TW202212377A - Resin composition, resin modifier, dispersion composition, member for automobile, and method for producing resin composition - Google Patents

Abstract

A resin composition including a reaction product (C) of a modified elastomer (A) and a reactive compound (B), wherein the resin composition satisfies conditions [I]-[II] below. [I] The modified elastomer (A) is (i) a block copolymer having a polymer block (A-1) derived from an aromatic vinyl compound and a polymer block (A-2) derived from a conjugated diene compound, (ii) a hydrogenated product of said block copolymer, or (iii) an olefin-based elastomer, each having a functional group capable of reacting with an oxazoline group or an epoxy group. [II] The reactive compound (B) has two or more of at least one type of group selected from the group consisting of oxazoline groups and epoxy groups, per molecule.

Description

Resin composition, resin modifier, dispersion composition, automotive component, and method for producing the resin composition

The present invention relates to a resin composition, a resin modifier, a dispersion composition, an automotive member, and a method for producing the resin composition.

Among the block copolymers having a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound, and a hydrogenated product thereof, are known to have Vibration-damping properties, and have been used for vibration-damping materials. The above-mentioned block copolymers and their hydrogenated products have physical properties such as sound insulation, heat resistance, impact resistance, and adhesiveness in addition to vibration damping properties, and are considered to be useful in various applications. use. For example, in order to improve mechanical properties such as vibration damping properties, flexibility, heat resistance, tensile strength, and impact resistance, it has been revealed that the peak temperature of tanδ or the amount of vinyl bonding is controlled by a specific styrenic compound and isoprene. Or hydrogenated block copolymers of conjugated diene compounds such as butadiene (for example, refer to Patent Documents 1 to 4). Moreover, the vibration damping property of a polyamide resin can be improved by adding the said hydrogenated block copolymer to a polyamide resin, for example.

As a method for improving the compatibility of non-polar materials such as styrene-based elastomers or olefin-based elastomers with polar resins, for example, it is known to modify the elastomer with maleic anhydride (hereinafter referred to as MAh modification). method (for example, refer to Patent Document 5). However, the maleic anhydride modification of the elastomer, the polar resin that can improve the compatibility is limited, such as polyphenylene sulfide (PPS), polycarbonate (PC), polybutylene terephthalate ( The effect of improving the compatibility of resins such as PBT) cannot be said to be sufficient.

唑啉系聚合物混練而得到

唑啉改質聚烯烴。而且，記載使用

唑啉改質聚烯烴作為聚乙烯(PE)及聚烯烴之相容劑。 [先前技術文獻] [專利文獻] As another method of improving the compatibility of the non-polar material with the polar resin, there is a method of adding a small amount of a compatibilizer which is reactive with the polar resin and has high compatibility with the non-polar material. For example, Patent Document 6 describes that MAh-modified polypropylene or carboxylic acid-modified polyethylene, which is a maleic acid-modified product of polypropylene (PP), is extruded with an extruder.

Obtained by kneading oxazoline polymers

oxazoline-modified polyolefins. Furthermore, the use of

The oxazoline-modified polyolefin is used as a compatibilizer for polyethylene (PE) and polyolefin. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2002-284830 Patent Document 2: International Publication No. 2000/015680 Patent Document 3: Japanese Patent Laid-Open No. 2006-117879 Patent Document 4: Japanese Patent Laid-Open No. 2010-053319 Patent Document 5: Japanese Patent Laid-Open No. 61-076518 Patent Document 6: Japanese Patent Laid-Open No. 2012-102231

[The problem to be solved by the invention]

唑啉基即使對於在彈性體的MAh化下無法充分提高相容性的上述各樹脂，也顯示高的反應性，因此若可將此等官能基導入至彈性體，則可期待相容性之改善，但以往未曾提案其之實用的方法。 專利文獻6中記載使用

唑啉改質聚烯烴作為PE及聚烯烴的相容劑，但作為應使其相容的物質，沒有記載使用彈性體。 又，畢竟相容劑並非對於彈性體形成新的共價鍵者。因此，在進一步提高彈性體對於極性樹脂的相容性、或提高對於更多種類的樹脂之相容性上，使用相容劑之方法不能說是有利的方法。 將上述嵌段共聚物或其氫化物或者烯烴系彈性體添加至極性樹脂等的其它樹脂而製作分散體組成物時，若被分散體成分對於上述其它樹脂的相容性低，則有變得不能充分提高所得之分散體組成物的加工性、成形性、及制振性或耐衝擊性等之力學物性等的問題。 epoxy or

The oxazoline group exhibits high reactivity even with respect to each of the above-mentioned resins whose compatibility cannot be sufficiently improved by MAhization of the elastomer. Therefore, if these functional groups can be introduced into the elastomer, the compatibility can be expected to increase. improvement, but no practical method has been proposed in the past. Use described in Patent Document 6

The oxazoline-modified polyolefin is used as a compatibilizer for PE and polyolefin, but there is no description of using an elastomer as a substance to be compatibilized. Also, after all, the compatibilizer is not one that forms new covalent bonds to the elastomer. Therefore, the method of using a compatibilizer cannot be said to be an advantageous method for further improving the compatibility of the elastomer with polar resins or improving the compatibility with more kinds of resins. When the above-mentioned block copolymer or its hydrogenated product or olefin-based elastomer is added to other resins such as polar resins to prepare a dispersion composition, if the compatibility of the components to be dispersed with the above-mentioned other resins is low, there may be problems. There is a problem that the processability, formability, and mechanical properties such as vibration damping and impact resistance of the obtained dispersion composition cannot be sufficiently improved.

Therefore, an object of the present invention is to provide a resin composition which exhibits high compatibility with many kinds of resins. Another object is to provide a dispersion composition which is excellent in formability and excellent in mechanical properties such as high vibration damping properties in a wide temperature range. [means to solve the problem]

In order to solve the above-mentioned problem, the inventors of the present invention have thought about the following invention, and found that the problem can be solved. That is, the present invention is as follows.

唑啉基或環氧基反應的官能基之(i)具有以源自芳香族乙烯基化合物的結構單元為主體的聚合物嵌段(A-1)與以源自共軛二烯化合物的結構單元為主體的聚合物嵌段(A-2)之嵌段共聚物、(ii)該嵌段共聚物之氫化物或(iii)烯烴系彈性體； [II]反應性化合物(B)係每1分子具有2個以上的選自包含

唑啉基及環氧基之群組的1種以上之基。 [2]一種樹脂改質劑，其包含上述樹脂組成物。 [3]一種分散體組成物，其含有上述樹脂組成物作為第1樹脂組成物(D)，且進一步含有基質樹脂(E)，第1樹脂組成物(D)係分散於基質樹脂(E)中。 [4]一種汽車用構件，其含有上述分散體組成物。 [5]一種樹脂組成物之製造方法，其係上述樹脂組成物之製造方法，其中藉由將改質彈性體(A)與反應性化合物(B)以熔融狀態混合而使兩者反應，生成反應物(C)。 [6]一種樹脂組成物之製造方法，其係上述樹脂組成物之製造方法，其中於熔融狀態的嵌段共聚物、前述嵌段共聚物之氫化物或烯烴系彈性體中，添加自由基起始劑、與含羧基的化合物及酸酐中之至少一者，接著添加反應性化合物(B)，而對於前述嵌段共聚物、前述嵌段共聚物之氫化物或前述烯烴系彈性體，導入羧基及源自酸酐的基中之至少一者，同時使反應性化合物(B)反應。 [7]一種樹脂組成物之製造方法，其係上述樹脂組成物之製造方法，其中於熔融狀態的嵌段共聚物、前述嵌段共聚物之氫化物或烯烴系彈性體中，添加含羧基的化合物及酸酐中之至少一者，而對於前述嵌段共聚物、前述嵌段共聚物之氫化物或前述烯烴系彈性體，導入羧基及源自酸酐的基中之至少一者，接著添加反應性化合物(B)，而使前述反應性化合物(B)對於導入有前述羧基及源自酸酐的基中之至少一者的前述嵌段共聚物、前述嵌段共聚物之氫化物或前述烯烴系彈性體進行反應。 [發明之效果] [1] A resin composition comprising a reactant (C) of a modified elastomer (A) and a reactive compound (B), which satisfies the following conditions [I] to [II] ]: [I] The modified elastomer (A) is a

(i) of functional groups reacted with oxazoline group or epoxy group has a polymer block (A-1) mainly derived from a structural unit derived from an aromatic vinyl compound and a structure derived from a conjugated diene compound A block copolymer of the polymer block (A-2) whose unit is the main body, (ii) a hydrogenated product of the block copolymer, or (iii) an olefin-based elastomer; [II] The reactive compound (B) is each 1 molecule has 2 or more selected from including

One or more groups of the group of an oxazoline group and an epoxy group. [2] A resin modifier comprising the above resin composition. [3] A dispersion composition comprising the above-mentioned resin composition as a first resin composition (D), and further comprising a matrix resin (E), wherein the first resin composition (D) is dispersed in the matrix resin (E) middle. [4] An automotive member comprising the above dispersion composition. [5] A method for producing a resin composition, which is the method for producing the above-mentioned resin composition, wherein the modified elastomer (A) and the reactive compound (B) are mixed in a molten state and reacted to produce Reactant (C). [6] A method for producing a resin composition, which is the method for producing the above-mentioned resin composition, wherein a block copolymer in a molten state, a hydrogenated product of the above-mentioned block copolymer, or an olefin-based elastomer is added with a radical A starting agent, and at least one of a carboxyl group-containing compound and an acid anhydride, followed by adding a reactive compound (B), and introducing a carboxyl group to the block copolymer, the hydrogenated product of the block copolymer, or the olefin-based elastomer and at least one of the groups derived from the acid anhydride, while reacting the reactive compound (B). [7] A method for producing a resin composition, which is the method for producing the above-mentioned resin composition, wherein a carboxyl group-containing At least one of a compound and an acid anhydride, and at least one of a carboxyl group and an acid anhydride-derived group is introduced into the block copolymer, the hydrogenated product of the block copolymer, or the olefin-based elastomer, followed by adding reactive compound (B), and the reactive compound (B) is used for the block copolymer, the hydrogenated product of the block copolymer, or the olefin-based elastic compound into which at least one of the carboxyl group and the acid anhydride-derived group is introduced. body reacts. [Effect of invention]

According to the present invention, it is possible to provide a resin composition showing high compatibility with many kinds of resins. Furthermore, according to the present invention, it is possible to provide a dispersion composition which is excellent in formability and excellent in mechanical properties such as high vibration damping properties in a wide temperature range.

[Form for carrying out the invention]

In this specification, the preferable rules can be selected arbitrarily, and the combination of the preferable rules can be said to be even better. In this specification, the description of "XX to YY" means "XX or more and YY or less". In this specification, regarding a preferable numerical range (for example, the range of a content etc.), a lower limit value and an upper limit value are described step by step, and can be combined with each independently. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", a combination of "preferable lower limit value (10)" and "preferable upper limit value (60)" may be "10 to 60". In this specification, "-unit" (herein, "-" represents a monomer) means "constituent unit derived from ...", for example, so-called "propylene unit" means "constituent unit derived from propylene". In this specification, for example, the term "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid", and the same applies to other similar terms. In this specification, the weight average molecular weight refers to the weight average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC). In the present specification, when it is referred to as "B mainly composed of A", it means that B contains at least more than 50% by mass of A.

唑啉基或環氧基反應的官能基之下述(i)、(ii)或(iii)。 (i)具有以源自芳香族乙烯基化合物的結構單元為主體的聚合物嵌段(A-1)與以源自共軛二烯化合物的結構單元為主體的聚合物嵌段(A-2)之嵌段共聚物 (ii)上述嵌段共聚物之氫化物 (iii)烯烴系彈性體 [II]反應性化合物(B)係每1分子具有2個以上的選自包含

唑啉基及環氧基之群組的1種以上之基。 此外，於本說明書中，有將上述樹脂組成物稱為「第1樹脂組成物(D)」或「樹脂組成物(D)」的情形。 [Resin composition] The resin composition of the embodiment of the present invention (hereinafter referred to as the resin composition of the present embodiment) is a reaction product (C) comprising a modified elastomer (A) and a reactive compound (B). ), the resin composition satisfies the following conditions [I] to [II]. [I] The modified elastomer (A) is a

The following (i), (ii) or (iii) of the functional group reacted with the oxazoline group or the epoxy group. (i) having a polymer block (A-1) composed mainly of a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) composed mainly of a structural unit derived from a conjugated diene compound ) block copolymer (ii) hydrogenated product of the above block copolymer (iii) olefin-based elastomer [II] Reactive compound (B) having 2 or more per molecule selected from the group consisting of

One or more groups of the group of an oxazoline group and an epoxy group. In addition, in this specification, the said resin composition may be called "1st resin composition (D)" or "resin composition (D)".

The reactant (C) contained in the resin composition (D) is produced as a reactant in which the modified part of the modified elastomer (A) reacts with the reactive compound (B) and the two are covalently bonded By. The resin composition (D) may consist only of the reactant (C), or may contain components other than the reactant (C). The resin composition (D) may further contain at least one of the modified elastomer (A) and the reactive compound (B) as components other than the reactant (C). The resin composition (D) may contain an elastomer (hereinafter referred to as an elastomer (A0)) before modification. In addition, the details of the reactant (C) will be described later.

The amount of the reactant (C) in the resin composition (D) is relative to the resin composition ( The total mass of D) is preferably 1 mass % or more, more preferably 5 mass % or more, and still more preferably 10 mass % or more. The upper limit of the content is not particularly limited as long as it is within a range that does not impair the effects of the present invention, but from the viewpoint of productivity, it is preferably 100 mass % or less, may be 90 mass % or less, or may be 80 mass % or less may be 70 mass % or less. In other words, the amount of the reactant (C) in the resin composition (D) is preferably 1 to 100 mass % with respect to the total mass of the resin composition (D). The elastomer (A0) before modification, the modified elastomer (A), and the reactive compound (B) that may be included in the resin composition (D) as components other than the reactant (C), before modification The content of the elastomer (A0) is regarded as A0M, the content of the modified elastomer (A) is regarded as AM, and the content of the reactive compound (B) is regarded as BM, from the matrix resin (E) or the area resin. From the viewpoint of improving the compatibility of (F), A0M is preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less with respect to the total mass of the resin composition (D). . Moreover, from the same viewpoint, AM is preferably 90 mass % or less, more preferably 70 mass % or less, and further preferably 50 mass % or less with respect to the total mass of the resin composition (D). Also, from the same viewpoint, BM is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably BM based on the total mass of the resin composition (D). 10 mass % or less. In other words, AM0 in the resin composition (D) is preferably 0 to 70 mass %, AM in the resin composition (D) is preferably 0 to 90 mass %, and BM in the resin composition (D) is preferably 0 to 90 mass % 0 to 50 mass %. Moreover, with respect to the total mass of the resin composition (D), preferably AM is 70 mass % or less, BM is 20 mass % or less; more preferably AM is 50 mass % or less, BM is 20 mass % or less; In the best series, AM is 50 mass % or less, and BM is 20 mass % or less. In other words, AM and BM in the resin composition (D) are preferably 0 to 70 mass % of AM and 0 to 20 mass % of BM. Also, when the content of the reactive compound (B) contained in the resin composition (D) is taken as B mass %, and the content of the reactant (C) is taken as C mass %, the difference between the content of the reactive compound (B) and the matrix resin (E) or the region From the viewpoint of improving the compatibility of the resin (F), the value of C/(B+C) is preferably 0.1 to 1.0, more preferably 0.3 to 1.0, still more preferably 0.5 to 1.0.

In the resin composition (D), by satisfying the above-mentioned condition [II], the reactant (C) has high compatibility with various kinds of resins, even for unmodified elastomers or general resins. Resins that are difficult to be compatible with modified elastomers (such as MAh elastomers) also show compatibility. Therefore, for example, when the reactant (C) is added to and mixed with the matrix resin (E) described later, the portion derived from the reactive compound (B) in the resin composition (D) is interposed between the reactant (C). ) and the matrix resin (E) to disperse the reactant (C) in the matrix resin (E). Then, a core-shell structure formed by a shell mainly composed of a site derived from the reactive compound (B) and a core (core) mainly composed of the reactant (C) is formed. In addition, since the portion of the reactive compound (B) having high compatibility with the matrix resin (E) in the reactant (C) is located on the outside, the reactant (C) is dispersed in the form of fine dots. in the matrix resin (E). In this way, even the elastomer (A0), which is hardly compatible with the matrix resin (E) as it is, is modified to become the reactant (C), and can be finely and uniformly dispersed in the matrix resin (E). Furthermore, it is considered to be related to showing high compatibility with many kinds of resins.

In addition, when the domain resin (F) described later is added to the reactant (C) and mixed, the reactant (C) and the domain are interposed between the reactant (C) and the domain by the moiety derived from the reactive compound (B) in the resin composition (D). The resin (F) exists between the resins (F) to disperse the domain resin (F) in the matrix of the resin composition (D). Then, a core-shell structure composed of a shell mainly composed of a site derived from the reactive compound (B) and a core mainly composed of the domain resin (F) is formed. In addition, since the site of the reactive compound (B) having high compatibility with the region resin (F) in the reactant (C) is located on the side of the region resin (F), the region resin (F) tends to become finely divided The dots are dispersed in the matrix of the resin composition (D). In this way, even if the elastomer (A0) which is incompatible with the domain resin (F) as it is is used, the elastomer (A0) is modified to become the reactant (C), so that the domain resin (F) can be made microscopic. and uniformly dispersed in the matrix of the resin composition (D).

In addition, since the reactant (C) contained in the resin composition (D) is easily dispersed in the matrix resin (E), the moldability of the matrix resin (E) after the addition of the resin composition (D) can be improved compared with that before the addition. increase, and the effect of improving the properties of the reactive compound (B) and the elastomer (A0) is likely to appear. In the resin composition (D) according to the embodiment of the present invention, by satisfying the above-mentioned condition [I], in the matrix resin (E) after adding the resin composition (D), vibration damping properties and impact resistance can be obtained. The mechanical properties such as sex are more improved than before the addition. In addition, since the domain resin (F) is easily dispersed in the reactant (C) contained in the resin composition (D), the elongation properties and flexibility of the resin composition (D) are ensured, and the domain is easily developed. Physical properties of resin (F).

