之群中之至少一種；且 包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量為10,000以上且50,000以下， 相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，合計包含上述(A-1)與上述(A-2)10質量份以上且90質量份以下，且包含上述(B)10質量份以上且90質量份以下。 [2] 如上述[1]所記載之母料組合物，其進而包含抗氧化劑(C)與潤滑劑(D)，且 相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，包含上述(C)0.1質量份以上且20質量份以下，且包含上述(D)0.1質量份以上且40質量份以下。 [3] 如上述[1]或[2]所記載之母料組合物，其中相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，合計包含上述(A-1)與上述(A-2)20質量份以上且50質量份以下，且包含上述(B)50質量份以上且80質量份以下。 [4] 如上述[1]至[3]中任一項所記載之母料組合物，其具有海島結構，該海島結構包含： 島相，其係由上述(A-1)及/或上述(A-2)所構成；及 海相，其係由上述(B)所構成。 [5] 如上述[4]所記載之母料組合物，其中上述島相之平均直徑未達5 μm。 [6] 如上述[5]所記載之母料組合物，其中上述島相之平均直徑未達1 μm。 [7] 如上述[1]至[6]中任一項所記載之母料組合物，其具有選自由顆粒、小顆粒、及粉體所組成之群中之任一種形狀。 [8] 如上述[1]至[7]中任一項所記載之母料組合物，其為聚苯醚母料組合物。 [9] 如上述[1]至[8]中任一項所記載之母料組合物，其可用作改質劑。 [10] 一種樹脂組合物之製造方法，其具有如下步驟： 將如上述[1]至[9]中任一項所記載之母料組合物、及 包含選自由熱塑性彈性體、軟質系熱塑性聚合物、橡膠、瀝青、密封劑、接著劑、熱熔接著劑、黏著劑、及塗料所組成之群中之至少任一種之媒體 於未達250℃之溫度條件下機械地進行混練。 [11] 如上述[10]所記載之樹脂組合物之製造方法，其中上述媒體為軟質系熱塑性聚合物，且 上述軟質系熱塑性聚合物係選自由聚烯烴系、聚胺基甲酸酯系、聚酯系、聚醯胺系、及聚氯乙烯系所組成之群中之一種以上。 [12] 如上述[10]中所記載之樹脂組合物之製造方法，其中上述媒體為熱塑性彈性體(E)， 該熱塑性彈性體(E)係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段、及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物；及至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物所組成之群中之一種或兩種以上。 [13] 如上述[10]至[12]中任一項所記載之樹脂組合物之製造方法，其中上述進行混練之步驟後之包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑未達5 μm。 [14] 一種樹脂組合物，其包含： 聚苯醚(A-1)、及/或具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基之官能基改性聚苯醚(A-2)； 嵌段共聚物(B)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段(b1)與至少1個共軛二烯化合物聚合物嵌段(b2)之嵌段共聚物之非氫化物(B-0)；包含至少1個乙烯基芳香族化合物聚合物嵌段(b1')與至少1個共軛二烯化合物聚合物嵌段(b2')之嵌段共聚物之氫化物(B-I)；及包含至少1個乙烯基芳香族化合物聚合物嵌段(b1'')及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)之嵌段共聚物之氫化物(B-II)所組成之群中之至少一種；及 媒體，其係選自由熱塑性彈性體、軟質系熱塑性聚合物、橡膠、瀝青、密封劑、接著劑、熱熔接著劑、黏著劑、及塗料所組成之群中之至少一種；且 包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量為10,000以上且50,000以下， 且包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑未達5 μm。 [15] 如上述[14]所記載之樹脂組合物，其中上述媒體為軟質系熱塑性聚合物， 上述軟質系熱塑性聚合物係選自由聚烯烴系、聚胺基甲酸酯系、聚酯系、聚醯胺系、及聚氯乙烯系所組成之群中之一種以上。 [16] 如上述[14]所記載之樹脂組合物，其中上述媒體為熱塑性彈性體(E)， 該熱塑性彈性體(E)係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段、及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物；及至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物所組成之群中之一種或兩種以上。 [17] 如上述[14]至[16]中任一項所記載之樹脂組合物，其中包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑未達1 μm。 [發明之效果][1] A master batch composition comprising the following components: polyphenylene ether (A-1), and / or a function having at least one functional group selected from the group consisting of a carboxyl group and a group derived from a carboxyl group Modified polyphenylene ether (A-2); and block copolymer (B), which is selected from the group consisting of a polymer block (b1) containing at least 1 vinyl aromatic compound and at least 1 conjugated diene compound Non-hydride (B-0) of block copolymer of polymer block (b2); contains at least 1 vinyl aromatic polymer block (b1 ') and at least 1 conjugated diene compound polymer Block (b2 ') block copolymer hydride (BI); and contains at least 1 vinyl aromatic polymer polymer block (b1' ') and at least 1 conjugated diene compound and vinyl aromatic At least one of the group consisting of a hydride (B-II) of a block copolymer of a random copolymer of a group compound (b3); and (A-1) and / or (A-2) The weight average molecular weight of the polyphenylene ether is 10,000 or more and 50,000 or less, and the total amount includes the above (A-1), (A-2), and (B) in total 100 parts by mass. A-1) The above (A-2) is 10 parts by mass or more and 90 parts by mass or less, and includes the above (B) 10 parts by mass or more and 90 parts by mass or less. [2] The masterbatch composition according to the above [1], further comprising an antioxidant (C) and a lubricant (D), in addition to (A-1), (A-2), and ( The total of 100 parts by mass of B) includes from 0.1 to 20 parts by mass of the above (C) and from 0.1 to 40 parts by mass of the above (D). [3] The master batch composition according to the above [1] or [2], in which the total amount includes the above-mentioned (A-1), (A-2), and (B) in total 100 parts by mass (A-1) 20 mass parts or more and 50 mass parts or less of the above (A-2), and 50 mass parts or more and 80 mass parts or less of the above (B). [4] The master batch composition according to any one of the above [1] to [3], which has a sea-island structure, and the sea-island structure includes: an island phase consisting of the above (A-1) and / or the above (A-2); and marine phase, which consists of (B) above. [5] The master batch composition according to the above [4], wherein the average diameter of the island phases is less than 5 μm. [6] The master batch composition according to the above [5], wherein the average diameter of the island phases is less than 1 μm. [7] The master batch composition according to any one of the above [1] to [6], which has any shape selected from the group consisting of particles, small particles, and powder. [8] The master batch composition according to any one of the above [1] to [7], which is a polyphenylene ether master batch composition. [9] The master batch composition according to any one of the above [1] to [8], which can be used as a modifier. [10] A method for producing a resin composition, comprising the steps of: selecting the master batch composition according to any one of the above [1] to [9], and including a polymer selected from the group consisting of a thermoplastic elastomer and a soft thermoplastic polymer At least any medium in the group consisting of rubber, asphalt, sealant, adhesive, hot-melt adhesive, adhesive, and coating is mechanically kneaded at a temperature of less than 250 ° C. [11] The method for producing a resin composition according to the above [10], wherein the medium is a soft thermoplastic polymer, and the soft thermoplastic polymer is selected from the group consisting of polyolefins, polyurethanes, One or more selected from the group consisting of polyester, polyamide, and polyvinyl chloride. [12] The method for producing a resin composition according to the above [10], wherein the medium is a thermoplastic elastomer (E), and the thermoplastic elastomer (E) is selected from the group consisting of polymerized by at least one vinyl aromatic compound Non-hydrogenated block copolymer of polymer block and at least 1 conjugated diene compound polymer block; contains at least 1 vinyl aromatic polymer block and at least 1 conjugated diene compound polymer Block hydride of block copolymer; block comprising random copolymer block of at least 1 vinyl aromatic polymer block and at least 1 conjugated diene compound and vinyl aromatic compound One or two or more of a group consisting of a hydride of a copolymer; and a non-hydride of a random copolymer of at least one vinyl aromatic compound and at least one conjugated diene compound. [13] The method for producing a resin composition according to any one of the above [10] to [12], wherein the step of performing the kneading includes the above (A-1) and / or the above (A-2) The average particle size of the polyphenylene ether is less than 5 μm. [14] A resin composition comprising: polyphenylene ether (A-1) and / or a functional group-modified polybenzene having at least one functional group selected from the group consisting of a carboxyl group and a group derived from a carboxyl group Ether (A-2); block copolymer (B), which is selected from the group consisting of at least one vinyl aromatic polymer polymer block (b1) and at least one conjugated diene compound polymer block (b2) ) Of the block copolymer (B-0); contains at least 1 vinyl aromatic polymer block (b1 ') and at least 1 conjugated diene compound polymer block (b2') Hydride (BI) of a block copolymer; and random copolymerization comprising at least one vinyl aromatic polymer polymer block (b1 '') and at least one conjugated diene compound and a vinyl aromatic compound At least one of the group consisting of the hydride (B-II) of the block copolymer of the polymer block (b3); and the medium, which is selected from the group consisting of thermoplastic elastomers, soft thermoplastic polymers, rubber, asphalt, seals At least one of the group consisting of an adhesive, an adhesive, a hot-melt adhesive, an adhesive, and a coating; and including the above (A-1) The weight average molecular weight of the polyphenylene ether of the above (A-2) is 10,000 or more and 50,000 or less, and the average dispersed particle diameter of the polyphenylene ether including the above (A-1) and / or the (A-2) is not Up to 5 μm. [15] The resin composition according to the above-mentioned [14], wherein the medium is a soft thermoplastic polymer, and the soft thermoplastic polymer is selected from the group consisting of polyolefins, polyurethanes, polyesters, One or more of a group consisting of a polyamide system and a polyvinyl chloride system. [16] The resin composition according to the above [14], wherein the medium is a thermoplastic elastomer (E), and the thermoplastic elastomer (E) is selected from the group consisting of a polymer block containing at least one vinyl aromatic compound and Non-hydrogenated block copolymers of at least 1 polymer block of conjugated diene compound; embedding of at least 1 polymer block of vinyl aromatic compound and at least 1 polymer block of conjugated diene compound Hydrogenation of block copolymers; hydrogenation of block copolymers comprising at least one polymer block of a vinyl aromatic compound and at least one random copolymer block of a conjugated diene compound and a vinyl aromatic compound One or two or more of the group consisting of a non-hydride of a random copolymer of at least one vinyl aromatic compound and at least one conjugated diene compound. [17] The resin composition according to any one of the above [14] to [16], wherein the average dispersed particle diameter of the polyphenylene ether containing the (A-1) and / or the (A-2) Up to 1 μm. [Effect of the invention]

若使用本發明之母料組合物，則可以簡便之步驟且於溫和之混練條件下，使具有充分之分子量之聚苯醚均一分散及相溶於熱塑性彈性體等媒體中。以上述方式所獲得之本發明之樹脂組合物之耐熱老化性優異。If the masterbatch composition of the present invention is used, polyphenylene ether having a sufficient molecular weight can be uniformly dispersed and dissolved in a medium such as a thermoplastic elastomer under simple kneading conditions and under mild kneading conditions. The resin composition of the present invention obtained in the above manner is excellent in heat aging resistance.

以下，對用以實施本發明之形態(以下，簡稱為「本實施形態」)詳細地進行說明。 以下之本實施形態為用以說明本發明之例示，並非旨在將本發明限定為以下之內容。本發明可於其主旨之範圍內進行各種變化而實施。Hereinafter, the form (hereinafter, abbreviated as "this embodiment") for implementing this invention is demonstrated in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following. The present invention can be implemented with various changes within the scope of the gist thereof.

[母料組合物] 本實施形態之母料組合物係包含如下成分者： 聚苯醚(A-1)、及/或具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基之官能基改性聚苯醚(A-2)；與 嵌段共聚物(B)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段(b1)與至少1個共軛二烯化合物聚合物嵌段(b2)之嵌段共聚物之非氫化物(B-0)；包含至少1個乙烯基芳香族化合物聚合物嵌段(b1')與至少1個共軛二烯化合物聚合物嵌段(b2')之嵌段共聚物之氫化物(B-I)；及包含至少1個乙烯基芳香族化合物聚合物嵌段(b1'')及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)之嵌段共聚物之氫化物(B-II)所組成之群中之至少一種；且 包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量為10,000以上且50,000以下， 相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，合計包含上述(A-1)與上述(A-2)10質量份以上且90質量份以下，且包含上述(B)10質量份以上且90質量份以下。[Masterbatch composition] The masterbatch composition of this embodiment includes the following components: polyphenylene ether (A-1) and / or having at least one selected from the group consisting of a carboxyl group and a group derived from a carboxyl group Functional group-modified polyphenylene ether (A-2); and block copolymer (B), which are selected from the group consisting of at least one vinyl aromatic compound polymer block (b1) and at least one Non-hydrogenated product (B-0) of block copolymer of conjugated diene compound polymer block (b2); contains at least 1 vinyl aromatic polymer polymer block (b1 ') and at least 1 conjugated diene A hydride (BI) of a block copolymer of an olefinic polymer polymer block (b2 '); and at least one vinyl aromatic polymer polymer block (b1' ') and at least one conjugated diene compound At least one of the group consisting of a hydrogenated product (B-II) of a block copolymer of a random copolymer block (b3) with a vinyl aromatic compound; and including the above (A-1) and / or the above The weight average molecular weight of the polyphenylene ether of (A-2) is 10,000 or more and 50,000 or less, based on 100 parts by mass of the total of the above (A-1), the above (A-2), and the above (B) Containing the sum of (A-1) and the above-mentioned parts (A-2) 10 parts by mass or more and 90 or less by mass, and including the parts (B) 10 parts by mass or more and 90 or less by mass.

本實施形態之母料組合物係基於如下目的而使用者：藉由使聚苯醚均一分散及相溶於熱塑性彈性體、軟質系熱塑性聚合物、橡膠、瀝青、密封劑、接著劑、熱熔接著劑、黏著劑、塗料等各種媒體中，而對上述媒體賦予耐熱老化性。此處所謂耐熱老化性，係指於50℃以上且200℃以下之高溫環境下進行熱老化一定時間所得之上述媒體相對於熱老化前之上述媒體之各種物性的保持率。The masterbatch composition of this embodiment is intended for users based on the purpose of uniformly dispersing and dissolving polyphenylene ether in thermoplastic elastomers, soft thermoplastic polymers, rubber, asphalt, sealants, adhesives, and heat welding In various media such as adhesives, adhesives, and coatings, heat-aging resistance is imparted to the media. Here, the term “heat-resistant aging resistance” refers to the retention rate of various physical properties of the above-mentioned media obtained by performing thermal aging under a high-temperature environment of 50 ° C. to 200 ° C. for a certain period of time with respect to the aforementioned media before thermal aging.

作為上述熱塑性彈性體，並不限定於以下，但例如可列舉如下熱塑性彈性體(E)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段、及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物；及至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物所組成之群中之一種或兩種以上。The thermoplastic elastomer is not limited to the following, but examples include the following thermoplastic elastomer (E), which is selected from the group consisting of a polymer block containing at least one vinyl aromatic compound and at least one conjugated diene compound. Non-hydrides of block copolymers of polymer blocks; hydrides of block copolymers comprising at least 1 vinyl aromatic polymer polymer block and at least 1 conjugated diene compound polymer block; comprising At least one polymer block of a vinyl aromatic compound, and at least one hydrogenated block copolymer of a random copolymer block of a conjugated diene compound and a vinyl aromatic compound; and at least one vinyl aromatic compound One or two or more of the group consisting of a non-hydride of a random copolymer of a family compound and at least one conjugated diene compound.

作為軟質系熱塑性聚合物，例如可列舉選自由聚烯烴系、聚胺基甲酸酯系、聚酯系、聚醯胺系、及聚氯乙烯系所組成之群中之一種以上之軟質系熱塑性聚合物。 作為橡膠，例如可列舉：異戊二烯橡膠、氯丁二烯橡膠、丁二烯橡膠、苯乙烯丁二烯橡膠、丙烯酸系橡膠、胺基甲酸酯橡膠等。 作為瀝青，例如可列舉：直餾瀝青、吹製瀝青等石油瀝青；湖瀝青、岩瀝青等天然瀝青。 作為密封劑，例如可列舉：熱塑性彈性體系密封劑、EVA(乙烯-乙酸乙烯酯)系密封劑、聚矽氧系密封劑、胺基甲酸酯系密封劑等。 作為接著劑，例如可列舉：丙烯酸系接著劑、橡膠系接著劑、聚矽氧系接著劑、胺基甲酸酯系接著劑、環氧系接著劑等。 作為熱熔接著劑，可列舉：EVA系接著劑、橡膠系接著劑、SIS(苯乙烯-異戊二烯-苯乙烯)系接著劑等。 作為黏著劑，例如可列舉：丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑、胺基甲酸酯系黏著劑等。 作為塗料，例如可列舉：丙烯酸系塗料、胺基甲酸酯系塗料、環氧系塗料等。Examples of the soft thermoplastic polymer include one or more soft thermoplastics selected from the group consisting of polyolefins, polyurethanes, polyesters, polyamides, and polyvinyl chlorides. polymer. Examples of the rubber include isoprene rubber, chloroprene rubber, butadiene rubber, styrene butadiene rubber, acrylic rubber, and urethane rubber. Examples of the asphalt include petroleum asphalt such as straight run asphalt and blown asphalt; natural asphalt such as lake asphalt and rock asphalt. Examples of the sealant include a thermoplastic elastomer sealant, an EVA (ethylene-vinyl acetate) sealant, a silicone sealant, and a urethane sealant. Examples of the adhesive include an acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive, an epoxy adhesive, and the like. Examples of the hot-melt adhesive include EVA-based adhesives, rubber-based adhesives, and SIS (styrene-isoprene-styrene) -based adhesives. Examples of the adhesive include an acrylic adhesive, a rubber adhesive, a silicone adhesive, and a urethane adhesive. Examples of the paint include acrylic paints, urethane paints, and epoxy paints.