In addition, from the viewpoint of enhancing the effect of improving the mechanical properties of the matrix resin (E) after adding the resin composition (D) or the resin composition (D) after adding the domain resin (F), in the resin composition ( In D), in addition to the reactant (C), the modified elastomer (A), the reactive compound (B), and the elastomer (A0), the content of the resin component contained is preferably 0 to 50% by mass, more preferably It is 0-30 mass %, More preferably, it is 0-20 mass %, More preferably, it is 0-10 mass %, Most preferably, it is 0-5 mass %.

Hereinafter, components constituting the resin composition of the present embodiment will be described. Moreover, the use of a resin composition, a dispersion composition, the use of a dispersion composition, the manufacturing method of a dispersion composition, etc. are also demonstrated.

唑啉基或環氧基反應的官能基之(i)具有以源自芳香族乙烯基化合物的結構單元(以下有簡稱為「芳香族乙烯基化合物單元」的情形)為主體的聚合物嵌段(A-1)與以源自共軛二烯化合物的結構單元(以下有簡稱為「共軛二烯單元」的情形)為主體的聚合物嵌段(A-2)之嵌段共聚物、(ii)該嵌段共聚物之氫化物或(iii)烯烴系彈性體。 從制振性及耐衝擊性等機械特性之觀點來看，改質彈性體(A)較佳為具有上述官能基的上述嵌段共聚物、或具有上述官能基的上述嵌段共聚物之氫化物，更佳為上述嵌段共聚物的改質物、或上述嵌段共聚物之氫化物的改質物。上述嵌段共聚物及其氫化物之詳細係如後述。 <Modified elastomer (A)> The modified elastomer (A) is defined in the above-mentioned condition [I], and has the properties of

(i) of the functional groups reacted with an oxazoline group or an epoxy group has a polymer block mainly composed of a structural unit derived from an aromatic vinyl compound (hereinafter abbreviated as "aromatic vinyl compound unit"). (A-1) a block copolymer with a polymer block (A-2) mainly composed of a structural unit derived from a conjugated diene compound (hereinafter referred to simply as a "conjugated diene unit"), (ii) a hydrogenated product of the block copolymer or (iii) an olefin-based elastomer. From the viewpoint of mechanical properties such as vibration damping properties and impact resistance, the modified elastomer (A) is preferably the above-mentioned block copolymer having the above-mentioned functional group, or the hydrogenation of the above-mentioned block copolymer having the above-mentioned functional group. A modified product of the above-mentioned block copolymer or a modified product of the hydrogenated product of the above-mentioned block copolymer is more preferred. Details of the above-mentioned block copolymer and its hydrogenated product will be described later.

唑啉基或環氧基反應的官能基之化合物(以下稱為反應性化合物(a))所具有的上述官能基，可舉出烷氧基矽基、羧基、胺基、羥基、酚性羥基、源自酸酐的基、酯基、巰基等。亦可具有此等中之2種以上。較佳為選自包含羧基、酚性羥基及源自酸酐的基之群組的1種或2種以上之官能基，從與

唑啉基或環氧基的反應性之觀點來看，更佳為選自包含羧基及源自酸酐的基之群組的1種或2種以上之官能基。作為能與

唑啉基或環氧基反應的官能基，從使反應性擠壓成為容易而適合工業化之觀點來看，特佳為選自包含源自馬來酸酐的基、源自琥珀酸酐的基、源自鄰苯二甲酸酐的基及羧基之群組的至少1種之基，尤其選自包含源自馬來酸酐的基及羧基之群組的至少1種之基。此外，本說明書中所謂酚性羥基，意指將芳香環的氫原子取代之羥基。 此處，所謂「源自馬來酸酐的基」，係下述中的至少一者之基：具有構成馬來酸酐之環的雙鍵之碳的一者成為鍵結臂(bonding hand)之結構的基；及具有馬來酸酐的2個CO中的一者之O成為鍵結臂之結構的基。所謂「源自琥珀酸酐的基」，係具有琥珀酸酐的2個CO中的一者之O成為鍵結臂之結構的基。所謂「源自鄰苯二甲酸酐的基」，係具有鄰苯二甲酸酐的2個CO中的一者之O成為鍵結臂之結構的基。 As the functional group used to introduce the above-mentioned functional group to modify the elastomer (A0), it has the ability to

The above-mentioned functional group possessed by the compound of the functional group reacted with an oxazoline group or an epoxy group (hereinafter referred to as a reactive compound (a)) includes an alkoxysilyl group, a carboxyl group, an amino group, a hydroxyl group, and a phenolic hydroxyl group. , groups derived from acid anhydrides, ester groups, mercapto groups, etc. There may be two or more of these. Preferably, one or two or more functional groups selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an acid anhydride-derived group are selected from the group consisting of

From the viewpoint of the reactivity of the oxazoline group or the epoxy group, it is more preferably one or more functional groups selected from the group consisting of a carboxyl group and an acid anhydride-derived group. as capable of

The functional group to be reacted with an oxazoline group or an epoxy group is particularly preferably selected from the group consisting of a group derived from maleic anhydride, a group derived from succinic anhydride, a source of A group of at least one kind selected from the group of a group derived from phthalic anhydride and a carboxyl group is particularly selected from a group of at least one kind selected from the group of a group derived from maleic anhydride and a carboxyl group. In addition, the phenolic hydroxyl group in this specification means the hydroxyl group which substituted the hydrogen atom of an aromatic ring. Here, the "group derived from maleic anhydride" refers to at least one of the following groups: a structure in which one of carbons having a double bond constituting a ring of maleic anhydride becomes a bonding hand. and a group in which O of one of the two COs of maleic anhydride becomes a structure of a bonding arm. The "group derived from succinic anhydride" refers to a group having a structure in which one of the two COs of succinic anhydride becomes a bonding arm. The "group derived from phthalic anhydride" refers to a group having a structure in which one of the two COs of phthalic anhydride has a structure in which O becomes a bonding arm.

The modified elastomer (A) has one or two or more of the above-mentioned functional groups in the molecule. From the viewpoint of easily securing fluidity, it is preferable to reduce the number of functional groups in the molecule of the modified elastomer (A), and it is more preferable to have, for example, only one of the functional groups in the molecule. In addition, the position of the functional group in the modified elastomer (A) is not particularly limited, but from the viewpoint of easy control of fluidity, it is preferable to have the functional group at the molecular end, and it is more preferable to have the functional group only at the molecular end. Has the above-mentioned functional group. The number of the functional groups in the modified elastomer (A) can be controlled, for example, by adjusting the amount of the radical initiator added in the method for producing the modified elastomer (A) described later. Moreover, in order to make the above-mentioned functional group exist at the molecular terminal of the modified elastomer (A), for example, as described later, a specific group such as a hydroxyl group can be introduced into the terminal when the elastomer (A0) is produced, and the above-mentioned functional group can be introduced. The reactive compound (a) is realized by a method of reacting the group.

It is desirable not to bind other substances such as the reactive compound (B) to the functional group of the modified elastomer (A) used for the production of the reactant (C).

From the viewpoint of further improving mechanical properties such as vibration damping properties and impact resistance, the block (A-1) having more than 70 mol% of aromatic vinyl monomer units and containing a conjugated diene monomer are preferred. A modified product of a block copolymer of 30 mol% or more of block (A-2) or a hydrogenated product thereof.

The aromatic vinyl compound unit is more preferably 80 mol % or more in the polymer block (A-1), more preferably 90 mol % or more, still more preferably 95 mol % or more, particularly preferably Essentially 100 mol%. In other words, the aromatic vinyl compound unit in the polymer block (A-1) is preferably 80 to 100 mol %. The conjugated diene unit in the polymer block (A-2) is preferably 50 mol % or more, more preferably 70 mol % or more, still more preferably, from the viewpoint of exhibiting excellent vibration damping properties It is 90 mol% or more, particularly preferably substantially 100 mol%. In other words, the conjugated diene unit in the polymer block (A-2) is preferably 50 to 100 mol %.

The modified elastomer (A) is more preferably a modified product of a hydrogenated product of a block copolymer of the polymer block (A-1) and the polymer block (A-2). The modified elastomer (A) is particularly preferably a modified product of the following hydrogenated products: a hydrogenated product of a block copolymer having a polymer block (A-1) and a polymer block (A-2), wherein the hydrogenation rate is It is 50-99 mol%. When the modified elastomer (A) is a modified product of a hydrogenated product of a block copolymer having a polymer block (A-1) and a polymer block (A-2), the modified elastomer (A) contains The upper limit of the content of the polymer block (A-1) is preferably 35% by mass or less, more preferably 22% by mass or less, still more preferably 18% by mass or less, and particularly preferably 15% by mass or less. When the modified elastomer (A) is a modified product of a hydrogenated product of a block copolymer having a polymer block (A-1) and a polymer block (A-2), the polymer block (A-2) The hydrogenation rate is preferably 88 mol% or more, more preferably 93 mol% or more. When the modified elastomer (A) is a modified product of a hydrogenated product of a block copolymer having a polymer block (A-1) and a polymer block (A-2), the weight of the modified elastomer (A) The average molecular weight is preferably 15,000-400,000, more preferably 20,000-300,000, further preferably 25,000-250,000, particularly preferably 30,000-200,000, and most preferably 40,000-180,000. The weight average molecular weight of the modified elastomer (A) can be adjusted, for example, by the amount of the polymerization initiator used in the polymerization.

When the modified elastomer (A) is a modified product of an olefin-based elastomer, examples of the olefin-based elastomer include Tafmer MA8510, MA9015, MD715, MH7010, MH7020, and MH5010 of acid-modified ethylene-α-olefin copolymers , MH5020, MH5040 (made by Mitsui Chemicals Co., Ltd.), etc.

From the viewpoint of reactivity with the reactive compound (B), the modified elastomer (A) is preferably a modified product derived from a compound having at least one of a carboxyl group and a group derived from an acid anhydride, and When the mass part relative to 100 parts by mass of the modified substance is expressed in phr, the modified mass is 0.01 to 1.0 phr, more preferably 0.02 to 0.5 phr, still more preferably 0.03 to 0.3 phr. In addition, in this specification, the modified mass is a value measured by acid value titration, and in detail, it is measured by the method described in Examples. The amount of modification in the modified elastomer (A) can be adjusted by adjusting the usage ratio, type, and the like of the modifier to be used.

From the viewpoint of improving heat shock resistance, the glass transition temperature of the modified elastomer (A) is preferably -100 to -30°C, more preferably -80 to -40°C, and further preferably -70～ -50°C. From the viewpoint of improving vibration damping properties, the glass transition temperature of the modified elastomer (A) is preferably -30 to +40°C, more preferably -15 to +30°C, further preferably -10 to +25 °C. In addition, in this specification, the glass transition temperature is a value measured using a differential scanning calorimeter (DSC) measuring apparatus, and specifically, it is measured by the method described in an Example. The glass transition temperature of the modified elastomer (A) can be adjusted, for example, by the content of the 3,4-bond and 1,2-bond of the conjugated diene.

(上述式(X)中，R ¹～R ³各自獨立地表示氫原子或碳數1～11的烴基，複數的R ¹～R ³可各自相同或相異)。 當使用嵌段共聚物或其氫化物作為彈性體(A0)時，脂環式骨架(X)較佳為被包含於其構成要素之包含源自共軛二烯化合物的結構單元之聚合物嵌段中。關於脂環式骨架(X)之詳細係如後述。 關於作為彈性體(A0)使用的嵌段共聚物或其氫化物之詳細係如後述。 The modified elastomer (A) preferably has a structure represented by the following formula (X) or a hydrogenated product thereof (hereinafter, this may be referred to as an alicyclic skeleton (X)).

(In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and plural R ¹ to R ³ may be the same or different from each other). When a block copolymer or a hydrogenated product thereof is used as the elastomer (A0), the alicyclic skeleton (X) is preferably a polymer block containing a structural unit derived from a conjugated diene compound contained in its constituent elements in the segment. Details of the alicyclic skeleton (X) will be described later. Details of the block copolymer or its hydrogenated product used as the elastomer (A0) will be described later.

唑啉基及環氧基之群組的1種以上之基。上述

唑啉基或環氧基係藉由與改質彈性體(A)之改質化部位反應，而生成反應物(C)。作為反應性化合物(B)，可舉出每1分子具有2個以上的選自包含

唑啉基及環氧基之群組的1種以上之基的樹脂或低分子化合物。 <Reactive compound (B)> As defined in the above condition [II], the reactive compound (B) has 2 or more per molecule selected from the group consisting of

One or more groups of the group of an oxazoline group and an epoxy group. the above

The oxazoline group or the epoxy group reacts with the modified site of the modified elastomer (A) to generate the reactant (C). As the reactive compound (B), there are 2 or more per molecule selected from the group consisting of

A resin or a low molecular compound of one or more groups of an oxazoline group and an epoxy group.

唑啉基及環氧基之群組的1種以上之基的熱塑性樹脂。於作為反應性化合物(B)的樹脂中，包含僅具備上述群組的任1種骨架之均聚物、具備上述群組中任意2種類以上的骨架之共聚物、及具備上述群組所包含的1種以上的骨架與其它骨架之共聚物，例如包含丙烯酸甲酯/聚苯乙烯隨機共聚物等之苯乙烯與(甲基)丙烯酸酯之共聚物。When the reactive compound (B) is a resin, preferably: an epoxy resin; or having at least one skeleton selected from the group consisting of polystyrene, polyacrylate, polymethacrylate, and polyolefin, and Each molecule has 2 or more selected from including

A thermoplastic resin based on one or more groups of an oxazoline group and an epoxy group. The resin as the reactive compound (B) includes a homopolymer having only any one of the skeletons of the above-mentioned group, a copolymer having any two or more skeletons of the above-mentioned group, and a copolymer having any of the above-mentioned groups. Copolymers of one or more skeletons and other skeletons, such as copolymers of styrene and (meth)acrylates including methyl acrylate/polystyrene random copolymers.

唑啉基及環氧基之群組的1種以上之基的低分子化合物。該低分子化合物之分子量例如為50～1000，較佳為100～500，進一步較佳為130～350，特佳為150～300。The reactive compound (B) may have 2 or more in 1 molecule selected from the group consisting of

A low-molecular-weight compound of one or more groups of an oxazoline group and an epoxy group. The molecular weight of the low molecular weight compound is, for example, 50 to 1000, preferably 100 to 500, more preferably 130 to 350, and particularly preferably 150 to 300.

唑啉基之低分子化合物，例如可舉出2,2’-雙(2-

唑啉)、1,2,4-參-(2-

唑啉基-2)-苯、1,4-雙(4,5-二氫-2-

唑基)苯、1,3-雙(4,5-二氫-2-

唑基)苯、2,3-雙(4-異丙烯基-2-

唑啉-2-基)丁烷、2,2’-雙-4-苄基-2-

唑啉、2,6-雙(異丙基-2-

唑啉-2-基)吡啶、2,2’-亞異丙基雙(4-三級丁基-2-

唑啉)、2,2’-亞異丙基雙(4-苯基-2-

唑啉)、2,2’-亞甲基雙(4-三級丁基-2-

唑啉)及2,2’-亞甲基雙(4-苯基-2-

唑啉)。於上述化合物之中，較佳為1,3-雙(4,5-二氫-2-

唑基)苯。as containing 2 or more in 1 molecule

Low molecular weight compounds of oxazoline groups, for example, 2,2'-bis(2-

oxazoline), 1,2,4-para-(2-

oxazolinyl-2)-benzene, 1,4-bis(4,5-dihydro-2-

azolyl)benzene, 1,3-bis(4,5-dihydro-2-

azolyl)benzene, 2,3-bis(4-isopropenyl-2-

oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-

oxazoline, 2,6-bis(isopropyl-2-

oxazolin-2-yl)pyridine, 2,2'-isopropylidenebis(4-tertiarybutyl-2-

oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-

oxazoline), 2,2'-methylenebis(4-tert-butyl-2-

oxazoline) and 2,2'-methylenebis(4-phenyl-2-

oxazoline). Among the above compounds, 1,3-bis(4,5-dihydro-2-

azolyl) benzene.

Examples of low molecular weight compounds having two or more epoxy groups in one molecule include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, new Pentylene Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerol Diglycidyl Ether, 2,2-Dibromoneopentyl Glycol Diglycidyl Ether, 3 ,4-Epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl)aminopropyltrimethoxysilane Equivalent to a compound having 2 epoxy groups in 1 molecule; 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4- ([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "Techmore VG3101L" manufactured by Mitsui Chemicals Co., Ltd.) or the like having three epoxy rings in the molecule Compounds; 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N,N-Diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 3- (N-allyl-N-epoxypropyl)aminopropyltrimethoxysilane and other compounds having 4 epoxy groups in the molecule.

Examples of the polyacrylate constituting the backbone of the reactive compound (B) include homopolymers of monomers such as methyl acrylate, butyl acrylate, and glycidyl acrylate, and copolymers with other monomers.

Examples of polymethacrylates constituting the skeleton of the reactive compound (B) include homopolymers of monomers such as polymethyl methacrylate, polyglycidyl methacrylate, and other monomers. copolymer.

Examples of the polyolefin constituting the skeleton of the reactive compound (B) include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; homopolypropylene, block Polypropylene, random polypropylene, etc.; α-olefin homopolymer or copolymer; propylene and/or ethylene and α-olefin copolymer, etc. As said alpha-olefin, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -Eicosene and other α-olefins having 20 or less carbon atoms, one or more of these can be used.

As the reactive compound (B), when an epoxy group-containing resin having a weight-average molecular weight of 100,000 or less, preferably 50,000 or less, and more preferably 20,000 or less is used, compared with other reactive compounds (B) It becomes easy to exhibit high compatibility for the reactant (C) in a small amount. In addition, if the reactive compound (B) different from the epoxy group-containing resin of the above-mentioned specific molecular weight is used, the usage amount tends to increase, but there is an advantage in that it becomes easy to uniformly disperse the reactant (C). In the matrix resin (E), it becomes easy to uniformly disperse the domain resin (F) in the reactant (C), and it becomes easy to stabilize the feed rate during continuous production such as extrusion molding, etc. .

唑啉基的苯乙烯系共聚物、環氧樹脂、含有環氧基的接枝共聚物、含有環氧基的丙烯酸系共聚物及含有環氧基的苯乙烯系共聚物。Hereinafter, the content that can be used as the reactive compound (B) will be explained.

An oxazoline group-containing styrene-based copolymer, an epoxy resin, an epoxy group-containing graft copolymer, an epoxy group-containing acrylic copolymer, and an epoxy group-containing styrene-based copolymer.

唑啉基的苯乙烯系共聚物) 含有

唑啉基的苯乙烯系共聚物係包含源自苯乙烯的結構單元與源自異丙烯基

唑啉等之含有

唑啉基的烯烴的結構單元之共聚物。 作為此含有

唑啉基的苯乙烯系共聚物中之源自含有

唑啉基的烯烴的結構單元之含量，沒有特別的限制，但從相容化效果之觀點來看，將該共聚物之質量當作100質量%時，較佳為2～50質量%，更佳為10～45質量%，特佳為15～40質量%。 相對於含有

唑啉基的苯乙烯系共聚物整體之質量，源自苯乙烯的結構單元及源自含有

唑啉基的烯烴的結構單元之合計含量較佳為50～100質量%，更佳為70～100質量%，進一步較佳為85～100質量%，最佳為100質量%。 此外，源自含有

唑啉基的烯烴的結構單元之有無及其含量係藉由NMR進行測定。 作為含有

唑啉基的苯乙烯系共聚物之市售品，可舉出苯乙烯與2-異丙烯基-2-

唑啉之共聚物的日本觸媒股份有限公司製「Epocros RPS-1005」及「Epocros PX-3-RP-5」等。 (contain

oxazoline-based styrene copolymer) containing

The oxazoline-based styrene-based copolymer contains a styrene-derived structural unit and an isopropenyl-derived

oxazoline, etc.

Copolymers of structural units of oxazoline-based olefins. as this contains

oxazoline-based styrene-based copolymers derived from

The content of the structural unit of the oxazoline-based olefin is not particularly limited, but from the viewpoint of the compatibilization effect, when the mass of the copolymer is taken as 100 mass %, it is preferably 2 to 50 mass %, more 10-45 mass % is preferable, and 15-40 mass % is especially preferable. relative to containing

The mass of the oxazoline-based styrene-based copolymer as a whole, the structural unit derived from styrene and the

The total content of the structural units of the oxazoline group olefin is preferably 50 to 100 mass %, more preferably 70 to 100 mass %, further preferably 85 to 100 mass %, and most preferably 100 mass %. In addition, derived from containing

The presence or absence of the structural unit of the oxazoline-based olefin and the content thereof were measured by NMR. as containing

Commercially available oxazoline-based styrene-based copolymers include styrene and 2-isopropenyl-2-

Copolymers of oxazoline are "Epocros RPS-1005" and "Epocros PX-3-RP-5" manufactured by Nippon Shokubai Co., Ltd., and the like.

(epoxy resin) The epoxy resin is not particularly limited as long as it has two or more epoxy groups in its structure, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolak. Novolac epoxy resin, cresol novolak epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate, hydantoin epoxy resin, etc. Nitrogen-containing ring epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, aliphatic epoxy resin, 4-functional epoxy resin, glycidylamine type epoxy resin, epoxy resin Propyl ether type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bicyclic type epoxy resin, naphthalene type epoxy resin, etc. Preferably, novolak-type epoxy resins such as phenol novolak-type epoxy resins or cresol novolak-type epoxy resins having three or more epoxy groups, tetrafunctional epoxy resins, and glycidylamine-based rings The oxygen resin is particularly preferably a tetrafunctional epoxy resin or a glycidylamine-based epoxy resin.

(graft copolymer containing epoxy group) The epoxy group-containing graft copolymer is a graft copolymer in which a polymer having an epoxy group is introduced as a side chain in a main chain derived from a polyolefin or an acrylonitrile-styrene copolymer. The mass ratio of the portion derived from the epoxy group-containing polymer in the epoxy group-containing graft copolymer is not particularly limited, but from the viewpoint of easily ensuring good compatibility, the graft copolymer When the mass of the branch copolymer is taken as 100 mass %, it is preferably 1 to 50 mass %, more preferably 3 to 40 mass %, and particularly preferably 5 to 30 mass %. Furthermore, the presence or absence of the epoxy group-containing polymer moiety in the epoxy group-containing graft copolymer and the content thereof were measured by NMR. As a commercial item of the graft copolymer containing an epoxy group, a graft copolymer having a polyolefin as a main chain and an ethylene-based polymer such as polystyrene as a side chain is mentioned by NOF Corporation. Modiper A4000 series of Modiper A4100, A4300, A4400, etc. are manufactured.

(Epoxy group-containing acrylic copolymer, epoxy group-containing styrene-based copolymer) The epoxy group-containing acrylic copolymer is a copolymer of a polymerizable unsaturated compound having an epoxy group and an acrylic polymerizable unsaturated compound. In addition, the epoxy group-containing styrene-based copolymer is a copolymer of a polymerizable unsaturated compound having an epoxy group and a styrene-based polymerizable unsaturated compound. The content of the structural unit derived from the epoxy group-containing polymerizable unsaturated compound in these epoxy group-containing copolymers is not particularly limited, but from the viewpoint of the compatibilization effect, the copolymerization When the mass of the material is taken as 100 mass %, it is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, and particularly preferably 20 to 60 mass %. In addition, the presence or absence of the structural unit derived from the polymerizable unsaturated compound which has an epoxy group, and its content are measured by NMR. As a commercial item of an epoxy group-containing acrylic copolymer or an epoxy group-containing styrene-based copolymer, Marproof (registered trademark) G-0105SA, G-0130SP, G- Marproof G series of 0150M, G-0250SP, G-1005S, etc.

唑啉基及環氧基之群組的1種以上之基上，不鍵結改質彈性體(A)等之其它物質。The reactive compound (B) for preparing the reactant (C) is preferably selected from the group consisting of

Other substances such as the modified elastomer (A) are not bonded to one or more groups of the group of oxazoline and epoxy groups.

唑啉基之合計含量成為指定之值。具體而言，以phr表示相對於反應性化合物(B)100質量份的質量份時，反應性化合物(B)的環氧基及

唑啉基之合計含量較佳為0.1～30phr，更佳為0.5～25phr，進一步較佳為1.0～20phr。 反應性化合物(B)的環氧基及

唑啉基之合計含量，可藉由控制用於製作反應性化合物(B)的原料單體之使用比例或種類之選擇、或其反應條件等而調整。 By using the above-mentioned compound as the reactive compound (B), the epoxy group of the reactive compound (B) and

The total content of oxazoline groups is a predetermined value. Specifically, when the mass parts relative to 100 parts by mass of the reactive compound (B) are expressed in phr, the epoxy groups of the reactive compound (B) and

The total content of the oxazoline groups is preferably 0.1 to 30 phr, more preferably 0.5 to 25 phr, and still more preferably 1.0 to 20 phr. The epoxy group of the reactive compound (B) and

The total content of oxazoline groups can be adjusted by controlling the use ratio of the raw material monomers for producing the reactive compound (B), the selection of the types, or the reaction conditions thereof.

唑啉基或環氧基反應，而作為兩者共價鍵結的反應物所生成者。 反應物(C)較佳為包含下式(1)～(4)所示的結構中之至少一個。

<Reactant (C)> As described above, the reactant (C) is the modified part of the modified elastomer (A) and the reactive compound (B) has.

An oxazoline group or an epoxy group reacts and is formed as a reactant of the two covalently bonded. The reactant (C) preferably contains at least one of the structures represented by the following formulae (1) to (4).

唑啉基之鍵結而生成的結構。上述式(2)及式(3)表示藉由改質彈性體(A)所具有的羧基與反應性化合物(B)所具有的環氧基之反應而生成的結構。上述式(4)表示藉由改質彈性體(A)所具有的源自酸酐之基與反應性化合物(B)所具有的

唑啉基之鍵結而生成的結構。The above formula (1) is represented by the carboxyl group which the modified elastomer (A) has and the reactive compound (B) having.

A structure formed by the bonding of oxazoline groups. The above-mentioned formula (2) and formula (3) represent a structure produced by the reaction of the carboxyl group which the modified elastomer (A) has and the epoxy group which the reactive compound (B) has. The above formula (4) is represented by the group derived from the acid anhydride and the reactive compound (B) which the modified elastomer (A) has.

A structure formed by the bonding of oxazoline groups.

[Resin modifier] The resin modifier of the embodiment of the present invention contains a resin composition (D). The resin modifier is a modifier that improves the processability, moldability, mechanical properties, etc. of the resin by adding it to the resin to be reformed. The above-mentioned resin modifier may be composed of a single substance of the resin composition (D), or may contain components other than the resin composition (D). Such components include, for example, processing aids, reinforcing agents, fillers, plasticizers, interconnecting cell agents, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, slip agents, antistatic agents, and antibacterial agents. agent, antifungal agent, dispersant, colorant, foaming agent, foaming aid, flame retardant, water repellent, water repellant, conductivity imparting agent, thermal conductivity imparting agent, electromagnetic wave shielding imparting agent, fluorescent agent, crystal nucleating agent, etc. The content of the resin composition (D) in the resin modifier is preferably 80% by mass or more, more preferably 90% by mass relative to the total mass of the resin modifier, from the viewpoint of easily securing sufficient compatibility. mass % or more, more preferably 95 mass % or more. The upper limit is not particularly limited, and may be 100% by mass, but from the viewpoint of easily securing good productivity, it can be, for example, 99.8% by mass or less. In other words, the content of the resin composition (D) in the resin modifier is preferably 80 to 100% by mass.

[Dispersion composition] <1st Dispersion Composition (M1)> The first dispersion composition of the embodiment of the present invention (hereinafter referred to as the dispersion composition (M1)) contains the above-mentioned resin composition as the first resin composition (D) and further contains a matrix resin (E) . Then, the first resin composition (D) is dispersed in the matrix resin (E).

As described above, the reactant (C) contained in the first resin composition (D) has a structure in which the reactive compound (B) is bonded to the modified site of the modified elastomer (A). Therefore, by melt-kneading the resin composition (D) and the matrix resin (E), for example, a dispersion composition in which the resin composition (D) is very finely dispersed in the matrix resin (E) can be obtained. Therefore, the above-mentioned dispersion composition (M1) is more excellent in processability and moldability than the matrix resin (E) alone. Moreover, since the reactant (C) is easily dispersed in the matrix resin (E), the above-mentioned dispersion composition (M1) or the molded product of the dispersion composition (M1) has a good appearance. In addition, in the above-mentioned dispersion composition (M1) or the molded article of the dispersion composition (M1), the characteristics due to the reactive compound (B) and the elastomer (A0) used as raw materials tend to appear. Since the dispersion composition (M1) of the embodiment of the present invention contains the resin composition (D) satisfying the above-mentioned condition [I], it is in the first dispersion composition (M1) or the dispersion composition (M1) described above. In molded products, mechanical properties such as vibration damping and impact resistance can be improved. In addition, by appropriately selecting the type of modified elastomer (A) or reactive compound (B) for obtaining the reactant (C), or the type of matrix resin (E), etc., the above-mentioned dispersion composition can be obtained. (M1) or a molded product thereof is excellent in physical properties such as tensile strength, elongation properties, and thermal shock resistance.

＜Core-shell structure＞ A preferred aspect of the dispersion composition (M1) is: the reactant (C) is dispersed in the matrix resin (E), and the dispersion diameter D (C) of the reactant (C) is the same as the diameter of the reactant (C) along this reactant (C) A dispersion composition having a core-shell structure in which the dispersion diameter D(B) of the component mainly derived from the site derived from the reactive compound (B) satisfies the relationship of D(C)<D(B) at the periphery of . Further, a preferred aspect of the dispersion composition (M1) is a dispersion composition that can exhibit a core-shell structure satisfying the relationship of D(C)<D(B) in the molded article of the dispersion composition thing. Here, the dispersion diameter refers to the volume-average dispersion diameter of the major diameter of the core-shell structure, and specifically, it is measured by the procedure described in the examples described later. Moreover, in the core-shell structure, in the shell mainly composed of the site derived from the reactive compound (B), one or a plurality of regions composed of different components from the reactant (C) are included. Examples of this region include reactive compound (B), modified elastomer (A), polymer or elastomer before modification, matrix resin (E), reactant (C), and matrix resin (E) The region constituted by the reactant of , the reactant of the reactive compound (B) and the matrix resin (E), etc. In this way, when a core-shell structure including a region composed of a different component from the reactant (C) exists, it becomes easy to improve impact resistance.

FIG. 1 is a schematic cross-sectional view showing an example of the core-shell structure in the molded article of the dispersion composition (M1) of the present embodiment. As shown in FIG. 1, the core-shell structure 10 is present in a matrix 20 composed of a matrix resin (E). The core-shell structure 10 includes a core 10a mainly composed of a reactant (C) and a shell 10b mainly composed of a site derived from the reactive compound (B). FIG. 2 is a schematic cross-sectional view showing another example of the core-shell structure in the molded article of the dispersion composition (M1) of the present embodiment. As shown in FIG. 2, the core-shell structure 11 includes a core 11a mainly composed of a reactant (C), a shell 11b mainly composed of a site derived from the reactive compound (B), and islands distributed in the core 11a. multiple regions. Examples of the plurality of regions include the region 11b of the reactive compound (B) as shown in FIG. 2 , the region 11c of the modified elastomer (A), and the region 11d of the polymer or elastomer before modification. The region of the matrix resin (E), the region of the reactant of the reactant (C) and the matrix resin (E), the region of the reactant of the reactive compound (B) and the matrix resin (E), etc. may also be contained in the core. 11a. FIG. 3 is an enlarged cross-sectional photograph showing an example of the core-shell structure using a transmission electron microscope (TEM), and FIG. 4 is a partially enlarged photograph of a part thereof. As shown in FIGS. 3 and 4 , in the matrix 20 formed of the matrix resin (E), a shell 11 b including a site derived from the reactive compound (B) as a main body, and a reactant (C) as the main body is formed. The core-shell structure of the core 11a of the main body. Moreover, in the core in FIG. 3 and FIG. 4, there exist several regions 11b-11d, such as the region of the reactive compound (B). In addition, most of the tiny dots inside the nucleus were dyed in specific parts of the modified elastomer (A).

The volume-average dispersion diameter (long diameter) of the core-shell structure in the dispersion composition (M1) or the molded product of the dispersion composition (M1) is preferably 0.01 to 10 μm, more preferably 0.03 to 8 μm, still more preferably is 0.05 to 6 μm. In addition, the dispersion diameter D(C) of the reactant (C) is substantially the same as the volume average dispersion diameter of the above-mentioned core-shell structure. The dispersion diameter D(C) of the reactant (C) is preferably 0.01 to 8 μm, more preferably 0.02 to 6 μm, further preferably 0.03 to 4 μm. In addition, the volume average dispersion diameter (short diameter) of the core-shell structure is not more than the above-mentioned volume average dispersion diameter (long diameter), preferably 0.005 to 8 μm, more preferably 0.015 to 6 μm, and still more preferably 0.02 to 5 μm. When the volume-average dispersion diameter of the core-shell structure is in the above numerical range, the dispersibility of the core-shell structure in the matrix resin (E) can be improved, and the dispersion composition (M1) or the dispersion composition (M1) can be obtained. The mechanical properties of the molded product become good.

<Matrix resin (E)> The matrix resin (E) is a component that serves as a base material for dispersing the first resin composition (D). As a matrix resin (E), a polar resin, a styrene resin, an epoxy resin, etc. are mentioned, for example. The so-called polar resins refer to resins with polar groups such as carboxyl groups, sulfonic acid groups, hydroxyl groups, cyano groups, etc., resins with ether bonds, ester bonds, amide bonds, thioether bonds, etc. in the resin, containing oxygen in the molecule, Resin of at least one of nitrogen, sulfur, and halogen, etc., is a resin that generates electron polarization in the molecule, and has thermoplasticity. The polar resin is preferably a resin having polar groups such as a sulfonic acid group and a cyano group, a resin having an ether bond, an ester bond, an amide bond, a thioether bond, etc. in the resin, and containing oxygen, nitrogen, sulfur, halogen in the molecule At least one of the resins and the like is more preferably a resin containing a resin having at least one of an ether bond, an ester bond, and an amide bond in the resin. Preferred polar resins are selected from the group consisting of nylon 6, nylon 66, nylon 610, nylon 9, nylon 6/66, nylon 66/610, nylon 6/11, nylon 6/12, Polyamide resins such as nylon 12, nylon 46, amorphous nylon, etc.; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, liquid crystal polymer (LCP ) and other polyester resins; polyacetal resins such as polyoxymethylene homopolymer, polyoxymethylene copolymer, etc.; polyphenylene sulfide (PPS) resin, polyphenylene ether resin, polyarylate resin (polyarylate resin), poly Ether resin, polyurethane resin, polyvinyl alcohol resin, polycarbonate (PC) resin, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, polyether ketone, polyether ether ketone, At least one kind selected from the group of polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, vinylon, triacetyl cellulose, xylene resin, acrylic resin, and polyester-based thermoplastic elastomer. More preferably, it is selected from the group consisting of polyamide resins, polyester resins, polyacetal resins, polyphenylene sulfide resins, polyurethane resins, polyvinyl alcohol resins, polycarbonate resins and polyester-based thermoplastic elastomers at least one of the groups.