關於使用本實施形態之母料組合物，使聚苯醚均一分散及相溶於上述各種媒體、即熱塑性彈性體等中之方法，並不限定於以下，但例如可列舉如下方法：適當使用雙軸擠出機、單軸擠出機、捏合機、班布里混合機、輥型混練機、高速攪拌機等混練機，將熱塑性彈性體等各種媒體與上述本實施形態之母料組合物機械地進行混練。 關於此時之混練溫度，就防止上述媒體之熱劣化之觀點而言，較佳為未達350℃，更佳為未達250℃，進而較佳為未達200℃。 再者，所謂聚苯醚「均一分散」之狀態，係指包含未達全部聚苯醚之5體積%之具有50 μm以上之粒徑之聚苯醚凝聚體的狀態。 又，所謂聚苯醚「相溶」之狀態係指聚苯醚之平均分散粒徑未達5 μm之狀態。The method of uniformly dispersing and dissolving polyphenylene ether in the above-mentioned various media, that is, thermoplastic elastomers, using the master batch composition of this embodiment is not limited to the following, but for example, the following methods can be cited: use Shaft extruder, single-shaft extruder, kneader, Banbury mixer, roll-type kneader, high-speed mixer and other kneaders, mechanically mix various media such as thermoplastic elastomer with the master batch composition of this embodiment Perform the mixing. With regard to the kneading temperature at this time, from the viewpoint of preventing thermal degradation of the aforementioned media, it is preferably less than 350 ° C, more preferably less than 250 ° C, and even more preferably less than 200 ° C. The "uniformly dispersed" state of the polyphenylene ether refers to a state including polyphenylene ether aggregates having a particle size of 50 μm or more, which is less than 5% by volume of the entire polyphenylene ether. The "compatible" state of the polyphenylene ether refers to a state where the average dispersed particle diameter of the polyphenylene ether is less than 5 μm.

聚苯醚「均一分散」及「相溶」於上述各種媒體中之狀態可使用穿透式電子顯微鏡(TEM)等加以確認。 對使用熱塑性彈性體作為上述媒體之情形時之聚苯醚之「均一分散」及「相溶」之狀態的確認，具體地進行說明。 自包含本實施形態之母料組合物與作為媒體之熱塑性彈性體之樹脂組合物切出長度10 mm×寬度5 mm×厚度3～4 mm之染色用試片，利用超薄切片機於染色用試片之端部製作切片切出用之平面。 於關於作為媒體之熱塑性彈性體，包含含有至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物、及/或至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物之情形時，使上述染色用試片浸漬於加入至耐熱容器中之2質量%四氯化鋨水溶液中，於水浴中隔水加熱80℃×30分鐘後提拉，進行冷卻直至達到常溫後，自耐熱容器中取出，進行水洗、乾燥。 藉由該染色操作，包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物、及至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物被染色，且於TEM觀察時觀察為黑色。 於關於作為媒體之熱塑性彈性體，包含含有至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物、及/或含有至少1個乙烯基芳香族化合物聚合物嵌段及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物之情形時，於超薄切片機上安裝加入有水之金剛石刀，自染色用試片之切片切出用之平面於水之上切出厚度85 nm之薄膜，並利用TEM觀察用Cu篩網進行撈取。預先將載有該薄膜之Cu篩網排列在不鏽鋼網之上。另外向玻璃乾燥器中之培養皿中添加三氯化釕n水合物0.1 g與純化水1 mL，使之溶解後，添加次亞氯酸鈉溶液5 mL，即刻載置載有Cu篩網之不鏽鋼網，該Cu篩網載有薄膜，對玻璃乾燥器蓋上蓋並靜置4分鐘後，取出Cu篩網。藉由該染色操作，包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物、及包含至少1個乙烯基芳香族化合物聚合物嵌段、及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物被染色，且於TEM觀察時觀察為黑色。The state of "uniform dispersion" and "miscibility" of polyphenylene ether in the above-mentioned various media can be confirmed using a transmission electron microscope (TEM) or the like. The confirmation of the state of "uniform dispersion" and "miscibility" of the polyphenylene ether when a thermoplastic elastomer is used as the medium will be specifically described. From the master batch composition of this embodiment and the resin composition of the thermoplastic elastomer as a medium, a test piece for dyeing with a length of 10 mm × width of 5 mm × thickness of 3 to 4 mm was cut, and a thin slicer was used for dyeing. The end of the test piece is made into a plane for cutting out. In regard to a thermoplastic elastomer as a medium, a non-hydride containing a block copolymer containing at least one vinyl aromatic polymer polymer block and at least one conjugated diene compound polymer block, and / or at least In the case of a non-hydride of a random copolymer of a vinyl aromatic compound and at least one conjugated diene compound, the above-mentioned dyeing test piece is immersed in a 2 mass% rhenium tetrachloride aqueous solution added to a heat-resistant container After heating in a water bath at 80 ° C. for 30 minutes, it was pulled and cooled until it reached normal temperature, and then taken out of the heat-resistant container, washed with water, and dried. By this dyeing operation, a non-hydride of a block copolymer including at least one vinyl aromatic polymer polymer block and at least one conjugated diene compound polymer block, and at least one vinyl aromatic compound The non-hydride of the random copolymer with at least one conjugated diene compound is dyed and is black when observed by TEM. The thermoplastic elastomer used as a medium comprises a hydride of a block copolymer containing at least one vinyl aromatic polymer polymer block and at least one conjugated diene compound polymer block, and / or containing at least In the case of a hydride of a block copolymer of a vinyl aromatic polymer polymer block and at least one random copolymer block of a conjugated diene compound and a vinyl aromatic compound, in an ultra-thin microtome A diamond knife with water was installed on it, and a film with a thickness of 85 nm was cut from the plane used for cutting out the slice of the dyeing test piece above the water, and it was removed by Cu screen using TEM observation. The Cu sieve carrying the film was arranged on a stainless steel net in advance. In addition, add 0.1 g of ruthenium trichloride n hydrate and 1 mL of purified water to a petri dish in a glass drier, and dissolve them. Then add 5 mL of sodium hypochlorite solution, and immediately place the Stainless steel mesh, the Cu mesh is loaded with a film, the glass dryer is covered and left for 4 minutes, and then the Cu mesh is taken out. By this dyeing operation, a hydride of a block copolymer including at least one vinyl aromatic polymer polymer block and at least one conjugated diene compound polymer block, and at least one vinyl aromatic polymer The compound polymer block and the hydrogenated product of the block copolymer of at least one random copolymer block of a conjugated diene compound and a vinyl aromatic compound are dyed, and are observed to be black in TEM observation.

藉由使用上述染色法，可使熱塑性彈性體成為黑色相，使聚苯醚成為白色相，而進行TEM觀察。 進而，藉由使用市售之圖像分析軟體對該TEM像照片進行圖像分析，可求出具有50 μm以上之粒徑之聚苯醚凝聚體相對於全部聚苯醚之面積分率、及聚苯醚之平均分散粒徑。再者，此處，具有50 μm以上之粒徑之聚苯醚凝聚體相對於全部聚苯醚之面積分率係視為與具有50 μm以上之粒徑之聚苯醚凝聚體相對於全部聚苯醚之體積分率同等。 藉由以上之操作，可確認聚苯醚「均一分散」及「相溶」於作為媒體之熱塑性彈性體中之狀態。By using the dyeing method described above, the thermoplastic elastomer can be made into a black phase, and the polyphenylene ether can be made into a white phase, and the TEM observation can be performed. Furthermore, by performing image analysis on the TEM image photograph using a commercially available image analysis software, the area fraction of polyphenylene ether aggregates having a particle size of 50 μm or more with respect to the entire polyphenylene ether, and The average particle size of polyphenylene ether. Here, the area fraction of polyphenylene ether aggregates having a particle size of 50 μm or more with respect to all polyphenylene ethers is considered to be the same as that of polyphenylene ether aggregates having a particle size of 50 μm or more with respect to all polyphenylene ethers. The volume fraction of phenyl ether is the same. By the above operation, the state of "uniform dispersion" and "miscibility" of the polyphenylene ether in the thermoplastic elastomer as a medium can be confirmed.

於上述中，對使用熱塑性彈性體作為媒體之情形時之聚苯醚之「均一分散」及「相溶」之狀態之確認進行了說明，關於使用其他材料作為媒體之情形時，例如可藉由適當使用光學顯微鏡、穿透式電子顯微鏡(TEM)、掃描式電子顯微鏡(SEM)、原子力顯微鏡(AFM)等進行觀察，而確認聚苯醚之「均一分散」及「相溶」之狀態。In the above, the confirmation of the state of "uniform dispersion" and "miscibility" of polyphenylene ether when using a thermoplastic elastomer as a medium has been explained. When using other materials as a medium, for example, An optical microscope, a transmission electron microscope (TEM), a scanning electron microscope (SEM), and an atomic force microscope (AFM) were used for observation, and the states of "uniform dispersion" and "miscibility" of the polyphenylene ether were confirmed.

(聚苯醚(A-1)、及具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基之官能基改性聚苯醚(A-2)) 本實施形態之母料組合物含有聚苯醚(A-1)、及/或具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基之官能基改性聚苯醚(A-2)(以下，存在記載為(A-1)成分、(A-1)、官能基改性聚苯醚(A-2)、(A-2)成分、(A-2)之情形)。 本實施形態之母料組合物中所使用之聚苯醚(A-1)並不限定於以下，但例如可列舉：包含下述式(1)所表示之單元結構之均聚物、及/或包含下述式(1)所表示之單元結構之共聚物。(Polyphenylene ether (A-1) and a functional group-modified polyphenylene ether (A-2) having at least one functional group selected from the group consisting of a carboxyl group and a group derived from a carboxyl group) Mother of this embodiment The composition contains polyphenylene ether (A-1) and / or a functional group-modified polyphenylene ether (A-2) having at least one functional group selected from the group consisting of a carboxyl group and a group derived from a carboxyl group ( Hereinafter, it may be described as (A-1) component, (A-1), functional group modified polyphenylene ether (A-2), (A-2) component, (A-2)). The polyphenylene ether (A-1) used in the master batch composition of this embodiment is not limited to the following, but examples thereof include a homopolymer containing a unit structure represented by the following formula (1), and / Or a copolymer containing a unit structure represented by the following formula (1).

[化1] [Chemical 1]

式(1)中，R1 、R2 、R3 、及R4 分別獨立地為氫原子、鹵素原子、碳原子數1～7之一級烷基、碳原子數1～7之二級烷基、苯基、鹵烷基、胺基烷基、烴氧基、及選自由至少2個碳原子隔開鹵素原子與氧原子之鹵代烴氧基所組成之群中之一價基。In formula (1), R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, and a secondary alkyl group having 1 to 7 carbon atoms. , A phenyl group, a haloalkyl group, an aminoalkyl group, a alkoxy group, and a monovalent group selected from the group consisting of a halogenated alkoxy group having at least 2 carbon atoms separating a halogen atom and an oxygen atom.

作為本實施形態之母料組合物中所使用之聚苯醚(A-1)，可使用公知者。並不限定於以下，但例如可列舉：聚(2,6-二甲基-1,4-苯醚)、聚(2-甲基-6-乙基-1,4-苯醚)、聚(2-甲基-6-苯基-1,4-苯醚)、聚(2,6-二氯-1,4-苯醚)等均聚物；2,6-二甲基苯酚與2,3,6-三甲基苯酚或2-甲基-6-丁基苯酚等其他酚類之共聚物等共聚物。 作為聚苯醚(A-1)，尤其是就獲取之容易性之觀點、以及向熱塑性彈性體等各種媒體中之均一分散性及相溶性之觀點而言，較佳為聚(2,6-二甲基-1,4-苯醚)、2,6-二甲基苯酚與2,3,6-三甲基苯酚之共聚物，更佳為聚(2,6-二甲基-1,4-苯醚)。 上述聚苯醚可單獨使用一種，亦可組合兩種以上而使用。As the polyphenylene ether (A-1) used in the master batch composition of this embodiment, a known one can be used. It is not limited to the following, but examples thereof include poly (2,6-dimethyl-1,4-phenyl ether), poly (2-methyl-6-ethyl-1,4-phenyl ether), and poly (2-methyl-6-phenyl-1,4-phenyl ether), poly (2,6-dichloro-1,4-phenyl ether) and other homopolymers; 2,6-dimethylphenol and 2 Copolymers such as 3,6-trimethylphenol or 2-methyl-6-butylphenol and other phenolic copolymers. As the polyphenylene ether (A-1), poly (2,6-) is particularly preferred from the viewpoint of ease of availability and the viewpoint of uniform dispersibility and compatibility in various media such as thermoplastic elastomers. Dimethyl-1,4-phenyl ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, more preferably poly (2,6-dimethyl-1, 4-phenyl ether). These polyphenylene ethers may be used alone or in combination of two or more.

聚苯醚(A-1)可藉由公知之方法進行製造。 作為聚苯醚(A-1)之製造方法，並不限定於以下，但例如可列舉：使用Hay之美國專利第3306874號說明書中所記載之亞銅鹽與胺之混合物作為觸媒，而使2,6-二甲苯酚氧化聚合之方法；或美國專利第3306875號說明書、美國專利第3257357號說明書、美國專利第3257358號說明書、日本專利特公昭52-17880號公報、日本專利特開昭50-51197號公報、及日本專利特開昭63-152628號公報等中所記載之其他方法等。The polyphenylene ether (A-1) can be produced by a known method. The production method of polyphenylene ether (A-1) is not limited to the following, but examples include the use of a mixture of a cuprous salt and an amine described in Hay's US Pat. No. 3306874 specification as a catalyst, Method for oxidative polymerization of 2,6-xylenol; or US Patent No. 3306875, US Patent No. 3257357, US Patent No. 3257358, Japanese Patent Publication No. 52-17880, Japanese Patent Publication No. 50 -51197 and other methods described in Japanese Patent Laid-Open No. 63-152628 and the like.

本實施形態之母料組合物中所含之具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基的官能基改性聚苯醚(A-2)係藉由使上述聚苯醚(A-1)與不飽和羧酸或其衍生物(G)進行反應而獲得。 作為不飽和羧酸或其衍生物(G)對於聚苯醚(A-1)之加成量，相對於聚苯醚(A-1)100質量%，較佳為0.01～10質量%。作為反應之條件，不限定於以下，例如可列舉於自由基產生劑之存在下或非存在下，於熔融狀態、溶液狀態或漿料狀態下，於80～350℃之溫度下進行之條件等。The functional group-modified polyphenylene ether (A-2) having at least one functional group selected from the group consisting of a carboxyl group and a group derived from a carboxyl group contained in the master batch composition of this embodiment is obtained by making the above Polyphenylene ether (A-1) is obtained by reacting with an unsaturated carboxylic acid or its derivative (G). The addition amount of the unsaturated carboxylic acid or its derivative (G) to the polyphenylene ether (A-1) is preferably 0.01 to 10% by mass based on 100% by mass of the polyphenylene ether (A-1). The conditions of the reaction are not limited to the following, and examples thereof include conditions in which a radical generator is present or non-existent in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C. .

作為不飽和羧酸或其衍生物(G)，並不限定於以下，但例如可列舉：順丁烯二酸、反丁烯二酸、檸康酸、甲基反丁烯二酸、烏頭酸、伊康酸、順式-4-環己烯-1,2-二羧酸、氯順丁烯二酸等不飽和二羧酸類；順丁烯二酸酐、檸康酸酐、烏頭酸酐、伊康酸酐、順式-4-環己烯-1,2-二羧酸二酐、氯順丁烯二酸酐等不飽和二羧酸二酐類；順丁烯二酸單甲酯、順丁烯二酸二甲酯、順丁烯二酸單乙酯、順丁烯二酸二乙酯、反丁烯二酸單甲酯、反丁烯二酸二甲酯、反丁烯二酸單乙酯、反丁烯二酸二乙酯等不飽和二羧酸之半酯及酯類。其中，較佳為順丁烯二酸、反丁烯二酸、檸康酸、甲基反丁烯二酸、伊康酸、順丁烯二酸酐，更佳為順丁烯二酸、順丁烯二酸酐。該等可單獨使用一種，亦可組合兩種以上而使用。The unsaturated carboxylic acid or its derivative (G) is not limited to the following, but examples thereof include maleic acid, fumaric acid, citraconic acid, methyl fumaric acid, and aconitic acid. , Ikonic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, chloromaleic acid and other unsaturated dicarboxylic acids; maleic anhydride, citraconic anhydride, aconitic anhydride, Ikon Unsaturated dicarboxylic dianhydrides such as acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic dianhydride, chloromaleic anhydride; maleic acid monomethyl ester, maleic acid Dimethyl acid, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, Half esters and esters of unsaturated dicarboxylic acids such as diethyl fumarate. Among them, maleic acid, fumaric acid, citraconic acid, methyl fumaric acid, itaconic acid, maleic anhydride, more preferred are maleic acid, maleic acid Oxalic anhydride. These can be used alone or in combination of two or more.