As the polyester-based thermoplastic elastomer used for the polar resin, for example, (i) aliphatic and/or alicyclic diols having 2 to 12 carbon atoms, (ii) aromatic dicarboxylic acids or alkyl esters thereof, and ( iii) Polyalkylene ether glycol (polyalkylene ether glycol) is used as a raw material, and is obtained by subjecting the oligomer obtained by esterification or transesterification to a polycondensation reaction. As a commercially available polyester-based thermoplastic elastomer, for example, Hytrel 3046 (registered trademark) manufactured by Du Pont-Toray Co., Ltd. is mentioned.

The particularly preferred matrix resin (E) is selected from the group consisting of polyamide resins, polyester resins, polyacetal resins, polyphenylene sulfide resins, polyphenylene ether resins, polyarylate resins, polyether resins, cyclic resins At least one kind of resin from the group of oxygen resin, styrene resin, and polycarbonate resin. As said styrene-type resin, hetero-row polystyrene, para-row polystyrene (SPS), ABS resin, AS resin, ACS resin, etc. are mentioned.

At least one of the glass transition temperature and the melting point of the matrix resin (E) is preferably 80°C or higher, more preferably 100°C or higher, and further preferably 150°C or higher. The glass transition temperature and the melting point were measured with a DSC measuring apparatus. When at least one of the glass transition temperature and the melting point is in the above-mentioned range, it becomes easy to make the mechanical properties of the dispersion composition good.

<Ratio of components in dispersion composition> When the mass of the resin composition (D) contained in the dispersion composition (M1) is regarded as D, and the mass of the matrix resin (E) is regarded as E, D/E is preferably 1/99 to 50/50, More preferably, it is 3/97-30/70, More preferably, it is 5/95-20/80. When D/E is in the above-mentioned range, the mechanical properties of the matrix resin can be suppressed from being greatly reduced, and the physical properties such as vibration damping properties can be improved. Moreover, in the dispersion composition (M1), in addition to the resin composition (D) and the matrix resin (E), an elastomer (A0) may be further contained. From the viewpoint of mechanical properties, the content of the elastomer (A0) is preferably 1 to 20 mass %, more preferably 1 to 10 mass %, still more preferably with respect to the total mass of the dispersion composition (M1). It is 1-5 mass %.

<Second dispersion composition (M2)> The dispersion composition of the second embodiment of the present invention (hereinafter referred to as the dispersion composition (M2)) contains the above-mentioned resin composition as the first resin composition (D), and further contains the domain resin (F) . Furthermore, the domain resin (F) is dispersed in the matrix formed of the first resin composition (D). The aforementioned domain resin (F) is not particularly limited, but the resins exemplified for the aforementioned matrix resin (E) are preferably used. In addition, the glass transition temperature and melting point of the domain resin (F) are preferably the same as those described for the matrix resin (E).

In addition, in the dispersion composition (M2) in which the resin (F) is dispersed in the matrix formed by the first resin composition (D) in the above-mentioned region, the mass of the resin composition (D) is regarded as D, When the mass of the domain resin (F) is taken as F, D/F is preferably 99/1 to 20/80, more preferably 90/10 to 20/80, and still more preferably 70/30 to 30/70. When D/F is in the above-mentioned range, the balance of mechanical properties such as flexibility and tensile strength is excellent, and physical properties such as vibration damping properties can be improved.

＜Additives＞ Various additives may be contained in the dispersion composition within a range not to impair the effects of the present invention. Examples of additives include talc, clay, mica, calcium silicate, glass, glass hollow spheres, glass fibers, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, boric acid Zinc, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite (barium ferrite), strontium ferrite, carbon black, graphite, carbon fiber, activated carbon, carbon hollow spheres, calcium titanate, lead zirconate titanate, silicon carbide, mica and other inorganic fillers; wood flour, starch and other organic fillers filler etc. Examples of the above-mentioned additives include adhesion-imparting resins, plasticizers, fillers, cross-linking agents (isocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, aziridine) cross-linking agent, amine resin, etc.), heat stabilizer, light stabilizer, ultraviolet absorber, infrared absorber, antioxidant, slip agent, colorant, antistatic agent, flame retardant, water repellent, water repellent , hydrophilicity imparting agent, conductivity imparting agent, thermal conductivity imparting agent, electromagnetic wave shielding imparting agent, light transmittance modifier, fluorescent agent, sliding property imparting agent, transparency imparting agent, anti-blocking agent agent), metal passivating agent, antibacterial agent, crystal nucleating agent, anti-cracking agent, anti-ozonant, anti-rodent agent, dispersant, tackifier, lightfast agent, weathering agent, anti-copper damage agent, reinforcing agent, anti-oxidant Molds, macrocyclic molecules (cyclodextrin, calixarene, cucurbituril, etc.). These additives may be used alone or in combination of two or more. The content of the above-mentioned additives in the dispersion composition is not limited, and can be appropriately adjusted according to the type of the additives or the application of the dispersion composition. When the dispersion composition contains the above additives, the content of the above additives may be, for example, 50 mass % or less, 45 mass % or less, 30 mass % or less, 20 mass % or less, 10 mass % or less with respect to 100 mass % of the total amount of the dispersion composition. The mass % or less may be 0.01 mass % or more, 0.1 mass % or more, 1 mass % or more, or 5 mass % or more. In other words, the content of the above-mentioned additives in the dispersion composition is preferably 0.01 to 50% by mass.

[Block copolymer or its hydrogenated product] The block copolymer or its hydrogenated product which can be used as the aforementioned elastomer (A0) will be described in terms of constituents, usage ratios, properties, and the like. Since the elastomer (A0) is the substance before the modification of the aforementioned modified elastomer (A), of course, the elastomer (A0) also has the polymer block (A-1) possessed by the modified elastomer (A) and polymer block (A-2). Therefore, the following description of the polymer block (A-1) and the polymer block (A-2) is based on what is common to the elastomer (A0) and the modified elastomer (A). (Constitution of polymer block (A-1)) The polymer block (A-1) constituting the block copolymer preferably has a structure derived from an aromatic vinyl compound used as a monomer from the viewpoint of mechanical properties such as vibration damping property and impact resistance. unit. The polymer block (A-1) preferably contains more than 70 mol % of structural units derived from an aromatic vinyl compound (hereinafter abbreviated as "aromatic vinyl compound"). In the case of "compound unit"), from the viewpoint of mechanical properties such as impact resistance, it is more preferably 80 mol % or more, more preferably 90 mol % or more, still more preferably 95 mol % or more, especially Preferably it is substantially 100 mol%. In other words, the content of the aromatic vinyl compound unit in the polymer block (A-1) is preferably more than 70 mol % and 100 mol % or less.

As said aromatic vinyl compound, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6- Dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-para-methylstyrene, β-methylstyrene o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-para-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene Styrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chloro Styrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chlorostyrene p-Chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene Styrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-tertiary butylstyrene, m-tertiary butyl styrene, p-tertiary butyl styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-chloromethyl styrene, m-chloromethyl styrene , p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, silyl-substituted styrene derivatives, indene, vinylnaphthalene, N-vinylcarboxylate azoles, etc. These aromatic vinyl compounds may be used individually by 1 type, and may use 2 or more types. Among them, styrene, α-methylstyrene, p-methylstyrene, and a mixture thereof are preferred, and styrene is more preferred, from the viewpoint of the production cost and the balance of physical properties.

烯、雙戊烯、亞甲基降莰烯、2-亞甲基四氫呋喃等之群組的至少1種。聚合物嵌段(A-1)含有該其它不飽和單體單元時的鍵結形態沒有特別的限制，可為隨機、錐狀之任一者。 The polymer block (A-1) may contain structural units derived from other unsaturated monomers other than the aromatic vinyl compound (hereinafter, abbreviated as "other unsaturated mono- body unit”), but in the polymer block (A-1), it is preferably 30 mol % or less, more preferably less than 20 mol %, still more preferably less than 15 mol %, still more preferably is less than 10 mol %, more preferably less than 5 mol %, and particularly preferably 0 mol %. In other words, the content of other unsaturated monomer units in the polymer block (A-1) is preferably 0 to 30 mol %. Examples of the other unsaturated monomers include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene. , isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8,9 pairs

At least one kind selected from the group of alkene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, and the like. The bond form when the polymer block (A-1) contains the other unsaturated monomer unit is not particularly limited, and may be either random or tapered.

The block copolymer should just have at least one said polymer block (A-1). When the block copolymer has two or more polymer blocks (A-1), those polymer blocks (A-1) may be the same or different. In addition, in this specification, "polymer blocks are different" means that in the case of monomer units constituting a polymer block, weight average molecular weight, stereoregularity, and monomer units having plural numbers, each monomer unit At least one of the ratio of , and the morphology of copolymerization (random, gradient, block) are different.

(weight average molecular weight of polymer block (A-1)) The weight average molecular weight (Mw) of the polymer block (A-1) is not particularly limited, but among the polymer blocks (A-1) contained in the block copolymer, at least one polymer block ( The weight average molecular weight of A-1) is preferably 3,000 to 60,000, more preferably 4,000 to 50,000. The fact that the block copolymer has at least one polymer block (A-1) having a weight average molecular weight within the above range can contribute to further improvement of the vibration damping property. On the other hand, in an embodiment in which impact resistance is particularly important, the weight average molecular weight of the polymer block (A-1) is preferably 3,000 to 30,000, more preferably 4,000 to 10,000. In addition, the weight average molecular weight is the weight average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC).

(Content of polymer block (A-1)) The content of the polymer block (A-1) in the block copolymer is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 16 mass % or less, particularly preferably 14 mass % or less. If it is 50 mass % or less, it has moderate flexibility, the tan δ peak strength does not decrease, and a block copolymer or a hydrogenated product thereof excellent in vibration damping property can be obtained. Moreover, the lower limit is preferably 1 mass % or more, more preferably 3 mass % or more, and further preferably 6 mass % or more. If it is 1 mass % or more, a block copolymer or a hydrogenated product thereof can be obtained which has mechanical properties such as impact resistance suitable for various uses of the dispersion composition, and handleability such as moldability and coatability. In other words, the content of the polymer block (A-1) in the block copolymer is preferably 1 to 50% by mass. Moreover, in one of the preferred embodiments of the present invention, the modified elastomer (A) has the above-mentioned functional group only at its molecular terminal. In this case, the upper limit of the content of the polymer block (A-1) in the modified elastomer (A) or the elastomer (A0) before modification is preferably 35% by mass or less, more preferably 33% by mass or less. mass % or less, more preferably 32 mass % or less. The lower limit value of the content of the polymer block (A-1) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. When the content of the polymer block (A-1) is in this range, the resin composition of the present invention is more likely to exhibit excellent balance of vibration damping, impact resistance and mechanical strength, which is preferable. In addition, content of the polymer block (A-1) in a block copolymer is the value calculated|required by ¹ H-NMR measurement, and is the value measured according to the method described in an Example more specifically.

(Constitution of polymer block (A-2)) The polymer block (A-2) constituting the block copolymer is a structural unit derived from a conjugated diene compound. From the viewpoint of vibration damping properties, the polymer block (A-2) preferably has a structural unit ( Hereinafter, it may be abbreviated as "unit containing alicyclic skeleton"). Moreover, the polymer block (A-2) may contain a structural unit derived from a conjugated diene compound not containing an alicyclic skeleton (X) (hereinafter, it may be abbreviated as "conjugated diene unit"). The total of the alicyclic skeleton-containing unit and the conjugated diene unit in the polymer block (A-2) is preferably 50 mol % or more, more preferably from the viewpoint of exhibiting excellent vibration damping properties. It is 70 mol% or more, more preferably 90 mol% or more, and particularly preferably substantially 100 mol%. In other words, the total of the unit containing an alicyclic skeleton and the conjugated diene unit in the polymer block (A-2) is preferably 50 to 100 mol %. When there are two or more polymer blocks (A-2) in the block copolymer, those polymer blocks (A-2) may be the same or different.

In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and plural R ¹ to R ³ may be the same or different from each other. The number of carbon atoms in the hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 (ie, a methyl group). In addition, the above-mentioned hydrocarbon group may be a straight chain or branched chain, and may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and formation of the alicyclic skeleton (X), it is particularly preferable that R ¹ to R ³ are each independently a hydrogen atom or a methyl group. In addition, when the block copolymer is hydrogenated, the vinyl group in the above formula (X) can be hydrogenated to form a hydrogenated product. Therefore, the hydrogenated skeleton of the vinyl group in the above formula (X) is also included in the meaning of the alicyclic skeleton (X) in the hydrogenated product.

The polymer block (A-2) is a structural unit derived from a conjugated diene compound, and the alicyclic skeleton (X) is derived from the conjugated diene compound. The alicyclic skeleton (X) is produced by anionic polymerization of a conjugated diene compound by the method described later, but at least one type of alicyclic skeleton (X) is contained in the compound containing the conjugated diene compound depending on the conjugated diene compound used. In the main chain of the unit of the alicyclic skeleton. By incorporating the alicyclic skeleton (X) into the main chain of the structural unit contained in the polymer block (A-2), the molecular motion becomes smaller and the glass transition temperature rises, and the tanδ around room temperature increases. The peak strength of the system is improved, which can show excellent vibration damping.

Examples of the conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, and 2-phenyl-1,3-butane. Diene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2 -Methyl-1,3-octadiene, 1,3,7-octatriene, farnesene, myrcene and chloroprene, etc. Among them, butadiene, isoprene, or a combination of butadiene and isoprene is preferable.

When butadiene and isoprene are used in combination, their blending ratio [isoprene/butadiene] (mass ratio) is not particularly limited, but is preferably 5/95 to 95/5, more preferably It is 10/90-90/10, More preferably, it is 40/60-70/30, Especially preferably, it is 45/55-65/35. In addition, when the mixing ratio [isoprene/butadiene] is represented by a molar ratio, it is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 40 /60～70/30, especially 45/55～55/45.

As a specific example, the alicyclic skeleton (X) mainly generated when butadiene, isoprene, or a combination of butadiene and isoprene is used as the conjugated diene compound will be described. When butadiene is used alone as a conjugated diene compound, an alicyclic skeleton (X) having a combination of the substituents of the following (i) is generated. That is, in this case, the alicyclic skeleton (X) becomes only an alicyclic skeleton in which R ¹ to R ³ are hydrogen atoms. Therefore, as an example of a preferable aspect of the block copolymer or its hydrogenated product, the polymer block (A-2) has a type of lipid in which R ¹ to R ³ are included in the main chain and are hydrogen atoms. Structural unit of cyclic skeleton (X).

Furthermore, when isoprene is used alone as the conjugated diene compound, two types of alicyclic skeletons (X) having a combination of the following substituents (v) and (vi) are mainly generated. Furthermore, when butadiene and isoprene are used in combination as the conjugated diene compound, six types of alicyclic skeletons (X) having combinations of substituents (i) to (vi) below are mainly generated. (i): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom (ii): R ¹ = hydrogen atom, R ² = methyl group, R ³ = hydrogen atom (iii): R ¹ = hydrogen atom atom, R ² = hydrogen atom, R ³ = methyl (iv): R ¹ = methyl, R ² = hydrogen atom, R ³ = hydrogen atom (v): R ¹ = methyl, R ² = methyl, R ³ =hydrogen atom (vi): R ¹ =methyl group, R ² =hydrogen atom, R ³ =methyl group

In the above formula (X), at least one alicyclic formula in the polymer block (A-2) is at least one of the alicyclic formula in the polymer block (A-2), from the viewpoint that the molecular motion becomes smaller due to the substituent having a hydrocarbon group and the vibration damping property is further improved. The skeleton (X) is preferably an alicyclic skeleton (X') in which at least one of the above-mentioned R ¹ to R ³ is a hydrocarbon group having 1 to 11 carbon atoms. Among them, the hydrocarbon group in the alicyclic skeleton (X') is more preferable from the viewpoint of the efficient formation of the alicyclic skeleton from the conjugated diene compound and the balance of mechanical properties such as vibration damping and impact resistance. is methyl. In particular, R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, and an alicyclic skeleton in which R ¹ to R ³ are not simultaneously a hydrogen atom is more preferable. That is, it is more preferable that the polymer block (A-2) has a structural unit including any one or more of the following alicyclic skeletons in the main chain: a combination of substituents having the above-mentioned (ii) to (vi) alicyclic skeleton.

(Amount of vinyl bond of polymer block (A-2)) When the structural unit constituting the polymer block (A-2) is any one of an isoprene unit, a butadiene unit, and a mixture unit of isoprene and butadiene, the unit is regarded as forming an alicyclic skeleton (X ) other than the bonding form of isoprene and butadiene, in the case of butadiene, 1,2-bonding, 1,4-bonding, and the 1,2-bond, 3,4-bond, 1,4-bond can be adopted in the case.

In the block copolymer and its hydrogenation, the content of the 3,4-bonded unit and the 1,2-bonded unit in the polymer block (A-2) (hereinafter referred to as "vinyl bond") The total is preferably 55 to 95 mol %, more preferably 63 to 95 mol %, still more preferably 70 to 95 mol %. Within the above range, excellent vibration damping properties can be exhibited. On the other hand, in an embodiment in which impact resistance is particularly important, the aforementioned vinyl bond amount is preferably 1-40 mol %, more preferably 2-30 mol %, still more preferably 3-20 mol % Ear %, particularly preferably 3 to 10 mol %. Here, the vinyl bond amount is a value calculated by ¹ H-NMR measurement according to the method described in the examples. In addition, when the polymer block (A-2) contains only butadiene, the aforementioned so-called "content of 3,4-bonded units and 1,2-bonded units" is renamed as "1,2-bonded units" Content of Bonding Units” is applicable.