藉由包含官能基改性聚苯醚(A-2)，可減少本實施形態之母料組合物之臭氣。 於本實施形態之母料組合物中，作為對聚苯醚進行官能基改性之方法，只要為可適宜地獲得官能基改性聚苯醚(A-2)之方法，則無特別限定。 作為具體之方法，可例示以下。即，可列舉如下方法： (i)藉由事先使聚苯醚(A-1)與不飽和羧酸或其衍生物(G)進行反應，而預先獲得官能基改性聚苯醚(A-2)，其後，使用其與其他成分混合，而製造母料組合物； (ii)於母料組合物之製造時，藉由在系統中使聚苯醚(A-1)與不飽和羧酸或其衍生物(G)進行反應，而獲得官能基改性聚苯醚(A-2)，同時製造母料組合物。By including the functional group-modified polyphenylene ether (A-2), the odor of the master batch composition of this embodiment can be reduced. In the master batch composition of this embodiment, the method for modifying the functional group of polyphenylene ether is not particularly limited as long as it is a method capable of appropriately obtaining the functional group-modified polyphenylene ether (A-2). As a specific method, the following can be exemplified. That is, the following methods can be enumerated: (i) A functional group-modified polyphenylene ether (A- is obtained in advance by reacting the polyphenylene ether (A-1) with an unsaturated carboxylic acid or its derivative (G) in advance). 2) After that, it is mixed with other ingredients to produce a masterbatch composition; (ii) During the production of the masterbatch composition, polyphenylene ether (A-1) and an unsaturated carboxylic acid are made in the system The acid or its derivative (G) is reacted to obtain a functional group-modified polyphenylene ether (A-2), and a master batch composition is produced.

本實施形態之母料組合物中所含之包含聚苯醚(A-1)、及/或官能基改性聚苯醚(A-2)之聚苯醚之重量平均分子量為10,000以上且50,000以下。 即，本實施形態之母料組合物中所含之聚苯醚成分整體之重量平均分子量為10,000以上且50,000以下。 藉由使包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量為10,000以上，包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物成為耐熱老化性優異者。就提高該耐熱老化性之觀點而言，包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量較佳為15,000以上，更佳為20,000以上。 另一方面，藉由使包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量為50,000以下，本實施形態之母料組合物之造粒穩定性變得良好。就提高該造粒穩定性之觀點而言，包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量較佳為45,000以下，更佳為40,000以下。 再者，聚苯醚(A-1)、及官能基改性聚苯醚(A-2)之重量平均分子量係藉由使用凝膠滲透層析(GPC)測定裝置之測定而獲得。 作為具體之GPC之測定條件，可列舉使用昭和電工股份有限公司製造之GPC系統21(管柱：使2根昭和電工股份有限公司製造之K-805L串聯、管柱溫度：40℃、溶劑：氯仿、溶劑流量：1.0 mL/min、樣品濃度：聚苯醚之1 g/L氯仿溶液)，製作標準聚苯乙烯(標準聚苯乙烯之分子量為3,650,000、2,170,000、1,090,000、681,000、204,000、52,000、30,200、13,800、3,360、1,300、550)之校準曲線之測定條件。關於檢測部之UV(Ultra Violet，紫外線)之波長，於標準聚苯乙烯之情形時可選擇254 nm，於聚苯醚之情形時可選擇283 nm。The weight average molecular weight of the polyphenylene ether containing polyphenylene ether (A-1) and / or functional group-modified polyphenylene ether (A-2) contained in the master batch composition of this embodiment is 10,000 or more and 50,000 the following. That is, the weight average molecular weight of the entire polyphenylene ether component contained in the master batch composition of this embodiment is 10,000 or more and 50,000 or less. By setting the weight average molecular weight of the polyphenylene ether containing the above-mentioned (A-1) and / or the above-mentioned (A-2) to 10,000 or more, the resin composition including the master batch composition of this embodiment and various media such as thermoplastic elastomers is combined. The material becomes excellent in heat aging resistance. From the viewpoint of improving the heat aging resistance, the weight average molecular weight of the polyphenylene ether containing the above (A-1) and / or the above (A-2) is preferably 15,000 or more, and more preferably 20,000 or more. On the other hand, by making the weight average molecular weight of the polyphenylene ether containing (A-1) and / or (A-2) above 50,000, the granulation stability of the master batch composition of this embodiment becomes good. From the viewpoint of improving the granulation stability, the weight average molecular weight of the polyphenylene ether containing the above-mentioned (A-1) and / or the above-mentioned (A-2) is preferably 45,000 or less, and more preferably 40,000 or less. The weight average molecular weight of the polyphenylene ether (A-1) and the functional group-modified polyphenylene ether (A-2) was obtained by measurement using a gel permeation chromatography (GPC) measurement device. Specific GPC measurement conditions include the use of GPC system 21 manufactured by Showa Denko Corporation (column: two K-805L manufactured by Showa Denko Corporation in series, column temperature: 40 ° C, solvent: chloroform) Solvent flow rate: 1.0 mL / min, sample concentration: 1 g / L chloroform solution of polyphenylene ether), standard polystyrene (standard polystyrene molecular weight is 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200 , 13,800, 3,360, 1,300, 550). Regarding the UV (Ultra Violet) wavelength of the detection section, 254 nm can be selected in the case of standard polystyrene, and 283 nm can be selected in the case of polyphenylene ether.

本實施形態之母料組合物相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，合計包含上述(A-1)與上述(A-2)10質量份以上且90質量份以下。 藉由使上述(A-1)及上述(A-2)合計為10質量份以上，包含本實施形態之母料組合物與熱塑性彈性體等媒體之樹脂組合物成為耐熱老化性優異者。另一方面，藉由使上述(A-1)及上述(A-2)合計為90質量份以下，上述(A-1)及上述(A-2)均一分散於包含本實施形態之母料組合物與熱塑性彈性體等媒體之樹脂組合物中。 作為上述(A-1)及上述(A-2)之合計量之較佳範圍，為15質量份以上且85質量份以下，作為進而較佳之範圍，為20質量份以上且80質量份以下，作為進而更佳之範圍，為20質量份以上且50質量份以下。The master batch composition according to this embodiment is 100 parts by mass of the total of the above (A-1), (A-2), and (B), and the total includes the above (A-1) and (A-2) 10 At least 90 parts by mass. When the total of the above (A-1) and the above (A-2) is 10 parts by mass or more, the resin composition containing the medium such as the master batch composition and the thermoplastic elastomer of the present embodiment is excellent in heat aging resistance. On the other hand, when the total of (A-1) and (A-2) is 90 parts by mass or less, the (A-1) and (A-2) are uniformly dispersed in the master batch including the embodiment. The composition and the resin composition of a medium such as a thermoplastic elastomer. A preferable range of the total amount of the above (A-1) and (A-2) is 15 parts by mass or more and 85 parts by mass or less, and a further preferable range is 20 parts by mass or more and 80 parts by mass or less, A more preferable range is 20 parts by mass or more and 50 parts by mass or less.

(嵌段共聚物(B)) 本實施形態之母料組合物含有嵌段共聚物(B)(以下，存在記載為嵌段共聚物(B)、(B)成分、(B)之情形)，其係 選自由包含至少1個乙烯基芳香族化合物聚合物嵌段(b1)與至少1個共軛二烯化合物聚合物嵌段(b2)之嵌段共聚物之非氫化物(B-0)；包含至少1個乙烯基芳香族化合物聚合物嵌段(b1')與至少1個共軛二烯化合物聚合物嵌段(b2')之嵌段共聚物之氫化物(B-I)；及包含至少1個乙烯基芳香族化合物聚合物嵌段(b1'')及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)之嵌段共聚物之氫化物(B-II) 所組成之群中之至少一種。(Block copolymer (B)) The master batch composition of this embodiment contains a block copolymer (B) (hereinafter, it may be described as a block copolymer (B), (B) component, and (B)) , Which is a non-hydride (B-0) selected from a block copolymer comprising at least one vinyl aromatic polymer polymer block (b1) and at least one conjugated diene compound polymer block (b2). ); A hydride (BI) of a block copolymer comprising at least 1 vinyl aromatic polymer polymer block (b1 ') and at least 1 conjugated diene compound polymer block (b2'); and Hydrogenated product of at least 1 vinyl aromatic polymer polymer block (b1 '') and at least 1 random copolymer block of conjugated diene compound and vinyl aromatic compound (b3) (B-II) at least one of the group.

＜包含至少1個乙烯基芳香族化合物聚合物嵌段(b1)與至少1個共軛二烯化合物聚合物嵌段(b2)之嵌段共聚物之非氫化物(B-0)＞ 作為本實施形態之母料組合物所使用之嵌段共聚物(B-0)之結構，並無特別限定，例如可列舉：式(b1)-(b2)所表示之二嵌段共聚物；式(b1)-(b2)-(b1)所表示之三嵌段共聚物；式(b1)-(b2)-(b1)-(b2)、式(b1)-(b2)-(b1)-(b2)-(b1)、式{(b1)-(b2)-}n X等所表示之多嵌段共聚物。 此處，式中之n為2以上且6以下之整數，X為偶合劑之反應殘基。 於本實施形態中，嵌段共聚物(B-0)可為單一結構，亦可為以任意比率包含複數種結構之混合物。<Non-hydride (B-0) of a block copolymer containing at least one vinyl aromatic polymer polymer block (b1) and at least one conjugated diene compound polymer block (b2)> The structure of the block copolymer (B-0) used in the master batch composition of the embodiment is not particularly limited, and examples thereof include the diblock copolymers represented by the formulae (b1) to (b2); the formula ( b1)-(b2)-(b1) triblock copolymer; formula (b1)-(b2)-(b1)-(b2), formula (b1)-(b2)-(b1)-( b2) A multi-block copolymer represented by formula ((b1)-(b2)-} n X). Here, n in the formula is an integer of 2 or more and 6 or less, and X is a reaction residue of a coupling agent. In this embodiment, the block copolymer (B-0) may have a single structure or a mixture including a plurality of structures at an arbitrary ratio.

作為乙烯基芳香族化合物聚合物嵌段(b1)所使用之乙烯基芳香族化合物，並不限定於以下，但例如可列舉：苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、及對甲基苯乙烯、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。 該等之中，就聚合性及物性之觀點而言，可適宜地使用苯乙烯、α-甲基苯乙烯、二乙烯苯。 該等乙烯基芳香族化合物可單獨使用一種，亦可併用兩種以上。The vinyl aromatic compound used as the vinyl aromatic compound polymer block (b1) is not limited to the following, but examples thereof include styrene, α-methylstyrene, o-methylstyrene, and m-styrene. Methylstyrene and p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p Aminoethylstyrene and the like. Among these, from the viewpoints of polymerizability and physical properties, styrene, α-methylstyrene, and divinylbenzene can be suitably used. These vinyl aromatic compounds may be used alone or in combination of two or more.

作為共軛二烯化合物聚合物嵌段(b2)所使用之共軛二烯化合物，並不限定於以下，但例如可列舉：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。 該等之中，就聚合性及物性之觀點而言，可適宜地使用1,3-丁二烯、2-甲基-1,3-丁二烯(異戊二烯)。 該等共軛二烯化合物可單獨使用一種，亦可併用兩種以上。The conjugated diene compound used as the conjugated diene compound polymer block (b2) is not limited to the following, but examples thereof include 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 and the like. Among these, from the viewpoints of polymerizability and physical properties, 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) can be suitably used. These conjugated diene compounds may be used alone or in combination of two or more.

於本實施形態中，共軛二烯化合物聚合物嵌段(b2)之微結構(順式、反式、乙烯基之比率)並無特別限定，可任意地進行選擇。 於共軛二烯化合物聚合物嵌段(b2)中，關於1,2-乙烯鍵量與3,4-乙烯鍵量之合計(以下，亦稱為「全部乙烯鍵量」)，就提高包含本實施形態之母料組合物與熱塑性彈性體之樹脂組合物之耐熱老化性的觀點而言，較佳為2%以上且80%以下，更佳為5%以上且60%以下。 再者，所謂全部乙烯鍵量，係指非氫化之共軛二烯化合物單元中之1,2-乙烯鍵量與3,4-乙烯鍵量之合計相對於1,2-乙烯鍵量、3,4-乙烯鍵量及1,4-共軛鍵量之合計的比率。全部乙烯鍵量可使用核磁共振裝置(NMR)進行測定而算出。In this embodiment, the microstructure (the ratio of cis, trans, and vinyl) of the polymer block (b2) of the conjugated diene compound is not particularly limited, and can be arbitrarily selected. In the conjugated diene compound polymer block (b2), the total amount of 1,2-ethylene bonds and 3,4-ethylene bonds (hereinafter, also referred to as "the total amount of ethylene bonds") is increased to include From the viewpoint of the heat aging resistance of the master batch composition and the thermoplastic elastomer resin composition of this embodiment, it is preferably 2% or more and 80% or less, and more preferably 5% or more and 60% or less. The total amount of ethylene bonds refers to the total amount of 1,2-ethylene bonds and 3,4-ethylene bonds in the non-hydrogenated conjugated diene compound unit. The total ratio of the amount of 4,4-ethylene bonds and the amount of 1,4-conjugated bonds. The total amount of ethylene bonds can be calculated by measuring using a nuclear magnetic resonance apparatus (NMR).

於本實施形態中，關於嵌段共聚物(B-0)之重量平均分子量，就提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物之耐熱老化性的觀點而言，較佳為50,000以上，更佳為100,000以上。 另一方面，就本實施形態之母料組合物之造粒穩定性之觀點而言，較佳為500,000以下，更佳為300,000以下。再者，此處所謂重量平均分子量可藉由GPC以苯乙烯換算分子量之形式求出。In this embodiment, regarding the weight average molecular weight of the block copolymer (B-0), from the viewpoint of improving the heat aging resistance of the resin composition including the master batch composition of this embodiment and various media such as thermoplastic elastomers, In other words, it is preferably 50,000 or more, and more preferably 100,000 or more. On the other hand, from the viewpoint of the granulation stability of the master batch composition of this embodiment, it is preferably 500,000 or less, and more preferably 300,000 or less. In addition, the weight average molecular weight here can be calculated | required by GPC as a styrene conversion molecular weight.

關於嵌段共聚物(B-0)中之乙烯基芳香族化合物聚合物嵌段(b1)之含量，就提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物之耐熱老化性的觀點而言，較佳為20質量%以上且70質量%以下，更佳為25質量%以上且65質量%以下。 再者，嵌段共聚物(B-0)中之乙烯基芳香族化合物聚合物嵌段(b1)之含量例如可藉由以下之方法進行測定。 根據藉由將四氧化鋨作為觸媒並利用氫過氧化第三丁基使未氫化之共聚物氧化分解之方法(I. M. Kolthoff, et al., J. Polym. Sci. 1,429 (1946)所記載之方法)所獲得之乙烯基芳香族化合物聚合物嵌段的質量，並基於下述式，可求出乙烯基芳香族化合物聚合物嵌段(b1)之含量。 乙烯基芳香族化合物聚合物嵌段之含量[質量%]＝(未氫化之共聚物中之乙烯基芳香族化合物聚合物嵌段之質量/未氫化之共聚物之質量)×100Regarding the content of the vinyl aromatic polymer polymer block (b1) in the block copolymer (B-0), the content of the resin composition including the master batch composition of this embodiment and the resin composition of various media such as a thermoplastic elastomer is increased. From the viewpoint of heat aging resistance, it is preferably 20% by mass or more and 70% by mass or less, and more preferably 25% by mass or more and 65% by mass or less. The content of the vinyl aromatic polymer polymer block (b1) in the block copolymer (B-0) can be measured, for example, by the following method. According to the method of oxidatively decomposing an unhydrogenated copolymer by using osmium tetroxide as a catalyst and using third butyl hydroperoxide (IM Kolthoff, et al., J. Polym. Sci. 1,429 (1946) Method) The mass of the vinyl aromatic polymer block obtained and the content of the vinyl aromatic polymer block (b1) can be determined based on the following formula. Content of vinyl aromatic polymer block [mass%] = (mass of vinyl aromatic polymer block in unhydrogenated copolymer / mass of unhydrogenated copolymer) x 100

作為嵌段共聚物(B-0)之製造方法，並無特別限定，例如可列舉以下之方法。 將正丁基鋰作為聚合觸媒，於環己烷溶劑中，將四氫呋喃作為全部乙烯鍵量調節劑，例如使苯乙烯與1,3-丁二烯進行陰離子活性聚合，藉此可合成具有特定之苯乙烯嵌段含量與重量平均分子量之嵌段共聚物。再者，聚合物結構可藉由調整單體之添加量進行控制，分子量可藉由調整觸媒量進行控制。The manufacturing method of a block copolymer (B-0) is not specifically limited, For example, the following methods are mentioned. N-butyllithium is used as a polymerization catalyst, and tetrahydrofuran is used as a total ethylene bond amount modifier in a cyclohexane solvent. For example, anionic living polymerization of styrene and 1,3-butadiene can be performed to synthesize specific compounds. A block copolymer of styrene block content and weight average molecular weight. Furthermore, the polymer structure can be controlled by adjusting the amount of monomer added, and the molecular weight can be controlled by adjusting the amount of catalyst.

＜嵌段共聚物之氫化物(B-I)＞ 作為本實施形態之母料組合物中所使用之包含至少1個乙烯基芳香族化合物聚合物嵌段(b1')與至少1個共軛二烯化合物聚合物嵌段(b2')之嵌段共聚物之氫化物(B-I)(氫化嵌段共聚物(B-I))的結構，並無特別限定，例如可列舉：式(b1')-(b2')所表示之二嵌段共聚物；式(b1')-(b2')-(b1')所表示之三嵌段共聚物；式(b1')-(b2')-(b1')-(b2')、式(b1')-(b2')-(b1')-(b2')-(b1')、式{(b1')-(b2')-}n X等所表示之多嵌段共聚物。 此處，式中之n為2以上且6以下之整數，X為偶合劑之反應殘基。 於本實施形態中，氫化嵌段共聚物(B-I)可為單一結構，亦可為以任意比率包含複數種結構之混合物。<Hydrohydride (BI) of block copolymer> The master batch composition used in this embodiment contains at least one vinyl aromatic polymer polymer block (b1 ') and at least one conjugated diene. The structure of the hydride (BI) (hydrogenated block copolymer (BI)) of the block copolymer of the compound polymer block (b2 ') is not particularly limited, and examples thereof include the formulae (b1') to (b2) Diblock copolymer represented by '); triblock copolymer represented by formula (b1')-(b2 ')-(b1'); formula (b1 ')-(b2')-(b1 ') -(b2 '), formula (b1')-(b2 ')-(b1')-(b2 ')-(b1'), formula ((b1 ')-(b2')-) n X, etc. Multiblock copolymer. Here, n in the formula is an integer of 2 or more and 6 or less, and X is a reaction residue of a coupling agent. In this embodiment, the hydrogenated block copolymer (BI) may have a single structure or a mixture including a plurality of structures at an arbitrary ratio.

作為乙烯基芳香族化合物聚合物嵌段(b1')中所使用之乙烯基芳香族化合物，並不限定於以下，但例如可列舉：苯乙烯、α-甲基苯乙烯、鄰、間、及對甲基苯乙烯、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。 該等之中，就聚合性及物性之觀點而言，可適宜地使用苯乙烯、α-甲基苯乙烯、二乙烯苯。 該等乙烯基芳香族化合物可單獨使用一種，亦可併用兩種以上。The vinyl aromatic compound used as the vinyl aromatic compound polymer block (b1 ') is not limited to the following, but examples thereof include styrene, α-methylstyrene, ortho, meta, and P-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene Wait. Among these, from the viewpoints of polymerizability and physical properties, styrene, α-methylstyrene, and divinylbenzene can be suitably used. These vinyl aromatic compounds may be used alone or in combination of two or more.

作為共軛二烯化合物聚合物嵌段(b2')所使用之共軛二烯化合物，並不限定於以下，但例如可列舉：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。 該等之中，就聚合性及物性之觀點而言，可適宜地使用1,3-丁二烯、2-甲基-1,3-丁二烯(異戊二烯)。 該等共軛二烯化合物可單獨使用一種，亦可併用兩種以上。The conjugated diene compound used as the conjugated diene compound polymer block (b2 ') is not limited to the following, but examples thereof include 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 and the like. Among these, from the viewpoints of polymerizability and physical properties, 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) can be suitably used. These conjugated diene compounds may be used alone or in combination of two or more.

於本實施形態中，共軛二烯化合物聚合物嵌段(b2')之微結構(順式、反式、乙烯基之比率)並無特別限定，可任意地進行選擇。 於共軛二烯化合物聚合物嵌段(b2')中，關於1,2-乙烯鍵量與3,4-乙烯鍵量之合計(以下，亦稱為「全部乙烯鍵量」)，就提高包含本實施形態之母料組合物與熱塑性彈性體之樹脂組合物之耐熱老化性的觀點而言，較佳為2%以上且80%以下，更佳為5%以上且60%以下。 再者，所謂全部乙烯鍵量，係指未氫化之共軛二烯化合物單元中之1,2-乙烯鍵量與3,4-乙烯鍵量之合計相對於1,2-乙烯鍵量、3,4-乙烯鍵量及1,4-共軛鍵量之合計的比率。全部乙烯鍵量可使用核磁共振裝置(NMR)進行測定而算出。In this embodiment, the microstructure (cis, trans, and vinyl ratio) of the conjugated diene compound polymer block (b2 ') is not particularly limited, and can be arbitrarily selected. In the conjugated diene compound polymer block (b2 '), the total amount of 1,2-ethylene bonds and 3,4-ethylene bonds (hereinafter, also referred to as "the total amount of ethylene bonds") is increased. From the viewpoint of the heat aging resistance of the resin composition including the master batch composition and the thermoplastic elastomer of this embodiment, it is preferably 2% or more and 80% or less, and more preferably 5% or more and 60% or less. The total amount of ethylene bonds refers to the total amount of 1,2-ethylene bonds and 3,4-ethylene bonds in the unhydrogenated conjugated diene compound unit. The total ratio of the amount of 4,4-ethylene bonds and the amount of 1,4-conjugated bonds. The total amount of ethylene bonds can be calculated by measuring using a nuclear magnetic resonance apparatus (NMR).

於本實施形態中，關於氫化嵌段共聚物(B-I)之重量平均分子量，就提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物之耐熱老化性的觀點而言，較佳為50,000以上，更佳為100,000以上。 另一方面，就本實施形態之母料組合物之造粒穩定性之觀點而言，較佳為500,000以下，更佳為300,000以下。再者，此處所謂重量平均分子量可藉由GPC以苯乙烯換算分子量之形式而求出。In this embodiment, regarding the weight average molecular weight of the hydrogenated block copolymer (BI), from the viewpoint of improving the heat aging resistance of the resin composition including the master batch composition and the thermoplastic elastomer in various media such as this embodiment , Preferably 50,000 or more, more preferably 100,000 or more. On the other hand, from the viewpoint of the granulation stability of the master batch composition of this embodiment, it is preferably 500,000 or less, and more preferably 300,000 or less. In addition, the weight average molecular weight here can be calculated | required by GPC as a styrene conversion molecular weight.

關於氫化嵌段共聚物(B-I)中之乙烯基芳香族化合物聚合物嵌段(b1')之含量，就提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物之耐熱老化性的觀點而言，較佳為20質量%以上且70質量%以下，更佳為25質量%以上且65質量%以下。 再者，氫化嵌段共聚物(B-I)中之乙烯基芳香族化合物聚合物嵌段(b1')之含量例如可藉由以下之方法進行測定。 根據藉由將四氧化鋨作為觸媒並利用氫過氧化第三丁基使未氫化之共聚物氧化分解之方法(I. M. Kolthoff, et al., J. Polym. Sci. 1,429 (1946)中所記載之方法)所獲得之乙烯基芳香族化合物聚合物嵌段之質量，並基於下述式，可求出乙烯基芳香族化合物聚合物嵌段(b1)之含量。 乙烯基芳香族化合物聚合物嵌段之含量[質量%]＝(未氫化之共聚物中之乙烯基芳香族化合物聚合物嵌段之質量/未氫化之共聚物之質量)×100Regarding the content of the vinyl aromatic polymer polymer block (b1 ') in the hydrogenated block copolymer (BI), the content of the resin composition including the master batch composition of this embodiment and the resin composition of various media such as a thermoplastic elastomer is increased. From the viewpoint of heat aging resistance, it is preferably 20% by mass or more and 70% by mass or less, and more preferably 25% by mass or more and 65% by mass or less. The content of the vinyl aromatic polymer polymer block (b1 ') in the hydrogenated block copolymer (B-I) can be measured, for example, by the following method. According to a method of oxidatively decomposing an unhydrogenated copolymer by using osmium tetroxide as a catalyst and using a third butyl hydroperoxide (IM Kolthoff, et al., J. Polym. Sci. 1,429 (1946) Method: The content of the vinyl aromatic polymer polymer block (b1) can be determined based on the mass of the obtained vinyl aromatic polymer polymer block based on the following formula. Content of vinyl aromatic polymer block [mass%] = (mass of vinyl aromatic polymer block in unhydrogenated copolymer / mass of unhydrogenated copolymer) x 100

於本實施形態中，氫化嵌段共聚物(B-I)中之乙烯基芳香族化合物聚合物嵌段(b1')中之芳香族雙鍵之氫化率並無特別限定，較佳為50%以下，更佳為30%以下，進而較佳為20%以下。In this embodiment, the hydrogenation rate of the aromatic double bond in the vinyl aromatic polymer polymer block (b1 ') in the hydrogenated block copolymer (BI) is not particularly limited, but is preferably 50% or less. It is more preferably 30% or less, and still more preferably 20% or less.

於本實施形態中，氫化嵌段共聚物(B-I)中之共軛二烯化合物聚合物嵌段(b2')中之脂肪族雙鍵之氫化率較佳為50%以上且100%以下，更佳為80%以上且100%以下，進而較佳為90%以上且100%以下。若氫化率為50%以上，則母料組合物之造粒穩定性優異。In this embodiment, the hydrogenation rate of the aliphatic double bond in the conjugated diene compound polymer block (b2 ') in the hydrogenated block copolymer (BI) is preferably 50% or more and 100% or less, more It is preferably 80% or more and 100% or less, and further preferably 90% or more and 100% or less. When the hydrogenation rate is 50% or more, the granulation stability of the masterbatch composition is excellent.

再者，氫化嵌段共聚物(B-I)中之共軛二烯化合物聚合物嵌段(b2')中之脂肪族雙鍵之氫化率可藉由將上述(B-I)、及上述(B-I)之未氫化物供於核磁共振裝置(NMR)並進行測定而算出。Furthermore, the hydrogenation rate of the aliphatic double bond in the polymer block (b2 ') of the conjugated diene compound in the hydrogenated block copolymer (BI) can be obtained by changing the above (BI) and the above (BI) The unhydrogenated product was measured by a nuclear magnetic resonance apparatus (NMR) and calculated.

作為氫化嵌段共聚物(B-I)之製造方法，並無特別限定，例如可列舉以下之方法。 將正丁基鋰作為聚合觸媒，於環己烷溶劑中，將四氫呋喃作為全部乙烯鍵量調節劑，例如使苯乙烯與1,3-丁二烯進行陰離子活性聚合，藉此合成具有特定之苯乙烯嵌段含量與重量平均分子量之嵌段共聚物。再者，聚合物結構可藉由調整單體之添加量進行控制，分子量可藉由調整觸媒量進行控制。 繼而，上述嵌段共聚物之氫化係例如將雙(環戊二烯基)二氯化鈦與正丁基鋰作為氫化觸媒，於氫壓5 kg/cm2 、溫度50℃下進行2小時氫化(例如記載於日本專利特開昭59-133203號公報中)。於該方法中，可1,3-丁二烯聚合物嵌段中之脂肪族雙鍵之99%以上被氫化，且苯乙烯聚合物嵌段中之芳香族雙鍵幾乎未氫化而殘留。The manufacturing method of a hydrogenated block copolymer (BI) is not specifically limited, For example, the following methods are mentioned. Using n-butyllithium as a polymerization catalyst and tetrahydrofuran as a total ethylene bond amount regulator in a cyclohexane solvent, for example, styrene and 1,3-butadiene are subjected to anionic living polymerization to synthesize a specific compound A block copolymer of styrene block content and weight average molecular weight. Furthermore, the polymer structure can be controlled by adjusting the amount of monomer added, and the molecular weight can be controlled by adjusting the amount of catalyst. Next, the hydrogenation of the block copolymer is performed using, for example, bis (cyclopentadienyl) titanium dichloride and n-butyllithium as a hydrogenation catalyst at a hydrogen pressure of 5 kg / cm 2 at a temperature of 50 ° C for 2 hours. Hydrogenation (for example, described in Japanese Patent Laid-Open No. 59-133203). In this method, more than 99% of the aliphatic double bonds in the 1,3-butadiene polymer block can be hydrogenated, and the aromatic double bonds in the styrene polymer block remain almost without hydrogenation.

＜嵌段共聚物之氫化物(B-II)＞ 作為本實施形態之母料組合物中所使用之包含至少1個乙烯基芳香族化合物聚合物嵌段(b1'')及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)的嵌段共聚物之氫化物(B-II)(氫化嵌段共聚物(B-II))之結構，並無特別限定，例如可列舉：式(b1'')-(b3)所表示之二嵌段共聚物、式(b1'')-(b3)-(b1'')所表示之三嵌段共聚物、式(b1'')-(b3)-(b1'')-(b3)、式(b1'')-(b3)-(b1'')-(b3)-(b1'')、式{(b1'')-(b3)-}n X等所表示之多嵌段共聚物。 此處，式中之n為2以上且6以下之整數，X為偶合劑之反應殘基。 於本實施形態中，氫化嵌段共聚物(B-II)可為單一結構，亦可為以任意比率包含複數種結構之混合物。<Hydrohydride (B-II) of block copolymer> The master batch composition used in this embodiment contains at least one vinyl aromatic polymer polymer block (b1 '') and at least one copolymer. The structure of the hydride (B-II) (hydrogenated block copolymer (B-II)) of the block copolymer of the random copolymer block (b3) of the random copolymer of the conjugated diene compound and the vinyl aromatic compound has no structure Specific limitations include, for example, diblock copolymers represented by the formulae (b1 '')-(b3), and triblock copolymers represented by the formulae (b1 '')-(b3)-(b1 '') , Formula (b1 '')-(b3)-(b1 '')-(b3), formula (b1 '')-(b3)-(b1 '')-(b3)-(b1 ''), formula {(b1 '')-(b3)-} n X is a multi-block copolymer. Here, n in the formula is an integer of 2 or more and 6 or less, and X is a reaction residue of a coupling agent. In this embodiment, the hydrogenated block copolymer (B-II) may have a single structure or a mixture including a plurality of structures at an arbitrary ratio.

作為上述嵌段(b1'')、及上述嵌段(b3)中所使用之乙烯基芳香族化合物，並不限定於以下，但例如可列舉：苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、及對甲基苯乙烯、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。 該等之中，就聚合性及物性之觀點而言，可適宜地使用苯乙烯、α-甲基苯乙烯、二乙烯苯。 該等乙烯基芳香族化合物可僅使用一種，亦可併用兩種以上。The vinyl aromatic compound used in the block (b1 '') and the block (b3) is not limited to the following, but examples thereof include styrene, α-methylstyrene, and o-methyl Styrene, m-methylstyrene, and p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N- Diethyl-p-aminoethylstyrene and the like. Among these, from the viewpoints of polymerizability and physical properties, styrene, α-methylstyrene, and divinylbenzene can be suitably used. These vinyl aromatic compounds may be used alone or in combination of two or more.

作為上述嵌段(b3)中所使用之共軛二烯化合物，並不限定於以下，但例如可列舉：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。 該等之中，就聚合性及物性之觀點而言，可適宜地使用1,3-丁二烯、2-甲基-1,3-丁二烯(異戊二烯)。 該等共軛二烯化合物可僅使用一種，亦可併用兩種以上。The conjugated diene compound used in the block (b3) is not limited to the following, but examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (iso Pentadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, etc. . Among these, from the viewpoints of polymerizability and physical properties, 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) can be suitably used. These conjugated diene compounds may be used alone or in combination of two or more.

於本實施形態中，嵌段(b3)中之共軛二烯化合物單元之微結構(順式、反式、乙烯基之比率)並無特別限定，可任意地進行選擇。 關於嵌段(b3)中之共軛二烯化合物單元之全部乙烯鍵量，就提高包含本實施形態之母料組合物與熱塑性彈性體之樹脂組合物之耐熱老化性的觀點而言，較佳為2%以上且80%以下，更佳為5%以上且60%以下。In this embodiment, the microstructure (the ratio of cis, trans, and vinyl) of the conjugated diene compound unit in the block (b3) is not particularly limited, and can be arbitrarily selected. The total ethylene bond amount of the conjugated diene compound unit in the block (b3) is preferable from the viewpoint of improving the heat aging resistance of the resin composition including the master batch composition and the thermoplastic elastomer of the embodiment. It is 2% or more and 80% or less, and more preferably 5% or more and 60% or less.

關於本實施形態之母料組合物所使用之氫化嵌段共聚物(B-II)之重量平均分子量，就提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物之耐熱老化性的觀點而言，較佳為50,000以上，更佳為100,000以上。另一方面，就母料組合物之造粒穩定性之觀點而言，較佳為500,000以下，更佳為300,000以下。 再者，此處所謂重量平均分子量可藉由GPC以苯乙烯換算分子量之形式而求出。Regarding the weight-average molecular weight of the hydrogenated block copolymer (B-II) used in the master batch composition of this embodiment, the resin composition including the master batch composition of this embodiment and various media such as thermoplastic elastomers is improved. From the viewpoint of heat aging resistance, it is preferably 50,000 or more, and more preferably 100,000 or more. On the other hand, from the viewpoint of the granulation stability of the masterbatch composition, it is preferably 500,000 or less, and more preferably 300,000 or less. In addition, the weight average molecular weight here can be calculated | required by GPC as a styrene conversion molecular weight.