(alicyclic skeleton (X) content of polymer block (A-2)) From the viewpoint of vibration damping properties, the polymer block (A-2) only needs to contain a structural unit containing an alicyclic skeleton (X) in the main chain, but from the viewpoint of exhibiting more excellent vibration damping properties From the viewpoint of easily suppressing the decrease in resin strength even at high temperature, the polymer block (A-2) preferably contains 1 mol% or more of the alicyclic skeleton (X), more preferably 1.1 mol% or more, more preferably 1.4 mol% or more, still more preferably 1.8 mol% or more, still more preferably 4 mol% or more, still more preferably 10 mol% or more, and particularly preferably 13 mol% or more More than mol%. In addition, the upper limit of the content of the alicyclic skeleton (X) in the polymer block (A-2) is not particularly limited as long as it is within a range that does not impair the effects of the present invention, but from the viewpoint of productivity , preferably 40 mol % or less, may be 30 mol % or less, may be 20 mol % or less, and may be 18 mol % or less. In other words, the content of the alicyclic skeleton (X) in the polymer block (A-2) is preferably 1 to 40 mol %. From the viewpoint of further improving the vibration damping properties, it is more preferable that the above-mentioned alicyclic skeleton (X') is contained in the polymer block (A-2) in an amount of 1 mol % or more, and still more preferably 1.3 mol %. Above, more preferably 1.6 mol % or more. The upper limit of the content of the alicyclic skeleton (X') is the same as the upper limit of the content of the alicyclic skeleton (X). In other words, the content of the alicyclic skeleton (X') in the polymer block (A-2) is preferably 1 to 40 mol %.

More specifically, the alicyclic skeleton content in each of the case of using isoprene, the case of using butadiene, or the case of using butadiene and isoprene in combination as the conjugated diene compound is as follows: the following. When using isoprene as the conjugated diene compound, in the polymer block (A-2), an alicyclic skeleton (X') having a combination of the substituents (v) and (vi) described above exists In the case of one or more kinds, the total content of them is preferably 1 mol % or more, more preferably 1.5 mol % or more, from the viewpoint of easily exhibiting the effect of more excellent vibration damping properties. From the viewpoint of obtaining the effect of excellent vibration damping properties within the range, it is more preferably 2 mol % or more, still more preferably 3 mol % or more, and particularly preferably 4 mol % or more. In addition, in the case of using isoprene, the upper limit of the above-mentioned total content is the same as the upper limit of the content of the alicyclic skeleton (X). In other words, in the case of using isoprene, the content of the alicyclic skeleton (X') having a combination of substituents (v) and (vi) in the polymer block (A-2) is preferably 1 to 40 Mol%.

In the case of using butadiene as the conjugated diene compound, in the polymer block (A-2), the content of the alicyclic skeleton (X) in the presence of the alicyclic skeleton (X) is likely to exhibit a more excellent vibration damping effect. From a viewpoint, it is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, still more preferably 20 mol% or more, still more preferably 25 mol% More preferably, it is 30 mol% or more. In addition, in the case of using butadiene, the upper limit of the content is the same as the upper limit of the content of the alicyclic skeleton (X). In other words, in the case of using butadiene, the content of the alicyclic skeleton (X) in the polymerized block (A-2) is preferably 5 to 40 mol %.

When butadiene and isoprene are used in combination as the conjugated diene compound, the polymer block (A-2) has the substituents (ii), (iii), (v), and (vi) above. When there are more than one type of alicyclic skeleton (X') in the combination, the total content of them is preferably 1 mol % or more, more preferably from the viewpoint of easily exhibiting the effect of more excellent vibration damping properties. It is 2 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, still more preferably 13 mol% or more. When butadiene and isoprene are used in combination, the upper limit of the total content is the same as the upper limit of the content of the alicyclic skeleton (X). In other words, when butadiene and isoprene are used in combination, the alicyclic skeleton having a combination of substituents (ii), (iii), (v), and (vi) in the polymer block (A-2) The total content of (X') is preferably 1 to 40 mol %. Furthermore, when butadiene and isoprene are used in combination as the conjugated diene compound, in the polymer block (A-2), an alicyclic formula having a combination of the substituents (i) to (vi) described above When one or more types of the skeleton (X) are present, the total content of those is preferably 1 mol % or more, and more preferably 5 mol % or more, from the viewpoint of easily exhibiting the effect of more excellent vibration damping properties. When butadiene and isoprene are used in combination, the upper limit of the total content is the same as the upper limit of the content of the alicyclic skeleton (X). In other words, when butadiene and isoprene are used in combination, the total content of the alicyclic skeleton (X) having a combination of substituents (i) to (vi) in the polymer block (A-2) is preferable 1 to 40 mol%.

In addition, the content of the above-mentioned alicyclic skeleton (X) (including (X')) contained in the block copolymer or its hydrogenated product is measured by ¹³ C-NMR of the block copolymer, from the polymer block ( The value obtained by the integrated value derived from the alicyclic skeleton (X) in A-2) is the value measured according to the method described in the Examples in more detail.

In addition, the block copolymer or its hydrogenated product can be specified on the alicyclic skeleton (X) when the hydrogenation rate of the polymer block (A-2) is 0 mol % or more and less than 50 mol %. The molar ratio of the bonded vinyl group and the bonded vinyl group on the main chain is contained. For example, in the alicyclic skeleton (X') having a combination of the substituents (ii), (iii), (v), and (vi), the ethylene bonded to the alicyclic skeleton (X') The chemical shift of the carbon atom at the end of the group ((a) of the following chemical formula) in ¹³ C-NMR appears in the vicinity of 107 to 110 ppm, and the carbon atom at the end of the vinyl group bonded to the main chain ((b of the following chemical formula) )) The chemical shifts in ¹³ C-NMR appear in the vicinity of 110-116 ppm. Furthermore, when the hydrogenation rate is 0 to 40 mol %, the peak area ratio measured by ¹³ C-NMR [peak area with chemical shift value of 107 to 110 ppm]/[peak area with chemical shift value of 110 to 116 ppm] usually becomes In the range of 0.01 to 3.00, the area is preferably 0.01 to 1.50, more preferably 0.01 to 1.00, still more preferably 0.01 to 0.50, still more preferably 0.01 to 0.50, from the viewpoint of exhibiting more excellent vibration damping properties 0.20.

In addition, with regard to the hydride, the peak derived from the carbon atom on the alicyclic skeleton (X) is hardly observed in the ¹³ C-NMR measurement, but the aforementioned substituent R ³ is a hydrocarbon group having 1 to 11 carbon atoms, which may be Peaks derived from carbon atoms on the alicyclic skeleton (X) bonded to a branched alkyl group derived from a vinyl group having the R ³ were observed. Thereby, when the hydrogenation rate of the polymer block (A-2) is 50 to 99 mol %, the hydrogenated product can be specified to be bonded to the branched alkyl group derived from the above-mentioned vinyl group having R ³ . The molar ratio of carbon atoms on the alicyclic skeleton (X) and carbon atoms on the main chain bonded to the branched alkyl group derived from the vinyl group.

For example, in the alicyclic skeleton (X) having the combination of the substituents (iii) and (vi), the carbon atom on the alicyclic skeleton (X) bonded to the isoprenyl group (the following The chemical shift in the ¹³ C-NMR of the chemical formula (c)) appears in the vicinity of 50.0 to 52.0 ppm, and the ¹³ of the carbon atom on the main chain bonded to the isoprenyl group (the following chemical formula (d)) Chemical shifts in C-NMR appear in the vicinity of 43.0-45.0 ppm. Furthermore, when the hydrogenation rate is 40 to 99 mol %, the peak area ratio measured by ¹³ C-NMR [the peak area of the chemical shift value of 50.0 to 52.0 ppm]/[the peak area of the chemical shift value of 43.0 to 45.0 ppm] Usually, it is in the range of 0.01 to 3.00. From the viewpoint of easily exhibiting more excellent vibration damping properties, the area is preferably in the range of 0.01 to 1.50, more preferably in the range of 0.01 to 1.00, and still more preferably in the range of 0.01 to 0.50. The range is more preferably 0.01 to 0.25. In addition, in more detail, the said peak area ratio can be measured according to the method described in an Example.

On the other hand, in an embodiment in which impact resistance is particularly important, the content of the alicyclic skeleton (X) (including (X')) is preferably 0 to 20 mol %, more preferably 0 to 10 mol % %, more preferably 0 to 5 mol %, particularly preferably substantially 0 mol %.

(weight average molecular weight of polymer block (A-2)) The weight average molecular weight of the total sum of the polymer blocks (A-2) contained in the block copolymer is preferably 15,000 to 800,000, more preferably 50,000 in the state before hydrogenation from the viewpoint of vibration damping properties and the like ~700,000, more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000 to 450,000. On the other hand, in an embodiment in which impact resistance is particularly important, the total weight average molecular weight of the polymer blocks (A-2) is preferably 15,000 to 800,000, more preferably 20,000 to 400,000, still more preferably 30,000 ~300,000, particularly preferably 30,000 to 200,000, and most preferably 35,000 to 150,000.

烯、雙戊烯、亞甲基降莰烯、2-亞甲基四氫呋喃、1,3-環戊二烯、1,3-環己二烯、1,3-環庚二烯、1,3-環辛二烯等之群組的至少1種化合物。 嵌段共聚物只要具有至少1個上述聚合物嵌段(A-2)即可。嵌段共聚物具有2個以上的聚合物嵌段(A-2)時，彼等聚合物嵌段(A-2)可相同或相異。 (Other Structural Units in the Polymer Block (A-2)) The polymer block (A-2) may contain other polymerization derived from the conjugated diene compound as long as the objects and effects of the present invention are not inhibited. Structural unit of a sexual monomer. In this case, in the polymer block (A-2), the content of structural units derived from other polymerizable monomers other than the conjugated diene compound is preferably less than 50 mol %, more preferably less than 30 mol % %, more preferably less than 20 mol %, still more preferably less than 10 mol %, particularly preferably 0 mol %. In other words, in the polymer block (A-2), the content of structural units derived from polymerizable monomers other than the conjugated diene compound is preferably 0 mol % or more and less than 50 mol %. As the other polymerizable monomer, for example, a group consisting of styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-tertiary butyl styrene is preferably used. Aromatic vinyl compounds such as styrene, 2,4-dimethylstyrene, N-vinylcarbazole, vinylnaphthalene and vinylanthracene, as well as methyl methacrylate, methyl vinyl ether, β- Pinene, 8,9 pair

alkene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3 -At least one compound of the group of cyclooctadiene and the like. The block copolymer should just have at least one said polymer block (A-2). When the block copolymer has two or more polymer blocks (A-2), those polymer blocks (A-2) may be the same or different.

(The bond pattern between the polymer block (A-1) and the polymer block (A-2)) The block copolymer is not limited as long as the polymer block (A-1) is bonded to the polymer block (A-2), and the bonding form may be linear, branched, radial, or a combination of these. Any of two or more bond styles. Among them, the bonding form of the polymer block (A-1) and the polymer block (A-2) is preferably a straight chain, and as an example, A represents the polymer block (A-1), and When the polymer block (A-2) is represented by B, the diblock copolymer represented by A-B, the triblock copolymer represented by A-B-A or B-A-B, and the tetrablock copolymer represented by A-B-A-B can be mentioned. compounds, pentablock copolymers represented by A-B-A-B-A or B-A-B-A-B, (A-B)nZ-type copolymers (Z represents a coupling agent residue, n represents an integer of 3 or more), etc. Among them, linear triblock copolymers or diblock copolymers are preferred, and A-B-A type triblock copolymers are preferably used from the viewpoints of flexibility, ease of production, and the like. Specific examples of the A-B-A type triblock copolymer include styrene-hydrogenated butadiene-styrene copolymer, styrene-hydrogenated isoprene-styrene copolymer, and styrene-hydrogenated butadiene / Isoprene-styrene copolymer, etc. That is, as a block copolymer, it is preferable to contain a copolymer selected from the group consisting of styrene-hydrogenated butadiene-styrene copolymer, styrene-hydrogenated isoprene-styrene copolymer, and styrene-hydrogenated butadiene. At least one of the group consisting of /isoprene-styrene copolymer, more preferably containing styrene-hydrogenated butadiene/isoprene-styrene copolymer.

Here, in this specification, when the same kind of polymer blocks are linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer block is treated as one polymer block. Accordingly, the above-mentioned examples are also included, and the polymer blocks that should be strictly labeled as Y-Z-Y (Z represents a coupling residue) are considered as a whole, except in cases where it is necessary to distinguish them from the individual polymer blocks Y in particular. The language is represented as Y. In this specification, since such a polymer block containing a coupling agent residue is treated as described above, for example, a block copolymer system containing a coupling agent residue should be strictly labeled as A-B-Z-B-A (Z represents a coupling agent residue) Labeled A-B-A, it is treated as an example of a triblock copolymer.

(Contents of polymer blocks (A-1) and (A-2)) In the block copolymer, as long as the object and effect of the present invention are not hindered, a polymerized block composed of other monomers than the aforementioned polymerized blocks (A-1) and (A-2) may be contained, but the aforementioned The total content of the polymer block (A-1) and the polymer block (A-2) is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably substantially 100% by mass. If it is 90 mass % or more, it becomes easy to obtain a dispersion composition which is easy to exhibit more excellent vibration damping properties. In other words, the total content of the polymer block (A-1) and the polymer block (A-2) in the block copolymer is preferably 90 to 100% by mass.

(weight average molecular weight of block copolymer or its hydrogenated product) The weight average molecular weight (Mw) of the block copolymer and its hydrogenated product in terms of standard polystyrene calculated by gel permeation chromatography is preferably 15,000 to 800,000, more preferably 50,000 to 700,000, and still more preferably It is 60,000 to 600,000, more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000 to 450,000. When the weight average molecular weight of the block copolymer and its hydrogenated product is 15,000 or more, the heat resistance becomes high, and when it is 800,000 or less, the handleability of the obtained resin composition becomes favorable. In addition, in the embodiment in which the modified elastomer (A) has the above-mentioned functional group only at the molecular end, the weight average molecular weight (Mw) of the block copolymer and its hydrogenated product is preferably 15,000 to 200,000, more preferably 20,000 to 150,000, more preferably 25,000 to 100,000, particularly preferably 30,000 to 90,000, and most preferably 40,000 to 80,000. With the weight average molecular weight (Mw) in this range, the reactant (C) contained in the resin composition (D) becomes easily dispersed by the matrix resin (E), and as a result it becomes easy to exhibit excellent impact resistance.

(Peak top temperature and intensity of tanδ of block copolymer or its hydrogenated product) The tanδ (loss tangent) of a block copolymer or its hydrogenated product is the ratio of loss elastic modulus/storage elastic modulus at a frequency of 1 Hz in dynamic viscoelasticity measurement, and the peak temperature and strength of tanδ greatly contribute to the system. Vibration and other physical properties. Here, the so-called peak-top intensity of tanδ refers to the value of tanδ when the peak of tanδ becomes the maximum. In addition, the so-called peak top temperature of tanδ means the temperature at which the peak of tanδ becomes the maximum.

(tanδ strength of block copolymer or its hydrogenated product) In this specification, the peak top temperature and strength of tanδ of the block copolymer or its hydrogenated product are produced by heating the block copolymer or its hydrogenated product at a temperature of 230° C. and a pressure of 10 MPa for 3 minutes to prepare a 1.0 mm thick A single-layer sheet was cut out into a disk shape, and this single-layer sheet was measured as a test piece. The measurement conditions were based on JIS K 7244-10 (2005), and were a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -70°C to +100°C, and a temperature increase rate of 3°C/min. In addition, the peak top temperature and tanδ intensity of the block copolymer or its hydrogenated product are values measured in more detail according to the method described in the examples.

The block copolymer or its hydrogenated product may have a peak-top intensity of tan δ of 1.0 or more according to the above measurement. In the higher ones, there are also 1.5 or more, and further 1.9 or more. The higher the peak strength of tanδ, the better the physical properties such as the vibration damping property at the temperature, and if it is 1.0 or more, sufficient vibration damping property can be obtained in the actual use environment. In addition, the block copolymer or its hydrogenated product has a peak top temperature of tanδ of preferably -50°C or higher, more preferably -40°C or higher, further preferably -30°C or higher from the viewpoint of vibration damping properties, etc. , more preferably -25°C or higher, and may be 0°C or higher. In addition, the upper limit of the peak top temperature of the above-mentioned tanδ may be within a range that does not impair the effects of the present invention, and may be +50°C or lower, +40°C or lower, or +35°C or lower. The range of the peak top temperature of tanδ is, for example, preferably -50 to +50°C, more preferably -40 to +40°C, still more preferably -30 to +30°C, still more preferably -25 to +25 °C. When the peak top temperature of the above-mentioned tanδ is -50°C or higher or +50°C or lower, sufficient vibration damping properties can be obtained in an actual use environment. On the other hand, in an embodiment in which impact resistance is particularly important, the upper limit of the peak temperature of tanδ is preferably -30°C or lower, more preferably -35°C or lower, and further preferably -40°C or lower , further better -43℃ or less. In the embodiment in which impact resistance is important, the lower limit of the peak top temperature of tan δ may be within a range that does not impair the effects of the present invention, and may be -100°C or higher or -90°C or higher. The range of the peak top temperature of tanδ is, for example, preferably -100 to -30°C, more preferably -90 to -35°C, more preferably -80 to -40°C, still more preferably -70～-43℃.

From the viewpoint of improving impact resistance and thermal shock resistance, the glass transition temperature of the block copolymer or its hydrogenated product is preferably -90 to -30°C, more preferably -80 to -40°C, still more preferably It is preferably -70 to -50°C. Moreover, from the viewpoint of improving the vibration damping property, it is preferably -30 to +40°C, more preferably -15 to +30°C, and further preferably -10 to +25°C.

[Production method] <Method for producing block copolymer> As a method for producing a block copolymer, for example, one or more conjugated diene compounds are used as monomers, and are polymerized by an anionic polymerization method to form an alicyclic compound contained in the main chain. The polymer block (A-2) of the structural unit of the skeleton (X), the monomer of the polymer block (A-1) is added, and the monomer of the polymer block (A-1) is further added successively as needed and conjugated diene compounds, thereby obtaining a method for block copolymers. For the method of generating the alicyclic skeleton (X) by the above-mentioned anionic polymerization method, a well-known technique can be used (for example, refer to the specification of US Pat. No. 3,966,691). The alicyclic skeleton (X) is formed at the end of the polymer by the depletion of the monomer, and the monomer is further added successively therein, whereby the polymerization can be started again from the alicyclic skeleton (X). Therefore, the presence or absence of the alicyclic skeleton (X) or its content can be adjusted by the sequential addition time of the monomer, the polymerization temperature, the type or addition amount of the catalyst, and the combination of the monomer and the catalyst. In addition, in the anionic polymerization method, an anionic polymerization initiator, a solvent, and a Lewis base as required can be used.

Examples of organolithium compounds that can be used as polymerization initiators for anionic polymerization in the above method include methyllithium, ethyllithium, n-butyllithium, tertiary butyllithium, tertiary butyllithium, Amyllithium, etc. Moreover, as a dilithium compound which can be used as a polymerization initiator, dilithium naphthalene, dilithium hexylbenzene, etc. are mentioned, for example. As said coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenyl benzoate etc. are mentioned, for example. The usage-amounts of these polymerization initiators and coupling agents are appropriately determined according to the desired weight average molecular weight of the block copolymer or its hydrogenated product. Usually, initiators such as alkyllithium compounds and dilithium compounds are used per 100 parts by mass of the total of the monomers of the polymer block (A) and the monomers such as the conjugated diene compound used for the polymerization. It is preferably used in a ratio of 0.01 to 0.2 parts by mass, and when a coupling agent is used, it is preferably used in a ratio of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the aforementioned monomers.

The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction, and examples include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; Aromatic hydrocarbons such as toluene, etc. In addition, the polymerization reaction is usually carried out at a temperature of 0 to 100°C, preferably 10 to 70°C, for 0.5 to 50 hours, preferably 1 to 30 hours.

啉等之胺類；三級丁酸鈉、三級戊酸鈉或異戊酸鈉等之脂肪族醇的鈉或鉀鹽、或者環己酸二烷基鈉、例如薄荷酸鈉(sodium mentholate)般的脂環式醇之鈉或鉀鹽等之金屬鹽等。此等路易斯鹼可單獨1種或組合2種以上而使用。 In addition, by adding a Lewis base as a co-catalyst during the polymerization of the conjugated diene compound, the content of the alicyclic skeleton (X) in the polymer block (A-2) or the 3,4- The content of bonding and 1,2-bonding. Examples of usable Lewis bases include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and 2,2-bis(2-tetrahydrofuranyl)propane (DTHFP); ethylene glycol dimethyl ether , Diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and other glycol ethers; triethylamine, N,N,N', N'-tetramethylenediamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), N-methyl

Amines such as linoline; sodium or potassium salts of aliphatic alcohols such as sodium tertiary butyrate, sodium valerate or sodium isovalerate, or dialkyl sodium cyclohexanoate, such as sodium mentholate Metal salts such as sodium or potassium salts of general alicyclic alcohols, etc. These Lewis bases can be used alone or in combination of two or more.

The addition amount of the Lewis base is based on how much the content of the above-mentioned alicyclic skeleton (X) is controlled, and when the above-mentioned polymer block (A-2) especially contains isoprene and/or butanediol derived from In the case of the olefinic structural unit, it is determined to what extent the vinyl bond amount of the isoprene unit and/or butadiene unit constituting the polymer block (A-2) is controlled. Therefore, there is no strict limit on the addition amount of the Lewis base, but it is usually preferably 0.1 per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as the polymerization initiator. It is used within the range of ~1,000 mol, preferably 1 to 100 mol.

The average feed rate of the conjugated diene compound (hereinafter referred to as "average diene feed rate"), from the viewpoint of increasing the content of the alicyclic skeleton (X), per 1 mole of active ends, Preferably it is 150kg/h or less, more preferably 110kg/h or less, still more preferably 55kg/h or less, may be 45kg/h or less, may be 30kg/h or less, and may be 22kg/h or less. The lower limit value is preferably 1 kg/h or more, more preferably 3 kg/h or more, more preferably 5 kg/h or more, and may be 7 kg/h per mol of the active end from the viewpoint of improving productivity. The above may be 10 kg/h or more, or 15 kg/h or more. In other words, the average diene feed rate is preferably 1 to 150 kg/h per 1 mole of the active end.

A block copolymer can be obtained by adding active hydrogen compounds such as alcohols, carboxylic acids, and water to stop the polymerization reaction after the anionic polymerization by the above-mentioned method. Furthermore, after the anionic polymerization is carried out by the above-mentioned method, the cyclic ether compound is reacted with the living anion active terminal of the obtained block copolymer, and active hydrogen such as alcohols, carboxylic acids, water, etc. is added by adding active hydrogen. The compound stops the polymerization reaction, and a block copolymer in which a hydroxyl group is introduced into the molecular terminal can be obtained. Although the said cyclic ether compound is not specifically limited, Preferably, ethylene oxide, propylene oxide, butylene oxide, oxetane, etc. are illustrated. Among them, from the viewpoint of the reactivity of the hydroxyl group introduced into the terminal, ethylene oxide and oxygen are preferred, and ethylene oxide is more preferred.

<Production method of hydride> When the block copolymer obtained by the above-mentioned production method is made into a hydrogenated product, a hydrogenation reaction (hydrogenation reaction) is carried out in an inert organic solvent in the presence of a hydrogenation catalyst. The hydrogenated product of the block copolymer can be obtained by hydrogenating the carbon-carbon double bond derived from the conjugated diene compound in the polymer block (A-2) in the block copolymer. In the hydrogenation reaction, the hydrogen pressure can be set to about 0.1-20 MPa, preferably 0.5-15 MPa, more preferably 0.5-5 MPa, and the reaction temperature can be set to about 20-250 °C, preferably 50-180 °C, more It is preferably 70 to 180°C, and the reaction time is usually about 0.1 to 100 hours, preferably 1 to 50 hours. Examples of hydrogenation catalysts include Reidel nickel; heterogeneous catalysts in which metals such as Pt, Pd, Ru, Rh, and Ni are supported on simple substances such as carbon, alumina, and diatomaceous earth; Ziegler-based catalysts composed of combinations of metal compounds, alkyl aluminum compounds, alkyl lithium compounds, etc.; metallocene-based catalysts, etc.

The hydride thus obtained can be solidified by pouring the polymerization reaction liquid into methanol or the like, and then heated or dried under reduced pressure, or the polymerization reaction liquid can be poured into hot water together with steam to make the solvent azeotrope. The so-called steam stripping, which is removed, is obtained by heating or drying under reduced pressure.

Whether or not to use the above-mentioned block copolymer or hydrogenated product can be specified according to the properties desired in various applications of the resin composition or dispersion composition. Similarly, the degree of hydrogenation of the carbon-carbon double bond in the polymer block (A-2) when it is made into a hydride can be adjusted according to various applications of the resin composition or dispersion composition. The desired performance is specified. For example, the higher the hydrogenation rate of the hydride, the better the heat resistance and weather resistance can be.

Therefore, the hydrogenation rate of the polymer block (A-2) may be 0 mol% or more (that is, the case of unhydrogenated is also included) and less than 50 mol% of the block copolymer or its hydrogenated product, and, The hydrogenation rate of the polymer block (A-2) may be a hydride of 50-99.9 mol %, or a hydride of 50-99 mol %. In addition, the above-mentioned hydrogenation rate is measured by ¹ H-NMR after hydrogenation, and among the structural units derived from the conjugated diene compound and the alicyclic skeleton (X) in the polymer block (A-2) are determined. The value of the content of carbon-carbon double bonds is a value measured according to the method described in the Examples in more detail.

<Production method of modified elastomer (A), reactant (C) and resin composition (D)> The resin composition (D) can be produced by a method for producing a reactant (C) by mixing the modified elastomer (A) and the reactive compound (B) in a molten state and reacting both. After the modified elastomer (A) is produced, it can be mixed with the reactive compound (B), and the elastomer (A0) can also be modified to generate the modified elastomer (A), and the reactive compound ( B) Reaction. Hereinafter, the former will be referred to as a first manufacturing method, and the latter will be referred to as a second manufacturing method.

唑啉基或環氧基反應的官能基之改質彈性體(A)。In the above-mentioned first production method, the modified elastomer (A) can be produced, for example, by adding a block copolymer in a molten state, a hydrogenated product of the aforementioned block copolymer, or an olefin-based elastomer. A radical initiator, and at least one of a carboxyl group-containing compound and an acid anhydride are melt-kneaded (reactive extrusion), whereby the block copolymer, the hydrogenated product of the block copolymer, or the olefin-based Elastomer, a method for obtaining a modified product by introducing at least one of a carboxyl group and an acid anhydride-derived group, and the like. Moreover, the modified elastomer (A) in which a hydroxyl group was introduce|transduced at a molecular terminal can also be manufactured by using the compound which has an epoxy group, for example, the said ethylene oxide or propylene oxide as a stopper at the time of superposition|polymerization. In addition, during the polymerization, a monomer having at least one of a carboxyl group and a group derived from an acid anhydride (for example, maleic anhydride) and a monomer having no such group may be copolymerized to produce a modified product. quality elastomer (A). In this way, by copolymerizing plural kinds of monomers, at the same time as the copolymerization, it is possible to obtain a compound having a compound capable of

Modified elastomer (A) of functional group reacted with oxazoline group or epoxy group.

唑啉基或環氧基反應的官能基之改質彈性體(A)。如此所得之改質彈性體(A)係藉由僅在分子末端具有上述官能基，而變得容易控制流動性。此外，如此地得到在分子末端具有上述官能基之改質彈性體(A)時，在分子末端具有羥基之彈性體亦可稱為進行用於導入能與

唑啉基或環氧基反應的官能基之改質前的彈性體，亦即彈性體(A0)。Moreover, in the above-mentioned first production method, the elastomer having a hydroxyl group at the molecular end may be produced, and to this elastomer having a hydroxyl group at the molecular end, at least one of a carboxyl group-containing compound and an acid anhydride may be added. its reaction, resulting in a molecular end with energy with

Modified elastomer (A) of functional group reacted with oxazoline group or epoxy group. Since the modified elastomer (A) obtained in this way has the above-mentioned functional group only at the molecular terminal, it becomes easy to control the fluidity. In addition, when the modified elastomer (A) having the above-mentioned functional group at the molecular terminal is obtained in this way, the elastomer having a hydroxyl group at the molecular terminal can also be referred to as a process for introducing energy with

The elastomer before modification of the functional group reacted with oxazoline or epoxy group, namely elastomer (A0).

When the elastomer having a hydroxyl group at the molecular end is represented by "R-OH", for example, the modified elastomer (A) obtained by adding phthalic anhydride and reacting it has the structure represented by the following formula (5), and adding succinic acid The modified elastomer (A) obtained by reacting acid anhydride has a structure represented by the following formula (6), and the modified elastomer (A) obtained by adding maleic anhydride and reacting it has the following formula (7) Structure.

In the above-mentioned first production method, after the modified elastomer (A) is produced, the reactant (C) is produced by adding and mixing the reactive compound (B) and an alkali catalyst as required. In this way, the resin composition (D) can be produced.

In the above-mentioned second production method, for example, by first adding a radical initiator, a carboxyl group-containing compound and an acid anhydride to a block copolymer in a molten state, a hydrogenated product of the aforementioned block copolymer, or an olefin-based elastomer. At least one of the above, a reactive compound (B) is added next, and at least one of a carboxyl group and an acid anhydride-derived group is introduced into the block copolymer, the hydrogenated product of the block copolymer, or the olefin-based elastomer. , and the production method of reacting the reactive compound (B) at the same time, the resin composition (D) can be produced. Moreover, the resin composition (D) can also be produced according to the said 2nd manufacturing method using the elastomer which has a hydroxyl group at a molecular terminal.

In the first production method, there is an advantage that the production of the modified elastomer (A) and the production of the reactant (C) are performed individually. In the second manufacturing method, the step of modifying the elastomer (A0) in advance can be omitted, which has the advantage of simplifying the manufacturing process.

Commonly used in the above-mentioned first and second production methods, the procedure for mixing and reacting each component is not particularly limited, and for example, it can be mixed and reacted using a kneading device. As the kneading device, a method generally used in this field can be used. For example, each component can be blended by using a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, a cone blender, or the like. It can be mixed with a mixer, or after mixing, it can be kneaded with a uniaxial or biaxial extruder, a kneader, or the like. The temperature at the time of melt-kneading can be appropriately set, but is usually 150 to 300°C, preferably 160 to 250°C.

In addition, in the above-mentioned first and second production methods, the usage amount of the raw material for obtaining the reactant (C) is not limited to this, but is relative to the elasticity for producing the modified elastomer (A). The amount of the reactive compound (B) used in 100 parts by mass of the body (A0) is, for example, 1 to 50 parts by mass.

In the said 1st and 2nd manufacturing method, as a radical initiator which can be used, 2, 5- dimethyl- 2, 5- di (tertiary butylperoxy) hexane is mentioned, for example. Moreover, in the above-mentioned 1st and 2nd production methods, triphenylphosphine; N,N-dimethyl-4-aminopyridine, bipyridine, 4-pyrrole are mentioned as base catalysts that can be used Amines such as epipyridine, ethylenediamine, ethylenetriamine, diethylaminopropylamine, phenylenediamine, etc.; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- Imidazoles such as phenylimidazole, etc.

In the production method of the resin composition (D), when the content of the reactive compound (B) contained in the resin composition (D) is regarded as B mass %, and the content of the reactant (C) is regarded as C mass % , the reaction rate expressed as C/(B+C) is preferably 0.1 to 1.0, more preferably 0.3 to 1.0, from the viewpoint of improving the compatibility with the matrix resin (E) or the zone resin (F). , more preferably 0.5 to 1.0. The above-mentioned reaction rate can be adjusted by the combination of the reactive compound (B) and the modified elastomer (A), the control of reaction conditions, and the like.

The obtained resin composition (D) can be in an appropriate form according to the application, the state of use, and the like, and can be in a granular form, a flake form, or a pellet form, for example.

<Manufacturing method of dispersion composition> The dispersion composition can be produced, for example, by heating and mixing the reactant (C), the matrix resin (E) or the zone resin (F), and additives as needed to an appropriate temperature. The core-shell structure can be easily formed by melt-kneading the reactant (C) and the matrix resin (E), or by melt-kneading the zone resin (F) and the reactant (C). The procedure of melt-kneading is not particularly limited, and for example, it can be prepared using a kneading apparatus. As the kneading device, a method generally used in this field can be used. For example, each component may be mixed by a mixer using a Henschel mixer, a V-blender, a belt blender, a drum blender, a cone blender, or the like, or after mixing, What is necessary is just to mix-knead by a uniaxial or biaxial extruder, a kneader or the like. The temperature at the time of melt-kneading can be appropriately set, but is usually 150 to 300°C, preferably 160 to 250°C.

The obtained dispersion composition can be in an appropriate form according to the application, the state of use, etc., for example, can be in the form of granules, scales, and pellets.

[Characteristics of dispersion composition] <Volume Average Dispersion Diameter> In the dispersion composition of the present embodiment or the molded article of the dispersion composition, the volume average dispersion diameter of the core-shell structure can be set to 0.01 to 10 μm, 0.03 to 8 μm, and further to 0.05 to 6 μm. . The core-shell structure in the matrix resin (E) or the core-shell structure in the matrix of the resin composition (D) can have good dispersibility because the volume-average dispersion diameter of the core-shell structure is in the above-mentioned range. The mechanical strength of the dispersion composition became good. The volume average dispersion diameter of the core-shell structure can be frozen and fractured by using liquid nitrogen. After etching the cross section, the samples with platinum etc. evaporated are observed by SEM. The average value of the major diameters of 50 holes was calculated as the average dispersion diameter, and in detail, it was measured by the procedure described in the examples.

<Loss factor> The dispersion composition of the present embodiment exhibits good vibration damping properties in a wide temperature range. The good vibration damping properties in a wide temperature range exhibited by the above-mentioned dispersion composition can be determined by the type of elastomer (A0), the type or content ratio of the monomer used in the aforementioned modified hydride, the vinyl bond Balance of bond amount and hydrogenation rate, selection of production method of modified hydride, control of other components of the modified hydride of the present invention, etc., or reactant (C) and matrix resin for dispersion composition (E) or the combination of the domain resin (F) and the adjustment of the content ratio and the like are achieved. For example, a test piece having a length of 200 mm, a width of 10 mm, and a thickness of 2 mm using the dispersion composition of the present embodiment is subjected to vibration suppression by the Central Exciting Method in accordance with JIS K 7391 (2008). In a damping test, the loss coefficient was measured, whereby the above-mentioned vibration damping property can be evaluated as follows. The above-mentioned loss coefficient at a frequency of 300 Hz and a temperature of 0° C. is preferably 0.008 or more. In addition, the said loss factor may be 0.020 or more and 0.030 or more. The above-mentioned loss coefficient at a frequency of 300 Hz and a temperature of 20° C. is preferably 0.008 or more. In addition, the said loss factor may be 0.020 or more and 0.030 or more. The above-mentioned loss coefficient at a frequency of 300 Hz and a temperature of 40° C. is preferably 0.008 or more. In addition, the said loss factor may be 0.020 or more and 0.030 or more. The above-mentioned loss coefficient at a frequency of 300 Hz and a temperature of 60° C. is preferably 0.008 or more. In addition, the said loss factor may be 0.020 or more and 0.030 or more. The above-mentioned loss coefficient at a frequency of 300 Hz and a temperature of 80° C. is preferably 0.008 or more. In addition, the said loss factor may be 0.020 or more and 0.030 or more. The above-mentioned loss coefficient at a frequency of 300 Hz and a temperature of 100° C. is preferably 0.008 or more. In addition, the said loss factor may be 0.020 or more and 0.030 or more.