於本實施形態中，氫化嵌段共聚物(B-II)中之乙烯基芳香族化合物聚合物嵌段(b1'')之含量較佳為5質量%以上且60質量%以下，更佳為8質量%以上且50質量%以下，進而較佳為10質量%以上且40質量%以下。 再者，氫化嵌段共聚物(B-II)中之乙烯基芳香族化合物聚合物嵌段(b1'')之含量例如可藉由以下之方法進行測定。 根據藉由將四氧化鋨作為觸媒並利用氫過氧化第三丁基使未氫化之共聚物氧化分解之方法(I. M. Kolthoff, et al., J. Polym. Sci. 1,429 (1946)中所記載之方法)所獲得之乙烯基芳香族化合物聚合物嵌段之質量，並基於下述式，可求出乙烯基芳香族化合物聚合物嵌段之含量。 乙烯基芳香族化合物聚合物嵌段之含量[質量%]＝(未氫化之共聚物中之乙烯基芳香族化合物聚合物嵌段之質量/未氫化之共聚物之質量)×100In this embodiment, the content of the vinyl aromatic polymer polymer block (b1 '') in the hydrogenated block copolymer (B-II) is preferably 5 mass% or more and 60 mass% or less, and more preferably 8 mass% or more and 50 mass% or less, and more preferably 10 mass% or more and 40 mass% or less. The content of the vinyl aromatic polymer polymer block (b1 '') in the hydrogenated block copolymer (B-II) can be measured, for example, by the following method. According to a method of oxidatively decomposing an unhydrogenated copolymer by using osmium tetroxide as a catalyst and using a third butyl hydroperoxide (IM Kolthoff, et al., J. Polym. Sci. 1,429 (1946) (Method) The mass of the vinyl aromatic compound polymer block obtained can be determined based on the following formula. Content of vinyl aromatic polymer block [mass%] = (mass of vinyl aromatic polymer block in unhydrogenated copolymer / mass of unhydrogenated copolymer) x 100

於本實施形態中，關於氫化嵌段共聚物(B-II)中之芳香族化合物單元之總量，就提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物之耐熱老化性的觀點而言，較佳為20質量%以上且70質量%以下，更佳為25質量%以上且65質量%以下，進而較佳為30質量%以上且60質量%以下。In this embodiment, regarding the total amount of aromatic compound units in the hydrogenated block copolymer (B-II), the resin composition including the master batch composition and the thermoplastic elastomer in various media such as the present embodiment is increased. From the viewpoint of heat aging resistance, it is preferably 20% by mass or more and 70% by mass or less, more preferably 25% by mass or more and 65% by mass or less, and still more preferably 30% by mass or more and 60% by mass or less.

於本實施形態中，氫化嵌段共聚物(B-II)中之芳香族雙鍵之氫化率並無特別限定，較佳為50%以下，更佳為30%以下，進而較佳為20%以下。 於本實施形態中，氫化嵌段共聚物(B-II)中之共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)中之脂肪族雙鍵之氫化率較佳為50%以上且100%以下，更佳為80%以上且100%以下，進而較佳為90%以上且100%以下。若(b3)中之脂肪族雙鍵之氫化率為50%以上，則母料組合物之造粒穩定性優異。 再者，上述氫化率可藉由供於核磁共振裝置(NMR)進行測定而算出。In this embodiment, the hydrogenation rate of the aromatic double bond in the hydrogenated block copolymer (B-II) is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and even more preferably 20%. the following. In this embodiment, the hydrogenation rate of the aliphatic double bond in the random copolymer block (b3) of the conjugated diene compound and the vinyl aromatic compound in the hydrogenated block copolymer (B-II) is better It is 50% or more and 100% or less, more preferably 80% or more and 100% or less, and still more preferably 90% or more and 100% or less. When the hydrogenation rate of the aliphatic double bond in (b3) is 50% or more, the granulation stability of the master batch composition is excellent. In addition, the said hydrogenation rate can be calculated by measuring in a nuclear magnetic resonance apparatus (NMR).

作為氫化嵌段共聚物(B-II)之製造方法，並無特別限定，可使用公知之方法。例如可列舉以下之方法。 將正丁基鋰作為聚合觸媒，於環己烷溶劑中，將四氫呋喃作為全部乙烯鍵量調節劑、及無規共聚合性調整劑，例如使苯乙烯與1,3-丁二烯進行陰離子活性聚合，藉此合成具有特定之苯乙烯嵌段含量與重量平均分子量之嵌段共聚物。再者，聚合物結構可藉由變更單體之添加量進行控制，分子量可藉由變更觸媒量進行控制。繼而，上述嵌段共聚物之氫化例如可藉由將雙(環戊二烯基)二氯化鈦與正丁基鋰作為氫化觸媒，於氫壓5 kg/cm2 、溫度50℃下進行2小時氫化，而1,3-丁二烯聚合物嵌段中之脂肪族雙鍵之99%以上被氫化，且苯乙烯聚合物嵌段中之芳香族雙鍵幾乎未氫化而殘留。The manufacturing method of a hydrogenated block copolymer (B-II) is not specifically limited, A well-known method can be used. Examples include the following methods. N-butyllithium is used as a polymerization catalyst, tetrahydrofuran is used as a total ethylene bond amount adjuster and a random copolymerizable adjuster in a cyclohexane solvent, for example, styrene is anionized with 1,3-butadiene Living polymerization, whereby a block copolymer having a specific styrene block content and weight average molecular weight is synthesized. Furthermore, the polymer structure can be controlled by changing the amount of monomer added, and the molecular weight can be controlled by changing the amount of catalyst. Then, the hydrogenation of the above block copolymer can be performed, for example, by using bis (cyclopentadienyl) titanium dichloride and n-butyllithium as a hydrogenation catalyst at a hydrogen pressure of 5 kg / cm 2 at a temperature of 50 ° C. After 2 hours of hydrogenation, more than 99% of the aliphatic double bonds in the 1,3-butadiene polymer block were hydrogenated, and the aromatic double bonds in the styrene polymer block remained almost without hydrogenation.

本實施形態之母料組合物相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，包含上述(B)10質量份以上且90質量份以下。 藉由使上述(B)為10質量份以上，上述(A-1)及上述(A-2)均一地分散於包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物中。另一方面，藉由使上述(B)為90質量份以下，包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物成為耐熱老化性優異者。 作為上述(B)之含量之較佳範圍，為15質量份以上且85質量份以下，作為進而較佳之範圍，為20質量份以上且80質量份以下，作為進而更佳之範圍，為50質量份以上且80質量份以下。The masterbatch composition according to this embodiment contains 10 parts by mass or more and 90 parts by mass or less of the total of 100 parts by mass of the above (A-1), (A-2), and (B). When the (B) is 10 parts by mass or more, the (A-1) and the (A-2) are uniformly dispersed in a resin composition containing various media such as the master batch composition and the thermoplastic elastomer of the embodiment. in. On the other hand, when the (B) is 90 parts by mass or less, the resin composition including the master batch composition and various media such as a thermoplastic elastomer according to this embodiment is excellent in heat aging resistance. The preferable range of the content of the above (B) is 15 parts by mass or more and 85 parts by mass or less, as a further preferred range, it is 20 parts by mass or more and 80 parts by mass or less, and as a more preferred range, it is 50 parts by mass. Above 80 parts by mass.

(海島結構之形態) 就提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物中之聚苯醚(A-1)、及/或官能基改性聚苯醚(A-2)之均一分散性及相溶性的觀點而言，較佳為本實施形態之母料組合物具有海島結構之形態，該海島結構包含由聚苯醚(A-1)、及/或官能基改性聚苯醚(A-2)所構成之島相(非連續相)、及由嵌段共聚物(B)所構成之海相(連續相)。(The form of the sea-island structure) The polyphenylene ether (A-1) and / or the functional group-modified polyphenylene ether (A-1) in the resin composition containing the master batch composition and the thermoplastic elastomer in various media such as this embodiment are improved. A-2) From the standpoint of uniform dispersibility and compatibility, it is preferred that the master batch composition of this embodiment has a sea-island structure, and the sea-island structure includes polyphenylene ether (A-1) and / or Island phase (discontinuous phase) composed of functional group-modified polyphenylene ether (A-2), and sea phase (continuous phase) composed of block copolymer (B).

尤其於上述形態中，就提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物中之聚苯醚(A-1)及/或官能基改性聚苯醚(A-2)與熱塑性彈性體等各種媒體之相溶性的觀點而言，島相之平均直徑較佳為未達5 mm，更佳為未達1 mm，進而較佳為未達500 nm。 形態中之島相之平均直徑可藉由混練機之選定、混練溫度、混練時間、及比能量等混練條件之設定、以及相溶劑之添加、聚苯醚(A-1)及官能基改性聚苯醚(A-2)之重量平均分子量之調整、及嵌段共聚物(B)之乙烯基芳香族化合物單元含量之調整等，而控制為上述數值範圍內。 具體而言，若使用雙軸擠出機作為混練機，則可減小島相之平均直徑。又，越提高混練溫度，延長混練時間，增大比能量，越可減小島相之平均直徑。又，藉由添加相容劑，可減小島相之平均直徑，藉由減小聚苯醚(A-1)及官能基改性聚苯醚(A-2)之重量平均分子量，可減小島相之平均直徑，藉由增加嵌段共聚物(B)之乙烯基芳香族化合物單元含量，可減小島相之平均直徑。 再者，上述形態可使用穿透式電子顯微鏡(TEM)而加以確認。 具體而言，使用超薄切片機切出母料組合物本身、或僅包含母料組合物之成形片，而製作用以形成超薄切片之平面。繼而，浸漬於加入至耐熱容器中之2質量%四氯化鋨水溶液中，於水浴中隔水加熱80℃×30分鐘後提拉，進行冷卻直至達到常溫後，自耐熱容器中取出，並進行水洗、乾燥。藉由該染色操作，嵌段共聚物(B-0)被染色，於TEM觀察時觀察為黑色。繼而，使用超薄切片機，自用以製作超薄切片之平面切出厚度85 nm之薄膜，對其進行TEM觀察。 藉由上述染色法，聚苯醚(A-1)及/或官能基改性聚苯醚(A-2)被觀察為白色，嵌段共聚物(B-0)被觀察為黑色，且可確認形態。 又，使用超薄切片機切出母料組合物本身、或僅包含母料組合物之成形片，而獲得厚度85 nm之超薄切片。將超薄切片撈取至TEM觀察用Cu篩網上，預先使載有薄膜之Cu篩網排列在不鏽鋼網之上。另外向玻璃乾燥器中之培養皿中添加三氯化釕n水合物0.1 g與純化水1 mL，使之溶解後，添加次亞氯酸鈉溶液5 mL，即刻載置載有Cu篩網之不鏽鋼網，該Cu篩網載有薄膜，對玻璃乾燥器蓋上蓋並靜置4分鐘後，取出Cu篩網。藉由該染色操作，嵌段共聚物(B-I)及嵌段共聚物(B-II)被染色，且於TEM觀察時觀察為黑色。 海島結構中之島相之平均直徑可藉由使用市售之圖像分析軟體，對該TEM像照片進行圖像分析而容易地求出。Especially in the above aspect, the polyphenylene ether (A-1) and / or the functional group-modified polyphenylene ether (A) in the resin composition containing the master batch composition and the thermoplastic elastomer in various media such as this embodiment are improved. -2) From the viewpoint of compatibility with various media such as thermoplastic elastomers, the average diameter of the island phase is preferably less than 5 mm, more preferably less than 1 mm, and even more preferably less than 500 nm. The average diameter of the island phase in the form can be determined by the selection of the kneading machine, the kneading temperature, the kneading time, and the specific energy, and the setting of the kneading conditions, as well as the addition of the phase solvent, polyphenylene ether (A-1), and functional group-modified polybenzene. The weight average molecular weight of the ether (A-2) is adjusted, and the content of the vinyl aromatic compound unit of the block copolymer (B) is adjusted to be within the above numerical range. Specifically, if a twin-screw extruder is used as the kneader, the average diameter of the island phase can be reduced. In addition, the higher the kneading temperature, the longer the kneading time, and the larger the specific energy, the smaller the average diameter of the island phase can be. In addition, by adding a compatibilizer, the average diameter of the island phase can be reduced, and by reducing the weight average molecular weight of the polyphenylene ether (A-1) and the functional group-modified polyphenylene ether (A-2), the island can be reduced The average diameter of the phases can be reduced by increasing the content of the vinyl aromatic compound unit of the block copolymer (B). The above morphology can be confirmed using a transmission electron microscope (TEM). Specifically, an ultra-thin slicer is used to cut out the masterbatch composition itself, or a shaped sheet containing only the masterbatch composition, to produce a plane for forming ultra-thin slices. Next, immerse it in a 2% by mass aqueous solution of osmium tetrachloride added to a heat-resistant container, heat it in a water bath at 80 ° C for 30 minutes, and then pull and cool until it reaches normal temperature. Then, take it out of the heat-resistant container and perform Wash and dry. By this dyeing operation, the block copolymer (B-0) was dyed, and was observed to be black when observed by TEM. Then, an ultra-thin slicer was used to cut out a film with a thickness of 85 nm from the plane used to make the ultra-thin section, and observed it by TEM. By the above dyeing method, the polyphenylene ether (A-1) and / or the functional group-modified polyphenylene ether (A-2) were observed as white, and the block copolymer (B-0) was observed as black. Confirm the form. In addition, an ultra-thin slicer was used to cut out the masterbatch composition itself or a formed sheet containing only the masterbatch composition to obtain an ultra-thin slice with a thickness of 85 nm. The ultra-thin sections were taken out onto a Cu sieve for TEM observation, and the Cu sieve carrying the film was arranged on the stainless steel net in advance. In addition, add 0.1 g of ruthenium trichloride n hydrate and 1 mL of purified water to a petri dish in a glass drier, and dissolve them. Then add 5 mL of sodium hypochlorite solution, and immediately place the Stainless steel mesh, the Cu mesh is loaded with a film, the glass dryer is covered and left for 4 minutes, and then the Cu mesh is taken out. By this dyeing operation, the block copolymer (B-I) and the block copolymer (B-II) were dyed, and were observed to be black when observed by TEM. The average diameter of the island phases in the sea-island structure can be easily obtained by image analysis of the TEM image photograph using commercially available image analysis software.

(抗氧化劑(C)) 關於本實施形態之母料組合物，就提高母料組合物之造粒穩定性之觀點、及提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物之耐熱老化性的觀點而言，相對於聚苯醚(A-1)、官能基改性聚苯醚(A-2)及嵌段共聚物(B)之合計100質量份，較佳為包含抗氧化劑(C)0.1質量份以上且20質量份以下，更佳為包含0.5質量份以上且10質量份以下，進而較佳為包含1質量份以上且5質量份以下。(Antioxidant (C)) Regarding the master batch composition of this embodiment, from the viewpoint of improving the granulation stability of the master batch composition, and improving the media including the master batch composition of this embodiment and the thermoplastic elastomer, etc. From the viewpoint of the heat aging resistance of the resin composition, compared with 100 parts by mass of the total of the polyphenylene ether (A-1), the functional group-modified polyphenylene ether (A-2), and the block copolymer (B), The antioxidant (C) is preferably contained in an amount of 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass.

作為抗氧化劑(C)，並不限定於以下，但例如可列舉：受阻酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、胺系抗氧化劑等。具體而言，可列舉：2,6-二第三丁基-4-(4,6-雙(辛硫基)-1,3,5-三-2-基胺基)苯酚(BASF公司製造之IRGANOX565)、季戊四醇四[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](BASF公司製造之IRGANOX1010、ADEKA股份有限公司製造之Adekastab AO-60)、1,3,5-三甲基-2,4,6-三(3,5-二第三丁基-4-羥基苄基)苯(BASF公司製造之IRGANOX1330)、3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯(BASF公司製造之IRGANOX1076、ADEKA股份有限公司製造之Adekastab AO-50)、亞磷酸三(2,4-二第三丁基苯基)酯(BASF公司製造之IRGAFOS168、ADEKA股份有限公司製造之Adekastab 2112)、3,9-雙(十八烷氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷(ADEKA股份有限公司製造之Adekastab PEP-8)、3,9-雙(2,6-二第三丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷(ADEKA股份有限公司製造之Adekastab PEP-36)、磷酸2,2'-亞甲基雙(4,6-二第三丁基苯基)2-乙基己酯(ADEKA股份有限公司製造之Adekastab HP-10)、3,3'-硫代雙丙酸二(十八烷基)酯(BASF公司製造之IRGANOX PS802FD)、N,N-二(十八烷基)羥基胺(BASF公司製造之IRGASTAB FS042)等。 該等可單獨地使用一種，亦可組合兩種以上而使用。The antioxidant (C) is not limited to the following, but examples thereof include hindered phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and amine-based antioxidants. Specific examples include 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-tri-2-ylamino) phenol (manufactured by BASF) IRGANOX565), pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (IRGANOX1010 manufactured by BASF Corporation, Adekastab AO-60 manufactured by ADEKA Corporation), 1 , 3,5-trimethyl-2,4,6-tris (3,5-di-third-butyl-4-hydroxybenzyl) benzene (IRGANOX 1330 manufactured by BASF), 3- (3,5-di Tertiary butyl-4-hydroxyphenyl) octadecyl propionate (IRGANOX 1076 manufactured by BASF, Adekastab AO-50 manufactured by ADEKA Co., Ltd.), and tris (2,4-di-tert-butyl phosphite) Phenyl) ester (IRGAFOS168 manufactured by BASF Corporation, Adekastab 2112 manufactured by ADEKA Corporation), 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9- Diphosphospiro [5,5] undecane (Adekastab PEP-8 manufactured by ADEKA Corporation), 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy)- 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane (Adekastab PEP-36 manufactured by ADEKA Corporation), 2,2'-methylene phosphate Bis (4,6-di-tert-butylphenyl) 2-ethylhexyl ester (ADEKA Corporation (Adekastab HP-10), 3,3'-thiobispropionate bis (octadecyl) ester (IRGANOX PS802FD, manufactured by BASF), N, N-bis (octadecyl) hydroxylamine (IRGASTAB FS042 manufactured by BASF). These may be used individually by 1 type, and may be used in combination of 2 or more type.