[Use of the dispersion composition] The aforementioned dispersion compositions can be used for various purposes. The dispersion composition of the present embodiment has excellent vibration damping properties and can be used for various applications. Therefore, the present invention also provides a vibration damping material, a film or a sheet, an adhesive or an adhesive, etc. using the dispersion composition of the present invention. Moreover, the dispersion composition of this invention can be used for each adhesive agent layer of a printed wiring board. Specifically, the above-mentioned dispersion composition is mixed with polyimide, polyimide, Substrates such as polyester, copper foil, and LCP have high adhesiveness, and reflow resistance and low dielectric properties can be expected. Moreover, it is also possible to provide a layered product having an X layer containing the dispersion composition of the present invention, and a Y layer layered on at least one surface of the X layer. As the laminated body, for example, a laminated glass is suitable, and by using the above-mentioned X layer as an interlayer film for laminated glass and the above-mentioned Y layer as a glass laminated glass, not only excellent vibration damping properties but also excellent vibration damping properties can be expected. Expect excellent sound insulation. Moreover, as a Y layer, what is necessary is just to select suitably according to various uses other than the said glass layer, For example, the layer containing thermoplastic resin other than the hydrogenated block copolymer of this invention, etc. are mentioned. Examples of the thermoplastic resin include polyvinyl acetal resins such as polyvinyl butyral (PVB), ionomers, ethylene-vinyl acetate copolymers, urethane resins, and polyamide resins.

Examples of other uses include pellets, bales, sound absorbing materials, sound insulating materials, dam rubber, shoe sole materials, floor materials, weather strips, floor mats, and front bulkhead partitions. Dash insulators, headliners, door panels, hoods, door seals, fender liners, ducts, etc. are also useful for these purposes. In addition, the dispersion composition of the present invention can also be used for various automotive components in the automotive field, such as the cooling of thermostat housings, radiator tanks, radiator hoses, water outlets, water pump housings, rear joints, etc. Parts; intake and exhaust system parts of intercooler tank, intercooler casing, turbine duct, EGR cooler box, resonator, throttle body, intake manifold, tail pipe, etc.; fuel delivery pipe, fuel tank, rapid Fuel system parts such as connectors, canisters, pump modules, oil pipes, oil filters, lock nuts, sealing materials, etc.; structural parts such as mounting brackets, torsion bars, cylinder top covers, etc.; bearing fixing Drive system parts such as actuators, gear tensioners, headlight actuating gears, HVAC gears, sliding door rollers, clutch peripheral parts, etc.; brake system parts such as air brake pipes; wiring harness connectors, motor parts, sensors in the engine room , ABS spool, combination switch, on-board switch, electronic control unit (ECU) box and other on-board electrical components; sliding door damper, door mirror support rod, door mirror bracket, interior mirror support Rods, roof rails, engine mounting brackets, intake ducts for air filters, door checkers, plastic chains, emblems, clamps, circuit breaker covers, cup holders, airbags, mudguards Panels, spoilers, radiator brackets, radiator grills, louver, air intakes, hood projections, rear doors, fuel sender modules, floor mats, instrument panels, dashboards , Front bulkhead insulation, rubber dam, weather strips, tires, etc.

In addition, various recorders such as televisions, Blu-ray recorders, HDD recorders, projectors, game consoles, digital cameras, home video, antennas, speakers, electronic dictionaries, IC recorders, FAX, and photocopiers in the home appliance field , Telephone, Intercom, Electric Cooker, Microwave Oven, Microwave Oven, Refrigerator, Dishwasher, Dish Dryer, IH Cooking Heater, Hot Plate, Vacuum Cleaner, Washing Machine, Charger, Sewing Machine, Iron, Dryer, Electric Bike, Air Cleaners, water purifiers, electric toothbrushes, lighting fixtures, air conditioners, outdoor units for air conditioners, dehumidifiers, humidifiers, and other electrical products, can be used in sealing materials, adhesives, adhesives, gaskets, O-rings Rings, belts, sound insulation materials, etc. Can also be used as fiber. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The method for evaluating the physical properties of the hydrogenated product and the modified elastomer (A) of the block copolymer obtained in the production example described later is shown below. (1) Content of polymer block (A-1) The block copolymer before hydrogenation was dissolved in CDCl ₃ and measured by ¹ H-NMR [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker) Temperature: 30°C], the content of the polymer block (A-1) was calculated from the ratio of the peak intensity derived from styrene and the peak intensity derived from diene.

(2) Weight average molecular weight (Mw) The polystyrene-equivalent weight average molecular weight (Mw) of the block copolymer or hydrogenated product was determined by gel permeation chromatography (GPC) measurement under the following conditions. In addition, in the following production examples 1 and 2, before adding the conjugated diene compound, a part of the reaction liquid was sampled from the pressure-resistant container, and by using the reaction liquid for GPC measurement, for only the polymer block Mw of (A-1) is also obtained by the same procedure. (GPC measurement device and measurement conditions) ・Device: GPC device "HLC-8020" (manufactured by Tosoh Co., Ltd.) ・Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Co., Ltd. are connected in series. ・Eluent: Tetrahydrofuran ・Flow rate of eluent: 0.7mL/min ・Sample concentration: 5mg/10mL ・Column temperature: 40℃ ・Detector: Differential refractive index (RI) detector ・Calibration curve : Prepared using standard polystyrene

(3) The hydrogenation rate in the polymer block (A-2) was measured by ¹ H-NMR, from the peak area of the residual olefin derived from isoprene and/or butadiene and the ratio of the peak area derived from ethylene, propylene and / or the ratio of the peak areas of butene.・Apparatus: NMR apparatus "ADVANCE 400 Nano bay" (manufactured by Bruker) ・Solvent: CDCl ₃

(4) Amount of vinyl bonds in polymer block (A-2) The block copolymer before hydrogenation was dissolved in CDCl ₃ and measured by ¹ H-NMR [device: "ADVANCE 400 Nano bay" (Bruker Company), measurement temperature: 30°C]. From the ratio of the total peak area of structural units derived from isoprene and/or butadiene to the following peak area, the vinyl bond amount (3,4-bonded unit and 1,2-bonded unit) was calculated the total content): 3,4-bonded units and 1,2-bonded units in isoprene structural units, 1,2-bonded units in butadiene structural units, or as derived from The structural units of the mixture of isoprene and butadiene correspond to the peak areas of the respective aforementioned bonding units.

(5) Content of alicyclic skeleton (X) in polymer block (A-2) 600 mg of the block copolymer before hydrogenation and 40 mg of Cr(acac) ₃ were dissolved in 4 mL of CDCl ₃ and used Quantitative ¹³ C-NMR measurement with a 10 mm NMR tube (pulse program: zgig, Inverse gated 1H decoupling method) [Apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 °C], and the content of each of the alicyclic skeletons X, X1 and X2 in the polymer block (A-2) was calculated by the following method. In addition, in Table 1, X, X1 and X2 represent the following alicyclic skeletons. X: Alicyclic skeleton having a combination of the following substituents (i) to (vi) X1: Alicyclic skeleton having a combination of the following (i) and (iv) substituents X2: Having the following (ii), Alicyclic skeleton (i) of combination of substituents of (iii), (v) and (iv): R ¹ =hydrogen atom, R ² =hydrogen atom, R ³ =hydrogen atom; (1,2Bd+Bd) (ii): R ¹ =hydrogen atom, R ² =methyl group, R ³ =hydrogen atom; (1,2Bd+1,2Ip) (iii): R ¹ =hydrogen atom, R ² =hydrogen atom, R ³ = Methyl; (1,2Bd+3,4Ip) (iv): R ¹ =methyl, R ² =hydrogen atom, R ³ =hydrogen atom; (1,2Ip+Bd) (v): R ¹ =methyl , R ² =methyl group, R ³ =hydrogen atom; (1,2Ip+1,2Ip) (vi): R ¹ =methyl group, R ² =hydrogen atom, R ³ =methyl group; (1,2Ip+3 ,4Ip) In addition, Ip represents isoprene, and Bd represents butadiene.

[Calculation method] Table 1-1 shows the structure of each peak and its origin. If the integral value of each peak is regarded as a～g, the integral value of each structure is shown in Table 1-2. The content of X, X1, and X2 can be calculated by (a+gc)/(a+b+c -d+e/2+2f), (gc)/(a+b+c-d+e/2+2f), and a/(a+b+c-d+e/2+2f) are calculated. Table 1-2 structure integral value St df 1,4Ip f 3,4Ip+1,2Ip b-(gc) 1.4Bd (e-(df)×4)/2 1,2Bd c X1 gc X2 a total a+b+c-d+e/2+2f

[Table 1] Table 1-1 Peak (ppm) structure integral value 108～110 X2 a 110～113 3,4Ip+1,2Ip+X1 b 113～116 1,2Bd c 122～127 1,4Ip+St d 127～132 1,4Bd×2+St×4 e 132～137 1,4Ip f 142～145 1,2Bd+X1 g

(6) Peak area ratio of ¹³ C-NMR The hydride of Production Example 1 was subjected to the above quantitative ¹³ C-NMR measurement [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C, solvent: CDCl ₃ ], and the peak area ratio [the peak area of the chemical shift value of 50.0 to 52.0 ppm]/[the peak area of the chemical shift value of 43.0 to 45.0 ppm] was calculated.

(7) Peak top temperature of tanδ, peak top intensity, maximum amplitude in the temperature range where tanδ becomes 1.0 or more, tanδ intensity at 20°C and 30°C For the following measurement, the hydrogenated product of the block copolymer was pressurized at a temperature of 230° C. and a pressure of 10 MPa for 3 minutes to prepare a single-layer sheet with a thickness of 1.0 mm. This single-layer sheet was cut out into a disk shape, and this was used as a test piece. In the measurement, based on JIS K 7244-10 (2005), as a parallel-plate vibration rheometer, a strain-controlled dynamic viscoelasticity device "ARES-G2" (manufactured by TA Instruments Japan) with a circular plate diameter of 8 mm was used. . The gap between the two flat plates is completely filled with the above-mentioned test piece, and vibration is applied to the above-mentioned test piece at a frequency of 0.1% of the strain amount and 1Hz, and the temperature is increased from -70°C to +100°C at a constant speed of 3°C/min. . Maintain the temperature of the above-mentioned test piece and circular plate until the measured values of shear loss elastic modulus and shear storage elastic modulus do not change, obtain the maximum value of the peak strength of tanδ (peak strength), and obtain the maximum value. value of the temperature (peak top temperature). In addition, the maximum amplitude in the temperature range where tan δ becomes 1.0 or more, and the tan δ strength at 20°C and 30°C were obtained. The larger the value, the better the vibration damping property.

Next, the physical property evaluation method of the modified elastomer (A) obtained in the below-mentioned production example is shown. (8) Modified mass of modified elastomer (A) The modified mass of maleic anhydride of modified elastomers a-1 to a-3 corresponding to modified elastomer (A) described later was measured by the following procedure. After dissolving 5 g of the modified elastomer (A) in 180 ml of toluene, 20 ml of ethanol was added to titrate with a 0.1 mol/L potassium hydroxide solution, and the modified mass was calculated using the following formula.・The amount of maleic anhydride modified (phr) = titration amount x 5.611/sample amount x 98 x 100/56.11 x 1000 , the modified TPE-2-1, modified TPE-2-2 and modified TPE-2-4 contain basic compounds in the polymer, and the correct modified amount cannot be obtained by the above titration, so according to ¹ H- The anhydride-modified mass of these modified elastomers was calculated by NMR. Specifically, in the modified TPE-2-1 to modified TPE-2-4, the proton (-CH ₂ -OH) (3.3 ppm) of the carbon with terminal hydroxyl group in the elastomer (AO) before modification was used. _β /( α+β), and this value is regarded as the acid anhydride modification rate. Then, the amount of acid anhydride modification was calculated from the acid anhydride modification rate.

(9) Glass transition temperature of modified elastomer (A) The glass transition temperatures of the modified elastomers a-1 to a-3 described later of the modified elastomer (A) were measured using a DSC measuring apparatus (DSC250 manufactured by TA Instruments Japan). Specifically, using the above-mentioned apparatus, the measurement was performed under the conditions of a temperature range of -120°C to +350°C and a temperature increase rate of 10°C/min, and the temperature of the inflection point of the baseline shift due to glass transition was regarded as glass transition. temperature.

[Production Example 1] (Production of hydrogenated product of block copolymer (TPE-1)) Nitrogen replacement was carried out, and 50 kg of cyclohexane as a solvent and 87 g of a cyclohexane solution (secondary butyllithium) with a concentration of 10.5 mass % as an anionic polymerization initiator were added to the dried pressure vessel. The substantial addition amount of lithium: 9.14g). After raising the temperature in the pressure vessel to 50°C, 1.0 kg of styrene (1) was added and polymerized for 1 hour. At a temperature of 50°C in the vessel, 63 g of 2,2-bis(2-tetrahydrofuran) was added as a Lewis base. base) propane (DTHFP), at the average diene feed rate shown in Table 2, after adding a mixed solution of 8.16 kg of isoprene and 6.48 kg of butadiene over 5 hours, it was polymerized for 2 hours, and further 1.0 kg of styrene (2) was added and polymerized for 1 hour, and the reaction was stopped by adding methanol to obtain a triblock copolymer comprising polystyrene-poly(isoprene/butadiene)-polystyrene reaction liquid. To this reaction solution, a Ziegler-based hydrogenation catalyst composed of nickel octoate and trimethylaluminum was added under a hydrogen atmosphere, and the reaction was carried out under the conditions of a hydrogen pressure of 1 MPa and 80° C. for 5 hours. After the reaction solution was left to cool and the pressure was released, the catalyst was removed by washing with water, and the polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer was obtained by vacuum drying The hydride (hereinafter referred to as TPE-1). Table 2 shows each raw material and its usage amount. In addition, Table 3 shows the result of the said physical property evaluation.

[Manufacturing example 2] (Production of hydrogenated block copolymer (TPE-2)) The same procedure as in Production Example 1 was carried out, except that the usage amount of each raw material was set to those shown in Table 2, ethylene oxide as a stopper was reacted, and then methanol was reacted to obtain a compound having a hydroxyl group at the molecular end. The hydrogenated product of polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer (hereinafter referred to as TPE-2). Table 2 shows each raw material and its usage amount. In addition, Table 3 shows the result of the said physical property evaluation.

[Table 2] Manufacturing Example 1 Manufacturing example 2 1 2 Hydrogenated products of block copolymers TPE-1 TPE-2 Usage amount (kg) Cyclohexane 50 50 Secondary butyllithium (10.5 mass % cyclohexane solution) 0.087 0.218 (A) Styrene (1) 1.0 1.7 Styrene (2) 1.0 1.7 (B) Isoprene 8.16 5.0 Butadiene 6.48 4.1 Lewis base DTHFP 0.063 0 Reaction conditions Diene polymerization temperature (℃) 50 50 Diene feed time (h) 5 5 Average diene feed rate per 1 mol of active end (kg/h) 20.5 5.1

[table 3] The hydrogenated product of the block copolymer used TPE-1 TPE-2 Structural unit of polymer block (A-1) St St Components constituting the polymer block (A-2) Ip/Bd Ip/Bd Mass ratio of components constituting polymer block (A-2) 55/45 55/45 Molar ratio of components constituting polymer block (A-2) 50/50 50/50 polymer structure A-1/A-2/A-1 (A/B/A) A-1/A-2/A-2 (A/B/A) functional group at the end of the molecule - OH Content (mass %) of polymer block (A-1) 12 28 Weight average molecular weight of polymer block (A-1) 8,300 5,000 Weight average molecular weight of hydrogenated block copolymers 167,000 53,000 Hydrogenation rate in polymer block (A-2) (mol%) 95 99 Amount of vinyl bond in polymer block (A-2) (mol%) 76 5 Hydrogenated content of X1 or X1 in block (A-2) (mol%) 5 0 The hydrogenated content of X2 or X2 in block (A-2) (mol%) 9.9 0 Hydrogenated content of X or X in block (A-2) (mol%) 14.9 0 Area ratio of ¹³ C-NMR after hydrogenation [50-52 ppm peak area]/[43-45 ppm peak area] 0.21 0.00 Glass transition temperature (℃) 4 -55 Peak top temperature of tanδ(℃) 14.9 -48 Peak intensity of tanδ 2.24 0.47 The maximum amplitude in the temperature range where tanδ≧1 (°C) 17.9 - tanδ intensity at 20°C, 1Hz 1.70 0.04 tanδ intensity at 30°C, 1Hz 0.81 0.05

The hydrogenated product TPE-1 of the block copolymer of Production Example 1 exhibits a peak-top strength of tanδ of 1.0 or more, and has a wide temperature range where tanδ≧1.0, so it is suitable for a wide range of applications as a vibration damping material. In particular, the tan δ strengths at 20° C. and 30° C. were high, and it was found that the vibration damping properties around room temperature were excellent. The hydrogenated product TPE-2 of the block copolymer of Production Example 2 had a glass transition temperature of -55°C, and was excellent in impact resistance and thermal shock resistance. In addition, in the above-mentioned TPE-2 series, there is no temperature region where tanδ≧1 is present on the lower temperature side than the peak of tanδ.

<Preparation of reactant (C) and resin composition (D) using TPE-1> The reactant (C) and the resin composition (D) were prepared by the following procedures. The components used for the preparation of the resin composition (D) are as follows. (Hydrogenated product of block copolymer) ・The above TPE-1 (modifier) ·maleic anhydride (radical initiator) ・Peroxide 1: 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexane (Perhexa 25B-40, manufactured by NOF Corporation) (alkali catalyst) ・N,N-Dimethyl-4-aminopyridine (Reactive Compound (B)) ・S-Ox-1: "Epocros RPS-1005" manufactured by Nippon Shokubai Co., Ltd. ・S-GMA-1: "Marproof G-0130SP" manufactured by NOF Corporation ・Epoxy-1: "EPICLON N-673" (cresol novolak type epoxy resin) manufactured by DIC Co., Ltd.