(潤滑劑(D)) 關於本實施形態之母料組合物，就提高母料組合物之造粒穩定性之觀點、及提高包含本實施形態之母料組合物與熱塑性彈性體等各種媒體之樹脂組合物之耐熱老化性的觀點而言，相對於聚苯醚(A-1)、官能基改性聚苯醚(A-2)及嵌段共聚物(B)之合計100質量份，較佳為包含潤滑劑(D)0.1質量份以上且40質量份以下，更佳為包含1質量份以上且35質量份以下，進而較佳為包含10質量份以上且30質量份以下。(Lubricant (D)) Regarding the master batch composition of this embodiment, from the viewpoint of improving the granulation stability of the master batch composition, and improving the media including the master batch composition of this embodiment and the thermoplastic elastomer, etc. From the viewpoint of the heat aging resistance of the resin composition, compared with 100 parts by mass of the total of the polyphenylene ether (A-1), the functional group-modified polyphenylene ether (A-2), and the block copolymer (B), The lubricant (D) is preferably contained in an amount of 0.1 parts by mass or more and 40 parts by mass or less, more preferably contained in an amount of 1 part by mass or more and 35 parts by mass or less, and further preferably contained in an amount of 10 parts by mass or more and 30 parts by mass or less.

作為潤滑劑(D)，並不限定於以下，但例如可列舉：石蠟、微晶石蠟、聚乙烯蠟等烴系潤滑劑；硬脂酸丁酯、硬脂酸單甘油酯、季戊四醇二硬脂酸酯、季戊四醇四硬脂酸酯、硬脂酸硬脂酯、伸乙基雙硬脂醯胺等脂肪酸酯系潤滑劑；二硬脂酸鎂、二硬脂酸鈣、二硬脂酸鋅、褐煤酸鈣等脂肪酸金屬鹽系潤滑劑。The lubricant (D) is not limited to the following, but examples include: hydrocarbon-based lubricants such as paraffin, microcrystalline paraffin, and polyethylene wax; butyl stearate, monoglyceryl stearate, and pentaerythritol distearate Fatty acid ester-based lubricants such as esters, pentaerythritol tetrastearate, stearate stearate, and diethylstearate; magnesium distearate, calcium distearate, zinc distearate , Calcium montanate and other fatty acid metal salt based lubricants.

(其他成分) 於本實施形態之母料組合物中，可於不損及本實施形態之效果之範圍內，視需要除含有上述(A-1)、(A-2)、及(B)～(D)成分以外，亦進而含有其他成分。 作為其他成分，並不限定於以下，但例如可列舉：紫外線吸收劑、光穩定劑、軟化劑、染料顏料、阻燃劑、阻燃助劑、防靜電劑、抗黏連劑、相溶劑等。(Other components) In the masterbatch composition of this embodiment, as long as the effect of this embodiment is not impaired, it may contain the above-mentioned (A-1), (A-2), and (B) as necessary. In addition to the (D) component, other components are further contained. The other components are not limited to the following, but examples include ultraviolet absorbers, light stabilizers, softeners, dyes, pigments, flame retardants, flame retardant additives, antistatic agents, anti-blocking agents, and phase solvents. .

(母料組合物之製造方法) 本實施形態之母料組合物之製造方法並無特別限定，可應用公知之方法。 例如可藉由使用雙軸擠出機、單軸擠出機、捏合機、班布里混合機、輥型混練機等混練機之熔融混練而進行製造。 就生產性之觀點而言，較佳為利用雙軸擠出機進行之熔融混練。混練溫度可考慮熔融黏度與分解溫度而設定為較佳之溫度，作為標準，為200℃以上且360℃以下，較佳為230℃以上且330℃以下。(Manufacturing method of the masterbatch composition) The manufacturing method of the masterbatch composition of this embodiment is not specifically limited, A well-known method can be applied. For example, it can be manufactured by melt-kneading using a kneading machine such as a biaxial extruder, a uniaxial extruder, a kneader, a Banbury mixer, a roll-type kneader, and the like. From the viewpoint of productivity, melt-kneading by a biaxial extruder is preferred. The kneading temperature can be set to a preferable temperature in consideration of the melt viscosity and the decomposition temperature. As a standard, it is 200 ° C or higher and 360 ° C or lower, preferably 230 ° C or higher and 330 ° C or lower.

(母料組合物之形狀) 就處理性之觀點而言，本實施形態之母料組合物較佳為具有選自由顆粒、小顆粒、及粉體所組成之群中之任一種形狀，更佳為顆粒及小顆粒。 為顆粒形狀時之直徑f並無特別限定，於包含本實施形態之母料組合物與熱塑性彈性體之樹脂組合物中，就提高上述(A-1)及上述(A-2)之均一分散性之觀點而言，較佳為1 mm以上且5 mm以下之範圍。 又，顆粒長度L/顆粒直徑f並無特別限定，就於包含本實施形態之母料組合物與熱塑性彈性體之樹脂組合物等各種媒體中，提高上述(A-1)及上述(A-2)之均一分散性之觀點而言，較佳為0.1以上且5以下之範圍。 顆粒之製造方法並無特別限定，可應用公知之方法。例如可列舉：於將自上述雙軸擠出機之模頭擠出之線料水冷後進行連續切斷之方法；於將自上述雙軸擠出機之模頭擠出之線料於輸送器上空氣冷卻後進行連續切斷之方法；於將自上述雙軸擠出機之模頭擠出之線料連續切斷後進行水冷之方法等。 小顆粒之平均粒徑並無特別限定，就於包含本實施形態之母料組合物與熱塑性彈性體之樹脂組合物中，提高上述(A-1)及上述(A-2)之均一分散性之觀點而言，較佳為100 μm以上且1 mm以下之範圍。小顆粒及粉體之製造方法並無特別限定，可應用公知之方法，例如可列舉將上述中所獲得之顆粒進行粉碎之方法等。(Shape of Masterbatch Composition) From the viewpoint of handleability, the masterbatch composition of the present embodiment preferably has any shape selected from the group consisting of granules, small particles, and powders, and more preferably For particles and small particles. The diameter f when it is in the shape of a particle is not particularly limited. In the resin composition including the master batch composition and the thermoplastic elastomer of this embodiment, the uniform dispersion of the above-mentioned (A-1) and (A-2) is improved. From the viewpoint of performance, a range of 1 mm to 5 mm is preferred. The particle length L / particle diameter f is not particularly limited. In various media including the master batch composition and the thermoplastic elastomer resin composition of the present embodiment, the above-mentioned (A-1) and (A- 2) From the viewpoint of uniform dispersion, the range of 0.1 or more and 5 or less is preferable. The method for producing the particles is not particularly limited, and a known method can be applied. For example, the method of continuously cutting the strands extruded from the die of the above-mentioned twin-screw extruder and cooling them continuously, and the method of extruding the strands from the die of the above-mentioned twin-screw extruder on a conveyor A method of continuous cutting after the upper air is cooled; a method of water cooling after continuously cutting the strands extruded from the die of the above-mentioned biaxial extruder. The average particle diameter of the small particles is not particularly limited. In the resin composition including the master batch composition and the thermoplastic elastomer of the embodiment, the uniform dispersibility of the above (A-1) and (A-2) is improved. From a viewpoint, the range of 100 micrometers or more and 1 mm or less is preferable. The method for producing small particles and powder is not particularly limited, and a known method can be applied, and examples thereof include a method of pulverizing the particles obtained in the above.

本實施形態之母料組合物可用作聚苯醚母料組合物。所謂聚苯醚母料組合物，係用以向媒體中添加聚苯醚之母料組合物，藉由本實施形態之母料組合物，可獲得如下效果，即能夠以簡便之步驟且於溫和之混練條件下使具有充分之分子量之聚苯醚均一分散及相溶。The master batch composition of this embodiment can be used as a polyphenylene ether master batch composition. The so-called polyphenylene ether masterbatch composition is a masterbatch composition for adding polyphenylene ether to the media. With the masterbatch composition of this embodiment, the following effects can be obtained, which can be achieved in a simple and gentle manner. Under mixing conditions, polyphenylene ether with sufficient molecular weight is uniformly dispersed and compatible.

本實施形態之母料組合物可用作改質劑。所謂改質劑，係為了改善媒體之物性、尤其是耐熱老化性而添加之成分，藉由本實施形態之母料組合物，可獲得如下效果，即能夠獲得耐熱老化性優異之樹脂組合物。The master batch composition of this embodiment can be used as a modifier. The so-called modifier is a component added to improve the physical properties of the medium, especially the heat aging resistance. The masterbatch composition of this embodiment can obtain the following effect, that is, a resin composition having excellent heat aging resistance can be obtained.

其次，對本實施形態之樹脂組合物、及其製造方法進行說明。Next, the resin composition of this embodiment and its manufacturing method are demonstrated.

[樹脂組合物] 本實施形態之樹脂組合物包含： 聚苯醚(A-1)、及/或具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基之官能基改性聚苯醚(A-2)； 嵌段共聚物(B)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段(b1)與至少1個共軛二烯化合物聚合物嵌段(b2)之嵌段共聚物之非氫化物(B-0)；包含至少1個乙烯基芳香族化合物聚合物嵌段(b1')與至少1個共軛二烯化合物聚合物嵌段(b2')之嵌段共聚物之氫化物(B-I)；及包含至少1個乙烯基芳香族化合物聚合物嵌段(b1'')及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)之嵌段共聚物之氫化物(B-II)所組成之群中之至少一種；及 媒體，其係選自由熱塑性彈性體、軟質系熱塑性聚合物、橡膠、瀝青、密封劑、接著劑、熱熔接著劑、黏著劑、及塗料所組成之群中之至少一種。 包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量為10,000以上且50,000以下，且 包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑未達5 μm。 如此，藉由具有充分之分子量之聚苯醚相溶於熱塑性彈性體等媒體中之結構，本實施形態之樹脂組合物顯示出優異之耐熱老化性。 包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑之較佳範圍未達1 mm，更佳為未達500 nm。[Resin Composition] The resin composition according to this embodiment includes: polyphenylene ether (A-1) and / or a functional group having at least one functional group selected from the group consisting of a carboxyl group and a group derived from a carboxyl group. Polyphenylene ether (A-2); block copolymer (B), which is selected from the group consisting of at least 1 vinyl aromatic polymer polymer block (b1) and at least 1 conjugated diene compound polymer. Non-hydride (B-0) of the block copolymer of segment (b2); contains at least 1 vinyl aromatic polymer polymer block (b1 ') and at least 1 conjugated diene compound polymer block ( b2 ') block copolymer hydride (BI); and at least one vinyl aromatic polymer polymer block (b1' ') and at least one conjugated diene compound and vinyl aromatic compound At least one of the group consisting of the hydride (B-II) of the block copolymer of the random copolymer block (b3); and a medium selected from the group consisting of thermoplastic elastomers, soft thermoplastic polymers, rubbers, At least one of the group consisting of asphalt, sealant, adhesive, hot-melt adhesive, adhesive, and coating. The weight average molecular weight of the polyphenylene ether containing the above (A-1) and / or the above (A-2) is 10,000 or more and 50,000 or less, and the polymer containing the above (A-1) and / or the above (A-2) The average dispersed particle size of phenyl ether was less than 5 μm. As described above, with the structure in which a polyphenylene ether phase having a sufficient molecular weight is dissolved in a medium such as a thermoplastic elastomer, the resin composition of this embodiment exhibits excellent heat aging resistance. The preferred range of the average dispersed particle diameter of the polyphenylene ether containing the above (A-1) and / or the above (A-2) is less than 1 mm, and more preferably less than 500 nm.

作為上述軟質系熱塑性聚合物，可使用選自由聚烯烴系、聚胺基甲酸酯系、聚酯系、聚醯胺系、及聚氯乙烯系所組成之群中之一種以上之軟質系熱塑性聚合物。As the soft thermoplastic polymer, one or more soft thermoplastics selected from the group consisting of polyolefins, polyurethanes, polyesters, polyamides, and polyvinyl chlorides can be used. polymer.

關於作為上述媒體之熱塑性彈性體，例如可使用如下熱塑性彈性體(E)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段、及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物；及至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物所組成之群中之一種或兩種以上。Regarding the thermoplastic elastomer as the medium, for example, the following thermoplastic elastomer (E) can be used, which is selected from the group consisting of at least one vinyl aromatic polymer polymer block and at least one conjugated diene compound polymer block. Non-hydrides of block copolymers; hydrides of block copolymers containing at least 1 vinyl aromatic polymer polymer block and at least 1 conjugated diene compound polymer block; containing at least 1 ethylene Based aromatic polymer polymer blocks, and hydrogenated block copolymers of at least one random copolymer block of a conjugated diene compound and a vinyl aromatic compound; and at least one vinyl aromatic compound and at least one One or two or more of the group consisting of a non-hydride of a random copolymer of a conjugated diene compound.

[樹脂組合物之製造方法] 本實施形態之樹脂組合物之製造方法包括如下步驟：將本實施形態之母料組合物與上述各種媒體 於未達250℃之溫度條件下機械地進行混練。 如此，藉由使用本實施形態之母料組合物，即便於未達250℃之相對溫和之混練條件下，亦可使具有充分之分子量之聚苯醚相溶於媒體中，並且可抑制由混練所引起之媒體之熱劣化。 較佳之混練溫度未達200℃，更佳為未達180℃，進而較佳為未達160℃。 上述所謂機械地進行混練之步驟，並不限定於以下，例如可列舉利用雙軸擠出機、單軸擠出機、捏合機、班布里混合機、輥型混練機、高速攪拌機等混練機進行混練之步驟。[Manufacturing method of resin composition] The manufacturing method of the resin composition of this embodiment includes the steps of mechanically kneading the master batch composition of this embodiment and the above-mentioned various media under a temperature of less than 250 ° C. In this way, by using the master batch composition of this embodiment, even under relatively mild kneading conditions up to 250 ° C, a polyphenylene ether phase having a sufficient molecular weight can be dissolved in the medium, and the kneading by kneading can be suppressed. Thermal degradation of the media caused. The preferred kneading temperature is less than 200 ° C, more preferably less than 180 ° C, and even more preferably less than 160 ° C. The above-mentioned steps of mechanically kneading are not limited to the following, and examples include kneading machines using a twin-screw extruder, a single-screw extruder, a kneader, a Banbury mixer, a roll-type kneader, and a high-speed mixer. Steps for mixing.

作為上述媒體，可使用選自由熱塑性彈性體、軟質系熱塑性聚合物、橡膠、瀝青、密封劑、接著劑、熱熔接著劑、黏著劑、及塗料所組成之群中之至少任一種媒體。As the medium, at least one medium selected from the group consisting of a thermoplastic elastomer, a soft thermoplastic polymer, rubber, asphalt, a sealant, an adhesive, a hot-melt adhesive, an adhesive, and a coating material can be used.

作為上述軟質系熱塑性聚合物，可使用選自由聚烯烴系、聚胺基甲酸酯系、聚酯系、聚醯胺系、及聚氯乙烯系所組成之群中之一種以上之軟質系熱塑性聚合物。As the soft thermoplastic polymer, one or more soft thermoplastics selected from the group consisting of polyolefins, polyurethanes, polyesters, polyamides, and polyvinyl chlorides can be used. polymer.

又，關於作為上述媒體之熱塑性彈性體，例如可使用如下熱塑性彈性體(E)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段、及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物；及至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物所組成之群中之一種或兩種以上。As the thermoplastic elastomer used as the medium, for example, the following thermoplastic elastomer (E) can be used, which is selected from the group consisting of at least one vinyl aromatic polymer polymer block and at least one conjugated diene compound polymer. Non-hydrides of block block copolymers; hydrides of block copolymers containing at least 1 vinyl aromatic polymer polymer block and at least 1 conjugated diene compound polymer block; containing at least 1 Polymer blocks of vinyl aromatic compounds, and hydrides of at least one block copolymer of random copolymer blocks of conjugated diene compounds and vinyl aromatic compounds; and at least one vinyl aromatic compound One or two or more of the group consisting of a non-hydride of a random copolymer of at least one conjugated diene compound.

上述進行混練之步驟後之包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑較佳為未達5 μm，更佳為未達1 mm，進而較佳為未達500 nm。 [實施例]The average dispersed particle diameter of the polyphenylene ether containing the above (A-1) and / or the above (A-2) after the above kneading step is preferably less than 5 μm, more preferably less than 1 mm, and more It is preferably less than 500 nm. [Example]

以下，列舉具體之實施例及比較例對本實施形態詳細地進行說明，但本發明並不受以下之實施例任何限定。Hereinafter, this embodiment will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

將下述製造例之母料組合物所使用之原材料示於以下。 [(A-1)成分] (A-1-1)：使2,6-二甲苯酚氧化聚合而獲得之重量平均分子量20,000之聚苯醚粉末 (A-1-2)：使2,6-二甲苯酚氧化聚合而獲得之重量平均分子量3,000之聚苯醚粉末 (A-1-3)：使2,6-二甲苯酚氧化聚合而獲得之重量平均分子量35,000之聚苯醚粉末 (A-1-4)：使2,6-二甲苯酚氧化聚合而獲得之重量平均分子量55,000之聚苯醚粉末The raw materials used in the master batch composition of the following manufacturing examples are shown below. [(A-1) Component] (A-1-1): Polyphenylene ether powder having a weight average molecular weight of 20,000 obtained by oxidative polymerization of 2,6-xylenol (A-1-2): 2,6 -Polyphenylene ether powder (A-1-3) having a weight average molecular weight of 3,000 obtained by the oxidative polymerization of xylenol: Polyphenylene ether powder (A) having a weight average molecular weight of 35,000 obtained by the oxidative polymerization of 2,6-xylenol (A -1-4): Polyphenylene ether powder having a weight average molecular weight of 55,000 obtained by oxidative polymerization of 2,6-xylenol

[(A-2)成分] (A-2-1)：藉由使用雙軸擠出機將聚苯醚粉末100質量份與順丁烯二酸酐(日本油脂股份有限公司製造、CRYSTAL MAN)2質量份進行熔融混練所獲得之重量平均分子量35,000之官能基改性聚苯醚。 順丁烯二酸酐加成量係藉由IR(Infrared Spectrophotometer，紅外分光光度計)測定，算出相對於聚苯醚100質量%為0.5質量%。[(A-2) Ingredient] (A-2-1): 100 parts by mass of polyphenylene ether powder and maleic anhydride (manufactured by Nippon Oil & Fats Co., Ltd., Crystal Man) by using a biaxial extruder 2 A functional group-modified polyphenylene ether having a weight average molecular weight of 35,000 obtained by melt-kneading parts by mass. The addition amount of maleic anhydride was measured by IR (Infrared Spectrophotometer), and calculated as 0.5% by mass based on 100% by mass of polyphenylene ether.

[(B)成分] (B1)：藉由使苯乙烯與1,3-丁二烯進行陰離子活性聚合，而獲得(苯乙烯聚合物嵌段)-(1,3-丁二烯聚合物嵌段)-(苯乙烯聚合物嵌段)-(1,3-丁二烯聚合物嵌段)所表示之四嵌段共聚物。 此時，全部乙烯鍵量為10%，苯乙烯嵌段含量為40質量%，重量平均分子量為100,000。 (B2)：藉由使苯乙烯與1,3-丁二烯進行陰離子活性聚合，而獲得(苯乙烯聚合物嵌段)-(1,3-丁二烯聚合物嵌段)-(苯乙烯聚合物嵌段)所表示之三嵌段共聚物。 此時，全部乙烯鍵量為10%，苯乙烯嵌段含量為30質量%，重量平均分子量為200,000。[(B) component] (B1): Anionic living polymerization of styrene and 1,3-butadiene to obtain (styrene polymer block)-(1,3-butadiene polymer Segment)-(styrene polymer block)-(1,3-butadiene polymer block) tetrablock copolymer. At this time, the total amount of ethylene bonds was 10%, the styrene block content was 40% by mass, and the weight average molecular weight was 100,000. (B2): (styrene polymer block)-(1,3-butadiene polymer block)-(styrene is obtained by anionic living polymerization of styrene and 1,3-butadiene Triblock copolymer represented by polymer block). At this time, the total amount of ethylene bonds was 10%, the styrene block content was 30% by mass, and the weight average molecular weight was 200,000.

[(C)成分] (C1)：亞磷酸三(2,4-二第三丁基苯基)酯(BASF公司製造、IRGAFOS168)[(C) component] (C1): Tris (2,4-di-tert-butylphenyl) phosphite (manufactured by BASF, IRGAFOS168)

[(D)成分] (D1)：伸乙基雙硬脂醯胺(花王股份有限公司製造、KAO WAX EB-FF)[(D) component] (D1): Ethylbisstearylamine (manufactured by Kao Corporation, KAO WAX EB-FF)

[製造例1] 母料組合物(MB1) 使用雙軸擠出機(池貝股份有限公司製造、PCM-30)，以表1所示之原料與組成構成，將氣缸溫度設定為250℃，將螺桿轉速設為150 rpm，將噴出量設為每小時7 kg，而進行熔融混練。 此時，於汽缸體上設置開口部(排氣口)，以減壓度0.09 MPa進行減壓抽吸，藉此去除殘留揮發分。 於對自模頭擠出之線料進行水冷後，進行連續切斷，而獲得顆粒形狀(顆粒直徑f4 mm、顆粒長度L4 mm)之母料組合物(MB1)。[Manufacturing Example 1] The master batch composition (MB1) was composed of the raw materials and compositions shown in Table 1 using a biaxial extruder (Ikegai Co., Ltd., PCM-30), and the cylinder temperature was set to 250 ° C. The screw rotation speed was set to 150 rpm, and the ejection amount was set to 7 kg per hour to perform melt kneading. At this time, an opening (exhaust port) is provided in the cylinder block, and reduced pressure suction is performed at a pressure reduction degree of 0.09 MPa, thereby removing residual volatiles. After the wire extruded from the die was water-cooled, continuous cutting was performed to obtain a master batch composition (MB1) having a particle shape (particle diameter f4 mm and particle length L4 mm).

[製造例2]母料組合物(MB2) 以表1所示之原料與組成構成，藉由與上述[製造例1]同樣之操作而獲得顆粒(顆粒直徑f4 mm、顆粒長度L4 mm)，其後使用粉碎機粉碎該顆粒，藉此獲得具有小顆粒形狀(平均粒徑500 μm)之母料組合物(MB2)。[Manufacturing Example 2] The master batch composition (MB2) was composed of the raw materials and compositions shown in Table 1, and granules (particle diameter f4 mm, particle length L4 mm) were obtained by the same operation as in the above [Manufacturing Example 1]. Thereafter, the particles were pulverized using a pulverizer, thereby obtaining a master batch composition (MB2) having a small particle shape (average particle diameter of 500 μm).

[製造例3～6及12]、[比較製造例7～10] 母料組合物(MB3)～(MB10)及(MB12) 以表1所示之原料與組成構成，藉由與上述[製造例1]同樣之操作，獲得具有顆粒形狀(顆粒直徑f4 mm、顆粒長度L4 mm)之母料組合物(MB3)～(MB10)及(MB12)。[Production Examples 3 to 6 and 12], [Comparative Production Examples 7 to 10] The master batch compositions (MB3) to (MB10) and (MB12) are composed of the raw materials and compositions shown in Table 1, Example 1] In the same manner, master batch compositions (MB3) to (MB10) and (MB12) having a particle shape (particle diameter f4 mm and particle length L4 mm) were obtained.

[比較製造例11] 母料組合物(MB11) 以表1所示之原料與組成構成，進行與上述[製造例1]同樣之操作，但線料斷裂頻繁地發生，而無法獲得顆粒形狀之母料組合物(MB11)。[Comparative Manufacturing Example 11] The master batch composition (MB11) was prepared with the raw materials and compositions shown in Table 1, and the same operation as in the above [Manufacturing Example 1] was performed, but strand breakage occurred frequently, and particle shapes were not obtained. Masterbatch composition (MB11).

[母料組合物之特性] (母料組合物之造粒穩定性) 基於下述評價基準評價母料組合物(MB1)～(MB12)之造粒穩定性。 -評價基準- ◎：於擠出步驟中，完全未發生線料斷裂，且線料表面較光滑。 ○：於擠出步驟中，完全未發生線料斷裂，但線料表面較粗糙。 △：於擠出步驟中，線料斷裂於10分鐘內以1～2次之頻度發生。 ×：於擠出步驟中，線料斷裂頻繁地發生。[Characteristics of Masterbatch Composition] (Granulation Stability of Masterbatch Composition) The granulation stability of the masterbatch compositions (MB1) to (MB12) was evaluated based on the following evaluation criteria. -Evaluation Criteria-：: In the extrusion step, no strand breakage occurred, and the strand surface was smooth. ○: In the extrusion step, strand breaks did not occur at all, but the strand surface was rough. △: In the extrusion step, strand breakage occurred within 1 to 2 times within 10 minutes. ×: In the extrusion step, strand breakage frequently occurred.

(母料組合物之形態) 依據下述順序而評價母料組合物(MB1)～(MB10)及(MB12)之形態。 使用超薄切片機(Leica Microsystems公司製造、Leica EM UC7)，對具有顆粒形狀之母料組合物(MB1)、(MB3)～(MB10)及(MB12)進行冷凍切削，而製作用以製作超薄切片之平面。 繼而，浸漬於加入至耐熱容器中之2質量%四氯化鋨水溶液中，於水浴中隔水加熱80℃×30分鐘後提拉，進行冷卻直至達到常溫後，自耐熱容器中取出，並進行水洗、乾燥。 繼而，使用超薄切片機，自用以製作超薄切片之平面冷凍切削厚度85 nm之薄膜，而獲得超薄切片。使用穿透式電子顯微鏡(Hitachi High-Technologies股份有限公司製造、HT7700)觀察所獲得之超薄切片。 將所獲得之TEM照片之白色部分作為聚苯醚(A-1)及官能基改性聚苯醚(A-2)(於以下之本說明書中之記載、及下述表1中，存在將上述(A-1)與上述(A-2)合併記載為聚苯醚(A)之情形)，將黑色部分作為嵌段共聚物(B)，確定了海島結構。 進而，使用市售之圖像分析軟體(Asahi Kasei Engineering股份有限公司製造、A-ZO KUN(商品名))對該TEM像照片進行圖像分析，藉此求出海島結構中之島之平均直徑。 關於具有小顆粒形狀之母料組合物(MB2)，依據上述順序，將粉碎前之顆粒供於染色、切削、TEM觀察、及圖像分析。(Form of masterbatch composition) The forms of the masterbatch compositions (MB1) to (MB10) and (MB12) were evaluated according to the following procedures. Using an ultra-thin slicer (Leica Microsystems, Leica EM UC7), the master batch composition (MB1), (MB3) to (MB10), and (MB12) having a particle shape were subjected to freeze cutting to produce an ultra-thin slicer. Plane for thin slices. Next, immerse it in a 2% by mass aqueous solution of osmium tetrachloride added to a heat-resistant container, heat it in a water bath at 80 ° C for 30 minutes, and then pull and cool until it reaches normal temperature. Then, take it out of the heat-resistant container and perform Wash and dry. Then, an ultra-thin slicer was obtained from a plane cryo-cut thickness of 85 nm using ultra-thin microtome to obtain ultra-thin sections. The obtained ultra-thin section was observed using a transmission electron microscope (Hitachi High-Technologies Co., Ltd., HT7700). The white portion of the obtained TEM photograph was defined as polyphenylene ether (A-1) and functional group-modified polyphenylene ether (A-2) (as described in the present specification below and in Table 1 below). When (A-1) and (A-2) are combined and described as polyphenylene ether (A)), the black portion is used as the block copolymer (B) to determine the sea-island structure. Furthermore, a commercially available image analysis software (manufactured by Asahi Kasei Engineering Co., Ltd., A-ZO KUN (trade name)) was used to perform image analysis on the TEM image photograph to obtain the average diameter of the islands in the island structure. Regarding the master batch composition (MB2) having a small particle shape, the particles before pulverization were subjected to dyeing, cutting, TEM observation, and image analysis according to the above-mentioned procedure.

(母料組合物之臭氣評價) 基於下述評價基準評價母料組合物(MB1)～(MB10)及(MB12)之臭氣。 -評價基準- 1：幾乎未感覺到臭氣。 2：略微感覺到臭氣。 3：明顯地感覺到臭氣。(Evaluation of odor of master batch composition) The odor of the master batch compositions (MB1) to (MB10) and (MB12) was evaluated based on the following evaluation criteria. -Evaluation Criterion-1: Hardly any odor was felt. 2: Smell is slightly felt. 3: Obvious odor was felt.

於表1中表示母料組合物之原料與組成構成、母料組合物之造粒穩定性、及母料組合物之形態。 表1中關於「-」，於製造例3、比較製造例10中，由於島相係由(B)成分所形成，故而意指未進行平均直徑之測定，於比較製造例11中，由於無法獲得母料組合物，故而意指未進行平均直徑之測定。Table 1 shows the raw materials and composition of the masterbatch composition, the granulation stability of the masterbatch composition, and the form of the masterbatch composition. "-" In Table 1 means that in Example 3 and Comparative Example 10, since the island phase was formed by the component (B), it means that the average diameter was not measured. In Comparative Example 11, it was impossible The masterbatch composition was obtained, which means that the measurement of the average diameter was not performed.

[表1] [Table 1]

其次，使用上述[製造例1～6及12]、[比較製造例7～10]之母料組合物與熱塑性彈性體，製造樹脂組合物，並進行特性之評價。Next, a resin composition was produced using the master batch composition and the thermoplastic elastomer of the above [Production Examples 1 to 6 and 12] and [Comparative Production Examples 7 to 10], and the characteristics were evaluated.

[實施例1]～[實施例7]、[比較例1]～[比較例4] 將上述中所獲得之母料組合物(MB1)～(MB10)及(MB12)、與作為熱塑性彈性體(E)之上述嵌段共聚物(B1)以母料組合物：嵌段共聚物＝20：80(質量比)之組成構成，於溫度130℃下進行輥型混練後，使用壓縮成型機，於溫度160℃、荷重80 kgf/cm2 之條件下進行5分鐘壓製，而製作依據ISO37標準之厚度2 mm之啞鈴狀1A型試片。[Example 1] to [Example 7], [Comparative Example 1] to [Comparative Example 4] The master batch compositions (MB1) to (MB10) and (MB12) obtained above were used as thermoplastic elastomers. The block copolymer (B1) of (E) is composed of a master batch composition: a block copolymer = 20:80 (mass ratio), and after roll-type kneading at a temperature of 130 ° C, a compression molding machine is used. It was pressed for 5 minutes at a temperature of 160 ° C and a load of 80 kgf / cm 2 to produce a dumbbell-shaped 1A test piece having a thickness of 2 mm according to the ISO37 standard.

[比較例5] 將聚苯醚粉末(A-1-1)、與作為熱塑性彈性體(E)之上述嵌段共聚物(B1)以聚苯醚：嵌段共聚物＝20：80(質量比)之組成構成，藉由與上述[實施例1]同樣之順序製作厚度2 mm之啞鈴狀1A型試片。[Comparative Example 5] Polyphenylene ether powder (A-1-1) and the above-mentioned block copolymer (B1) as a thermoplastic elastomer (E) were prepared by polyphenylene ether: block copolymer = 20: 80 (mass Ratio), a dumbbell-shaped 1A-type test piece having a thickness of 2 mm was prepared in the same procedure as in the above-mentioned [Example 1].

[比較例6] 將聚苯醚粉末(A-1-2)、與作為熱塑性彈性體(E)之上述嵌段共聚物(B1)以聚苯醚：嵌段共聚物＝20：80(質量比)之組成構成，藉由與上述[實施例1]同樣之順序製作厚度2 mm之啞鈴狀1A型試片。[Comparative Example 6] Polyphenylene ether powder (A-1-2) and the above-mentioned block copolymer (B1) as a thermoplastic elastomer (E) were prepared by polyphenylene ether: block copolymer = 20: 80 (mass Ratio), a dumbbell-shaped 1A-type test piece having a thickness of 2 mm was prepared in the same procedure as in the above-mentioned [Example 1].

[樹脂組合物之特性] (將母料組合物混練而成之樹脂組合物之耐熱老化性) 對於將上述中所獲得之啞鈴狀試片於120℃環境下進行了熱老化12小時之樣品與未熱老化之樣品，依據ISO37標準，於拉伸速度500 mm/min之條件下進行拉伸試驗，並測定拉伸強度。 藉由下述式算出拉伸強度保持率，並基於下述之評價基準評價耐熱老化性。 拉伸強度保持率[%]＝{進行了熱老化之樣品之拉伸強度[MPa]/未熱老化之樣品之拉伸強度[MPa]}×100 -評價基準- ◎：於120℃環境下經過12小時後之拉伸強度保持率為95%以上 ○：於120℃環境下經過12小時後之拉伸強度保持率為90%以上且未達95% △：於120℃環境下經過12小時後之拉伸強度保持率為80%以上且未達90% ×：於120℃環境下經過12小時後之拉伸強度保持率未達80%[Characteristics of Resin Composition] (The heat aging resistance of the resin composition obtained by kneading the masterbatch composition) For the sample obtained by subjecting the dumbbell-shaped test piece obtained above to heat aging at 120 ° C for 12 hours, For non-heat-aged samples, a tensile test was performed at a tensile speed of 500 mm / min in accordance with the ISO37 standard, and the tensile strength was measured. The tensile strength retention was calculated by the following formula, and the heat aging resistance was evaluated based on the following evaluation criteria. Tensile strength retention [%] = {Tensile strength of samples subjected to heat aging [MPa] / Tensile strength of samples not subjected to heat aging [MPa]} × 100-Evaluation criteria-◎: at 120 ° C The retention rate of tensile strength after 12 hours has exceeded 95% ○: The retention rate of tensile strength after 12 hours has passed at 120 ° C is 90% or more and less than 95% △: 12 hours have passed at 120 ° C The subsequent tensile strength retention rate is 80% or more and less than 90% ×: The tensile strength retention rate does not reach 80% after 12 hours at 120 ° C

(將母料組合物混練而成之樹脂組合物中之聚苯醚(A)之均一分散性及相溶性) 依據下述順序而評價上述中所獲得之啞鈴狀試片之形態。 使用超薄切片機(Leica Microsystems公司製造、Leica EM UC7)，將啞鈴試片進行冷凍切削，而製作用以製作超薄切片之平面。 繼而，浸漬於加入至耐熱容器中之2質量%四氯化鋨水溶液中，於水浴中隔水加熱80℃×30分鐘後提拉，進行冷卻直至達到常溫後，自耐熱容器中取出，進行水洗、乾燥。 繼而，使用超薄切片機，自用以製作超薄切片之平面冷凍切削厚度85 nm之薄膜，而獲得超薄切片。 使用穿透式電子顯微鏡(Hitachi High-Technologies股份有限公司製造、HT7700)觀察所獲得之超薄切片。 將所獲得之TEM照片之白色部分作為聚苯醚(A)，將黑色部分作為熱塑性彈性體，並使用圖像分析軟體(Asahi Kasei Engineering股份有限公司製造、A-ZO KUN(商品名))進行圖像分析，藉此求出白色部分之面積之直方圖，基於下述評價基準而評價均一分散性及相溶性。 ＜均一分散性＞ ○：包含未達全部聚苯醚(A)之面積之5%之具有50 μm以上之直徑之聚苯醚(A)凝聚體。 ×：包含全部聚苯醚(A)之面積之5%以上之具有50 μm以上之直徑之聚苯醚(A)凝聚體。 ＜相溶性＞ ◎：全部聚苯醚(A)之平均分散粒徑未達500 nm。 ○：全部聚苯醚(A)之平均分散粒徑為500 nm以上且未達1 mm。 △：全部聚苯醚(A)之平均分散粒徑為1 μm以上未達5 mm。 ×：全部聚苯醚(A)之平均分散粒徑為5 μm以上。 於表2中表示評價結果。(Homogeneous dispersibility and compatibility of the polyphenylene ether (A) in the resin composition obtained by kneading the master batch composition) The form of the dumbbell-shaped test piece obtained in the above was evaluated according to the following procedure. An ultra-thin slicer (Leica Microsystems, Leica EM UC7) was used to freeze cut the dumbbell test pieces to produce a flat surface for making ultra-thin slices. Next, it was immersed in a 2 mass% rhenium tetrachloride aqueous solution added to a heat-resistant container, heated at 80 ° C for 30 minutes in a water bath, and then pulled and cooled until it reached normal temperature. Then, it was taken out of the heat-resistant container and washed with water. ,dry. Then, an ultra-thin slicer was obtained from a plane cryo-cut thickness of 85 nm using ultra-thin microtome to obtain ultra-thin sections. The obtained ultra-thin section was observed using a transmission electron microscope (Hitachi High-Technologies Co., Ltd., HT7700). The white portion of the obtained TEM photograph was defined as polyphenylene ether (A), and the black portion was defined as a thermoplastic elastomer. Image analysis software (manufactured by Asahi Kasei Engineering Co., Ltd., A-ZO KUN (trade name)) was used. Image analysis was performed to obtain a histogram of the area of the white portion, and uniform dispersibility and compatibility were evaluated based on the following evaluation criteria. <Homogeneous dispersibility> ○: A polyphenylene ether (A) aggregate having a diameter of 50 μm or more including less than 5% of the area of the entire polyphenylene ether (A). ×: A polyphenylene ether (A) aggregate having a diameter of 50 μm or more including 5% or more of the area of the entire polyphenylene ether (A). <Compatibility> ◎: The average dispersed particle diameter of all polyphenylene ethers (A) is less than 500 nm. ○: The average dispersed particle diameter of all polyphenylene ethers (A) is 500 nm or more and less than 1 mm. Δ: The average dispersed particle diameter of all polyphenylene ether (A) is 1 μm or more and less than 5 mm. ×: The average dispersed particle diameter of all polyphenylene ether (A) is 5 μm or more. The evaluation results are shown in Table 2.

[表2] [Table 2]

本申請案係基於2017年6月14日於日本專利廳提出申請之日本專利申請(日本專利特願2017-116679、日本專利特願2017-116686)、2017年12月20日於日本專利廳提出申請之日本專利申請(日本專利特願2017-243649、日本專利特願2017-243662)者，其內容係以參照之形式併入至本文中。 [產業上之可利用性]This application is based on a Japanese patent application filed with the Japan Patent Office on June 14, 2017 (Japanese Patent Application No. 2017-116679, Japanese Patent Application No. 2017-116686), and filed with the Japanese Patent Office on December 20, 2017 For Japanese patent applications (Japanese Patent Application No. 2017-243649, Japanese Patent Application No. 2017-243662), the contents of which are incorporated herein by reference. [Industrial availability]

若使用本發明之母料組合物，則可以簡便之步驟且於溫和之混練條件下，使具有充分之分子量之聚苯醚均一分散及相溶於熱塑性彈性體等中。以上述方式獲得之本發明之樹脂組合物係耐熱老化性優異。 本發明之母料組合物、及本發明之樹脂組合物作為輪胎構件用橡膠之改質劑、道路鋪設用瀝青改質劑、防水用、隔音用及制振用瀝青片材之改質劑、熱熔接著劑、密封材、及纜線被覆材等，具有產業上之可利用性。If the masterbatch composition of the present invention is used, a polyphenylene ether having a sufficient molecular weight can be uniformly dispersed and dissolved in a thermoplastic elastomer or the like in a simple process and under mild kneading conditions. The resin composition of the present invention obtained as described above is excellent in heat aging resistance. The master batch composition of the present invention and the resin composition of the present invention are used as modifiers for rubbers for tire members, asphalt modifiers for road paving, asphalt modifiers for waterproofing, sound insulation, and vibration control, Hot-melt adhesives, sealing materials, and cable coating materials are industrially available.

Claims (17)

一種母料組合物，其係包含如下成分者： 聚苯醚(A-1)、及/或具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基之官能基改性聚苯醚(A-2)；與 嵌段共聚物(B)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段(b1)與至少1個共軛二烯化合物聚合物嵌段(b2)之嵌段共聚物之非氫化物(B-0)；包含至少1個乙烯基芳香族化合物聚合物嵌段(b1')與至少1個共軛二烯化合物聚合物嵌段(b2')之嵌段共聚物之氫化物(B-I)；及包含至少1個乙烯基芳香族化合物聚合物嵌段(b1'')及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)之嵌段共聚物之氫化物(B-II)所組成之群中之至少一種；且 包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量為10,000以上且50,000以下， 相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，合計包含上述(A-1)與上述(A-2)10質量份以上且90質量份以下，且包含上述(B)10質量份以上且90質量份以下。A master batch composition comprising the following components: polyphenylene ether (A-1), and / or a functional group modified with at least one functional group selected from the group consisting of a carboxyl group and a group derived from a carboxyl group Polyphenylene ether (A-2); and block copolymer (B), which is selected from the group consisting of at least one vinyl aromatic polymer polymer block (b1) and at least one conjugated diene compound polymer. Non-hydride (B-0) of the block copolymer of segment (b2); contains at least 1 vinyl aromatic polymer polymer block (b1 ') and at least 1 conjugated diene compound polymer block ( b2 ') block copolymer hydride (BI); and at least one vinyl aromatic polymer polymer block (b1' ') and at least one conjugated diene compound and vinyl aromatic compound At least one of the group consisting of the hydride (B-II) of the block copolymer of the random copolymer block (b3); and a polymer comprising the above (A-1) and / or the above (A-2) The weight average molecular weight of phenyl ether is 10,000 or more and 50,000 or less, and the total amount of (A-1) and (A-1) and (B) is 100 parts by mass based on the total of (A-1) and The above (A-2) is 10 parts by mass or more and 90 parts by mass or less, and includes the above (B) 10 parts by mass or more and 90 parts by mass or less. 如請求項1之母料組合物，其進而包含抗氧化劑(C)與潤滑劑(D)，且 相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，包含上述(C)0.1質量份以上且20質量份以下，且包含上述(D)0.1質量份以上且40質量份以下。The masterbatch composition according to claim 1, further comprising an antioxidant (C) and a lubricant (D), and 100 masses relative to the total of (A-1), (A-2), and (B) above. Part, which contains 0.1 mass part or more and 20 mass parts or less of (C) mentioned above, and contains 0.1 mass part or more and 40 mass parts or less of (D) mentioned above. 如請求項1或2之母料組合物，其中相對於上述(A-1)、上述(A-2)及上述(B)之合計100質量份，合計包含上述(A-1)與上述(A-2)20質量份以上且50質量份以下，且包含上述(B)50質量份以上且80質量份以下。For example, the masterbatch composition of claim 1 or 2 includes the above (A-1) and the above (A-1), (A-2), and (B) in total 100 parts by mass. A-2) 20 parts by mass or more and 50 parts by mass or less, and including (B) 50 parts by mass or more and 80 parts by mass or less. 如請求項1至3中任一項之母料組合物，其具有海島結構，該海島結構包含： 島相，其係由上述(A-1)及/或上述(A-2)所構成；及 海相，其係由上述(B)所構成。If the masterbatch composition of any one of claims 1 to 3 has a sea-island structure, the sea-island structure includes: an island phase composed of (A-1) and / or (A-2) above; And marine facies, which are composed of (B) above. 如請求項4之母料組合物，其中上述島相之平均直徑未達5 μm。For example, the master batch composition of claim 4, wherein the average diameter of the island phase is less than 5 μm. 如請求項5之母料組合物，其中上述島相之平均直徑未達1 μm。For example, the master batch composition of claim 5, wherein the average diameter of the island phases is less than 1 μm. 如請求項1至6中任一項之母料組合物，其具有選自由顆粒、小顆粒、及粉體所組成之群中之任一種形狀。The master batch composition according to any one of claims 1 to 6, which has a shape selected from the group consisting of granules, small granules, and powders. 如請求項1至7中任一項之母料組合物，其為聚苯醚母料組合物。The master batch composition according to any one of claims 1 to 7, which is a polyphenylene ether master batch composition. 如請求項1至8中任一項之母料組合物，其可用作改質劑。The masterbatch composition as claimed in any one of claims 1 to 8 which can be used as a modifier. 一種樹脂組合物之製造方法，其具有如下步驟： 將如請求項1至9中任一項之母料組合物、及 包含選自由熱塑性彈性體、軟質系熱塑性聚合物、橡膠、瀝青、密封劑、接著劑、熱熔接著劑、黏著劑、及塗料所組成之群中之至少任一種之媒體 於未達250℃之溫度條件下機械地進行混練。A method for producing a resin composition, comprising the steps of: adding the master batch composition according to any one of claims 1 to 9 and including a material selected from the group consisting of a thermoplastic elastomer, a soft thermoplastic polymer, rubber, asphalt, and a sealant; The media of at least any one of the group consisting of adhesive, hot melt adhesive, adhesive, and coating are mechanically kneaded at a temperature of less than 250 ° C. 如請求項10之樹脂組合物之製造方法，其中上述媒體為軟質系熱塑性聚合物，且 上述軟質系熱塑性聚合物係選自由聚烯烴系、聚胺基甲酸酯系、聚酯系、聚醯胺系、及聚氯乙烯系所組成之群中之一種以上。The method for manufacturing a resin composition according to claim 10, wherein the medium is a soft thermoplastic polymer, and the soft thermoplastic polymer is selected from the group consisting of polyolefin, polyurethane, polyester, and polyfluorene. One or more of amine-based and polyvinyl chloride-based groups. 如請求項10之樹脂組合物之製造方法，其中上述媒體為熱塑性彈性體(E)， 該熱塑性彈性體(E)係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段、及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物；及至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物所組成之群中之一種或兩種以上。The method for manufacturing a resin composition according to claim 10, wherein the medium is a thermoplastic elastomer (E), and the thermoplastic elastomer (E) is selected from the group consisting of a polymer block containing at least one vinyl aromatic compound and at least one Non-hydrogenated block copolymers of conjugated diene compound polymer blocks; block copolymers comprising at least 1 vinyl aromatic polymer block and at least 1 conjugated diene compound polymer block Hydride; hydride of a block copolymer comprising at least one polymer block of a vinyl aromatic compound and at least one random copolymer block of a conjugated diene compound and a vinyl aromatic compound; and One or two or more of the group consisting of a non-hydride of a random copolymer of at least one vinyl aromatic compound and at least one conjugated diene compound. 如請求項10至12中任一項之樹脂組合物之製造方法，其中上述進行混練之步驟後之包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑未達5 μm。The method for producing a resin composition according to any one of claims 10 to 12, wherein the average dispersed particles of the polyphenylene ether (A-1) and / or (A-2) described above after the step of performing the kneading are performed. The diameter does not reach 5 μm. 一種樹脂組合物，其包含： 聚苯醚(A-1)、及/或具有選自由羧基及由羧基衍生之基所組成之群中之至少一種官能基之官能基改性聚苯醚(A-2)； 嵌段共聚物(B)，其係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段(b1)與至少1個共軛二烯化合物聚合物嵌段(b2)之嵌段共聚物之非氫化物(B-0)；包含至少1個乙烯基芳香族化合物聚合物嵌段(b1')與至少1個共軛二烯化合物聚合物嵌段(b2')之嵌段共聚物之氫化物(B-I)；及包含至少1個乙烯基芳香族化合物聚合物嵌段(b1'')及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段(b3)之嵌段共聚物之氫化物(B-II)所組成之群中之至少一種；及 媒體，其係選自由熱塑性彈性體、軟質系熱塑性聚合物、橡膠、瀝青、密封劑、接著劑、熱熔接著劑、黏著劑、及塗料所組成之群中之至少一種；且 包含上述(A-1)及/或上述(A-2)之聚苯醚之重量平均分子量為10,000以上且50,000以下， 且包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑未達5 μm。A resin composition comprising: polyphenylene ether (A-1) and / or a functional group-modified polyphenylene ether (A) having at least one functional group selected from the group consisting of a carboxyl group and a group derived from a carboxyl group. -2); a block copolymer (B), which is selected from the group consisting of at least one vinyl aromatic polymer polymer block (b1) and at least one conjugated diene compound polymer block (b2) Non-hydrogenated block copolymer (B-0); block comprising at least 1 vinyl aromatic polymer polymer block (b1 ') and at least 1 conjugated diene compound polymer block (b2') Copolymer hydride (BI); and random copolymer block containing at least 1 vinyl aromatic polymer block (b1 '') and at least 1 conjugated diene compound and vinyl aromatic compound (b3) at least one of the group consisting of the hydride (B-II) of the block copolymer; and a medium selected from the group consisting of a thermoplastic elastomer, a soft thermoplastic polymer, rubber, asphalt, a sealant, and At least one of the group consisting of an adhesive, a hot-melt adhesive, an adhesive, and a coating; and including the above (A-1) and / or The weight average molecular weight of the polyphenylene ether of (A-2) is 10,000 or more and 50,000 or less, and the average dispersed particle diameter of the polyphenylene ether containing the above (A-1) and / or the above (A-2) is less than 5 μm. 如請求項14之樹脂組合物，其中上述媒體為軟質系熱塑性聚合物，且 上述軟質系熱塑性聚合物係選自由聚烯烴系、聚胺基甲酸酯系、聚酯系、聚醯胺系、及聚氯乙烯系所組成之群中之一種以上。The resin composition according to claim 14, wherein the medium is a soft thermoplastic polymer, and the soft thermoplastic polymer is selected from the group consisting of polyolefins, polyurethanes, polyesters, polyamides, And more than one of the group consisting of polyvinyl chloride. 如請求項14之樹脂組合物，其中上述媒體為熱塑性彈性體(E)， 該熱塑性彈性體(E)係選自由包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之非氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段與至少1個共軛二烯化合物聚合物嵌段之嵌段共聚物之氫化物；包含至少1個乙烯基芳香族化合物聚合物嵌段、及至少1個共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段之嵌段共聚物之氫化物；及至少一種乙烯基芳香族化合物與至少一種共軛二烯化合物之無規共聚物之非氫化物所組成之群中之一種或兩種以上。The resin composition according to claim 14, wherein the medium is a thermoplastic elastomer (E), and the thermoplastic elastomer (E) is selected from the group consisting of at least one vinyl aromatic polymer polymer block and at least one conjugated dimer. Non-hydrides of block copolymers of olefin polymer blocks; hydrides of block copolymers comprising at least 1 vinyl aromatic polymer block and at least 1 conjugated diene compound polymer block ; A hydride of a block copolymer comprising at least one polymer block of a vinyl aromatic compound and at least one random copolymer block of a conjugated diene compound and a vinyl aromatic compound; and at least one ethylene One or two or more of the group consisting of a non-hydride of a random copolymer of a base aromatic compound and at least one conjugated diene compound. 如請求項14至16中任一項之樹脂組合物，其中包含上述(A-1)及/或上述(A-2)之聚苯醚之平均分散粒徑未達1 μm。The resin composition according to any one of claims 14 to 16, wherein the average dispersed particle diameter of the polyphenylene ether containing the above (A-1) and / or the above (A-2) is less than 1 μm.
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