[Production Examples 3 to 5] (Production of Resin Compositions D-1, D-2 and Modified Elastomer a-1) Using a twin-screw extruder (“ZSK26mc” (26mmϕ, L/D=56), manufactured by Coperion Corporation), the mixture was blended as shown in Table 4 under the conditions of a cylinder temperature of 210°C and a screw rotation number of 300rpm. Melt kneading is performed. In this way, resin compositions D-1 and D-2 in which TPE-1 was modified and the modified substance and the reactive compound (B) were covalently bonded were obtained (that is, the resin compositions were prepared by the above-mentioned second production method. D-1, D-2). Furthermore, except that the reactive compound (B) was not added, the modification reaction was carried out under the same conditions as the above-mentioned with the same blending as the resin composition D-1 of Production Example 3 shown in Table 4, thereby The modified elastomer a-1 of the modified elastomer (A) was obtained. The glass transition temperature of the modified elastomer a-1 was 4°C, and the modified mass of maleic anhydride was 0.15 phr. In addition, the reactive compound (B) is side-fed from the middle of the extruder. In addition, in the measurement of the glass transition temperature of the modified elastomer (A) and the amount of maleic anhydride modified, the aforementioned modified elastomer a-1 was used.

[Production Examples 6 to 10] (Manufacture of resin compositions D-3 to D-5, modified elastomers a-2 and a-3) Using a twin-screw extruder (“ZSK26mc” (26mmϕ, L/D=56) manufactured by Coperion Corporation), under the conditions of a barrel temperature of 210°C and a screw rotation number of 300rpm, the blends shown in Table 5 were melt-kneaded. . In this way, resin compositions D-3 to D-5 in which TPE-1 was modified and at the same time the modified substance and the reactive compound (B) were covalently bonded were obtained (that is, the resin compositions were prepared by the above-mentioned second production method). D-3 to D-5). In addition, except that the reactive compound (B) was not added, the modification reaction was carried out under the same conditions as those of Production Examples 6 and 7 shown in Table 5, and modified elasticity was obtained. Modified elastomers a-2 and a-3 of body (A). The glass transition temperature of the modified elastomer a-2 was 4°C, and the modified mass of maleic anhydride was 0.13 phr. The glass transition temperature of the modified elastomer a-3 was 4°C, and the modified mass of maleic anhydride was 0.2 phr. In addition, the reactive compound (B) is side-fed from the middle of the extruder. In addition, the above-mentioned modified elastomers a-2 and a-3 were used in the measurement of the glass transition temperature of the modified elastomer (A) and the measurement of the amount of maleic anhydride modified.

[Residual amount of reactive compound (B) in resin composition] For the resin compositions D-1 to D-5, in order to confirm the degree of reaction of the reactive compound (B), the obtained resin composition was reprecipitated to remove the unreacted reactive compound (B). From the weight change before and after reprecipitation, the residual amount of the reactive compound (B) in each resin composition was measured. The results are shown in Tables 4 and 5.

[Table 4] Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 D-1 D-2 a-1 Blending ratio (parts by mass) TPE-1 100 100 100 maleic anhydride 0.2 0.2 0.2 Peroxide-1 0.5 0.5 0.5 (B) S-Ox-1 10 30 0 Content (mass %) of (B) in the composition 6 17 0 Content (mass %) of reactant (C) in composition 18 38 0 C/(B+C) 0.75 0.69 0

[table 5] Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Production Example 9 Manufacturing Example 10 D-3 D-4 D-5 a-2 a-3 Blending ratio (parts by mass) TPE-1 100 100 100 100 100 maleic anhydride 0.3 0.3 0.3 0.3 0.3 Peroxide-1 0.1 0.3 0.3 0.1 0.3 (B) S-GMA-1 30 30 10 0 0 Content (mass %) of (B) in the composition 20 18 8 0 0 Content (mass %) of reactant (C) in composition 42 50 27 0 0 C/(B+C) 0.68 0.74 0.77 0 0

<Preparation of dispersion composition> [Example 1, 2] [Comparative example 1, 2] As the matrix resin (E), the following mixture (PC/ABS) of polycarbonate resin (PC) and ABS resin (ABS) was used, blended as shown in Table 6, and a biaxial extruder (Coperion Corporation) was used. "ZSK26Mc" was produced, and the dispersion compositions of Examples 1, 2 and Comparative Example 1 were produced by melt-kneading under the conditions of a barrel temperature of 250° C. and a screw rotation number of 300 rpm. The measurement results are shown in Table 6 below. In addition, in Table 6, as Comparative Example 2, the measurement data of the case of using only PC/ABS are also reported. In addition, in Table 6, when the dispersion composition contains the reactant (C), it is indicated by the symbol "Y", and when the dispersion composition does not contain the reactant (C), it is indicated by the symbol "N". The same applies to Table 7 and Tables 10 to 13 to be described later. ＜Resin＞ ・PC/ABS: "Iupilon MB2212R" (manufactured by Mitsubishi Engineering-Plastics Co., Ltd.)

[Examples 3 to 6] [Comparative Examples 3 to 6] As the matrix resin (E), the following polyphenylene sulfide (PPS) resin was used, blended as shown in Table 7, and a biaxial extruder ("ZSK26Mc" manufactured by Coperion Corporation) was used at a barrel temperature of 300°C. 2. Melt kneading was carried out under the condition of screw rotation number of 300 rpm, and the dispersion compositions of Examples 3 to 6 and Comparative Examples 3 to 5 were prepared. In addition, in Table 7, as Comparative Example 6, the measurement data of the case where only PPS resin was used are also reported. Furthermore, in Example 6, components other than the matrix resin (E) were obtained by immersing the obtained dispersion composition in toluene in which the matrix resin (E) was insoluble, and reprecipitating the components eluted in the toluene. By GPC analysis of the obtained components, it was confirmed that a component having the molecular weights of (A) and (B) combined was formed, so it was determined that the reaction product (C) was produced. ＜Resin＞ ・PPS resin: "Torelina A900" (manufactured by Toray Co., Ltd.)

[Evaluation of physical properties] The procedure for evaluating the physical properties of the composition thus obtained is shown below. In addition, the volume average dispersion diameter was not measured about the molded article in which the core-shell structure was not observed.

(loss factor at 0°C, 20°C, 40°C, 60°C, 80°C and 100°C) The obtained composition was injection-molded with an injection molding machine (“EC75SX”, manufactured by Toshiba Machine Co., Ltd.) to produce a sheet of 200 mm in length×40 mm in width×2 mm in thickness. This sheet was cut out with a length of 200 mm, a width of 10 mm and a thickness of 2 mm, and a contact tip was attached to the center using an adhesive mainly composed of α-cyanoacrylate to obtain a sample. Next, the above-mentioned sample was set in a loss coefficient measurement system (Brüel & Kjær Corporation, Vibration Exciter Model 4809; Impedance Head Model 80001). A contact tip attached to the center of the sample was attached to the front end of the exciting force detector built in the impedance head. Vibration is applied to the central part of the laminate in the frequency range of 0 to 8,000 Hz, and the excitation force and acceleration waveform at this point are detected, thereby performing vibration suppression by the central excitation method in accordance with JIS K 7391 (2008). In the test, the excitation force at the center portion and the acceleration signal representing the acceleration waveform were detected. For each sample, the measurement was performed at temperatures of 0°C, 20°C, 40°C, 60°C, 80°C, and 100°C. Based on the obtained excitation force and the velocity signal obtained by integrating the acceleration signal, the mechanical impedance of the excitation point (central part of the sample to which the vibration is applied) is obtained. Then, an impedance curve is created with the horizontal axis being frequency and the vertical axis being the above-mentioned mechanical impedance, the half width of the second peak (2nd mode) from the low frequency side, and the temperature of each sample is obtained. loss factor below. In addition, the larger the value of the loss coefficient, the higher the vibration damping effect. The results are shown in Tables 6 and 7.

(formation of core-shell structure) The obtained composition was injection-molded with an injection molding machine (“EC75SX”, manufactured by Toshiba Machine Co., Ltd.) to produce a sheet of 200 mm in length×40 mm in width×2 mm in thickness. This sheet was cut out with a length of 200 mm, a width of 10 mm, and a thickness of 2 mm, and was used as a test piece. The presence or absence of a core-shell structure was confirmed by observing the cross section of this test piece with a transmission electron microscope (TEM). In addition, the test piece was embedded in epoxy resin after cutting, and ultrathin sectioned to about 100 μm, and stained with ruthenium tetroxide for cross-sectional observation. 3 and 4 show enlarged cross-sectional photographs of Example 2 observed by TEM.

(Volume Average Dispersion Diameter) The above-mentioned test piece used for the measurement of tan δ was freeze-fractured using liquid nitrogen, the cross section was etched with xylene, and then a sample was prepared by vapor deposition with platinum, and observed with SEM. In the obtained image, the average value of the long diameters of 50 holes formed by etching was taken as the volume average dispersion diameter. The results are shown in Tables 6-7. In addition, about Examples 7-13 and Comparative Examples 7-9 mentioned later, the volume average dispersion diameter was measured similarly, and Table 10-12 shows the result.

(extrusion processability) When pelletizing the strands from the twin-screw extruder in Examples 3 to 6 and Comparative Examples 3 to 5 using a granulator (water-cooled granulator KM-150N manufactured by Katsu Seisakusho Co., Ltd.) , the case where pellets are obtained is regarded as "A", and the case where no pellets are obtained due to poor cutting of the strands is regarded as "C". The results are shown in Table 7. In addition, about the comparative example 6, PPS was formed and pelletized by the same procedure, and the extrusion workability was evaluated.

(Appearance of molded product) The obtained resin composition was injection-molded with an injection molding machine (“EC75SX”, manufactured by Toshiba Machine Co., Ltd.) to produce a sheet of 200 mm in length×40 mm in width×2 mm in thickness. The appearance of the molded product was visually confirmed, and the appearance of defects such as surface peeling was regarded as "C", and if it did not occur, it was regarded as "A". The results are shown in Table 7.

[Table 6] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Blending ratio (parts by mass) PC/ABS 90 90 90 100 D-1 11 - - - D-2 - 13 - - TPE-1 - - 10 - Containing of reactant (C) Y Y N N Volume Average Dispersion Diameter (μm) 3 3 20 - Loss factor(0℃) 0.022 0.022 0.021 0.011 Loss factor (20℃) 0.035 0.034 0.033 0.011 Loss factor (40℃) 0.022 0.020 0.020 0.012 Loss factor (60℃) 0.017 0.016 0.016 0.013 Loss factor (80℃) 0.016 0.016 0.016 0.014 Loss factor (100℃) 0.019 0.020 0.019 0.018

[Table 7] Example 3 Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Blending ratio (parts by mass) PPS 90 90 90 90 90 90 90 100 D-2 13 - - - - - - - D-3 - 13 - - - - - D-4 - - 13 - - - - - (A) a-2 - - - 10 10 - - - TPE-1 - - - - - 10 10 - (B) S-GMA-1 - - - 3 - - 3 - Containing of reactant (C) Y Y Y Y N N N N Extrusion processability A A A A A C A A Appearance of the molded product A A A A C - C A Volume Average Dispersion Diameter (μm) 5 1.5 1.2 1.5 10 - 8 - Loss factor(0℃) 0.018 0.019 0.018 0.016 0.014 - 0.017 0.004 Loss factor (20℃) 0.021 0.020 0.020 0.019 0.022 - 0.023 0.003 Loss factor (40℃) 0.009 0.008 0.009 0.008 0.010 - 0.011 0.003 Loss factor (60℃) 0.007 0.007 0.007 0.007 0.005 - 0.009 0.003 Loss factor (80℃) 0.008 0.008 0.009 0.008 0.005 - 0.009 0.003

From Tables 6 and 7, it can be seen that in the molded articles using the dispersion compositions of Examples 1 to 6, a core-shell structure is formed, the dispersion diameter can be made very small, and the value of the loss coefficient at 0°C to 100°C can be increased. . In addition, it was found that the molded articles using the dispersion compositions of Examples 3 to 6 exhibited good extrusion moldability and had a good appearance. On the other hand, in the molded article using the dispersion composition of Comparative Example 1, which does not contain the reactant (C), the dispersion diameter is significantly larger than that of the Example, and the dispersibility is inferior to that of Examples 1 and 2. The molded product also showed a tendency to decrease in loss coefficient from room temperature to low temperature compared with the molded products of Examples 1 and 2. In addition, it can be seen that the molded articles using the compositions of Comparative Examples 3 and 5 that do not contain the reactant (C) also have a very large dispersion diameter compared with the molded articles of Examples 3 to 6, and poor appearance occurs, especially in Comparative Examples. The molded product of 3 has lower loss coefficients at low temperature and high temperature than the molded products of Examples 3 to 6. Furthermore, it turned out that the molded article using the composition of the comparative example 4 which does not contain a reactant (C) does not form a core-shell structure, and also has poor extrusion processability.

<Preparation of reactant (C) and resin composition (D) using TPE-2> The reactant (C) and the resin composition (D) were prepared by the following procedures. The components used for the preparation of the resin composition (D) are as follows. (Hydrogenated product of block copolymer) ・The above TPE-2 (modifier) ・Succinic anhydride (alkali catalyst) ・N,N-Dimethyl-4-aminopyridine ・4-Pyrrolopyridine ·Triphenylphosphine (Reactive Compound (B)) ・Epoxy-1: "EPICLON N-673" (cresol novolak type epoxy resin) manufactured by DIC Co., Ltd. ・Epoxy-2: "TETRAD-C" by Mitsubishi Gas Chemical Co., Ltd. (tetrafunctional glycidylamine-based epoxy resin)

唑啉基或環氧基反應的官能基之改質彈性體的改質TPE-2-1～改質TPE-2-4。 [Production Examples 11 to 14] (Production of modified TPE-2-1 to modified TPE-2-4) Using an MS-type pressure kneader (manufactured by MORIYAMA Co., Ltd.), the raw materials shown in Table 8 and the The blending amount was melt-kneaded at 150°C for 10 minutes. Thereby, succinic anhydride is bonded to the terminal hydroxyl group of TPE-2 of the hydrogenated block copolymer, and the molecular terminal has

Modified TPE-2-1 to Modified TPE-2-4 of modified elastomer of functional group reacted with oxazoline group or epoxy group.

[Production Examples 15 to 24] Using the above-mentioned modified TPE-2-1 to modified TPE-2-4, with the raw materials and blending amounts shown in Table 9, an MS-type pressure kneader (manufactured by MORIYAMA Co., Ltd.) was used in the same manner as above. It melt-kneaded at 150 degreeC for 15 minutes. Thereby, the resin compositions D-6 to D-15 in which the modified TPE-2-1 to modified TPE-2-4 and the reactive compound (B) are covalently bonded (that is, with the above-mentioned No. 1. Production method Resin compositions D-6 to D-15) were produced.

[Content of reactant (C) in resin composition] For the resin compositions D-6 to D-15, the modification ratios from the above-mentioned modified TPE-2-1 to modified TPE-2-4 to the reactant (C) were measured by the following procedure. Initially, 5 g of the obtained resin composition was completely dissolved in 50 mL of toluene to obtain a solution. Next, each 100 mL of acetone and methanol as a weak solvent was added to the solution, followed by stirring. Then, by filtration using a nylon mesh ("N-NO.200HD" manufactured by NBC Meshtec Co., Ltd.), the generated precipitate was obtained on the mesh. By drying the obtained precipitate, the resin composition from which the unreacted reactive compound (B) was removed was obtained. 1 g of the resin composition obtained above was completely dissolved in 10 mL of THF to obtain a solution. Next, 5 mL of 0.2N hydrochloric acid was added to the aforementioned solution, and the mixture was stirred for 30 minutes to allow the hydrochloric acid to react with the epoxy groups in the resin composition. Next, an excess amount of hydrochloric acid was titrated with a 0.1N potassium hydroxide ethanol solution, and the amount of epoxy group modification was calculated using the following formula. Then, the content of the reactant (C) in the resin composition was calculated using the following calculation formula from the mass modification of the epoxy group. ・Amount of modified epoxy group (mol/g)=(titration amount of blank (L)-titration amount (L))×0.1 ・Content (mass %) of the reactant (C) in the resin composition = (weight average molecular weight of TPE-2 × modified amount of epoxy group (mol/g))/(1 molecule of reactive compound (B) Number of epoxy groups-1) In addition, in the blank titration, the same operation was performed without adding the modified TPE, and the titer was calculated|required. Then, the mass of the reactive compound (B) contained in the resin composition was determined from the content of the reactant (C) in the resin composition. Furthermore, when the content of the reactive compound (B) contained in the above-mentioned resin composition is taken as B mass % and the content of the reactant (C) is taken as C mass %, the expression expressed by C/(B+C) is calculated. The value of the response rate. The results are shown in Table 9.

[Table 8] Manufacturing Example 11 Production Example 12 Production Example 13 Production Example 14 Modified TPE-2-1 Modified TPE-2-2 Modified TPE-2-3 Modified TPE-2-4 Blending ratio (parts by mass) TPE-2 100 100 100 100 Succinic anhydride 0.4 0.4 2 2 N,N-Dimethyl-4-aminopyridine 0.07 0.24 - - 4-Pyrrolidinopyridine - - - 0.09 Anhydride modified quality (phr) 0.14 0.16 0.11 0.11 Acid anhydride modification rate (%) 80 90 60 60 Glass transition temperature (℃) -55 -55 -55 -55

[Table 9] Production Example 15 Manufacturing Example 16 Production Example 17 Production Example 18 Manufacturing Example 19 Manufacturing Example 20 Production Example 21 Production Example 22 Production Example 23 Production Example 24 D-6 D-7 D-8 D-9 D-10 D-11 D-12 D-13 D-14 D-15 Blending ratio (parts by mass) Modified TPE-2-1 100 100 100 - 100 100 100 100 - - Modified TPE-2-2 - - - - - - - - 100 - Modified TPE-2-3 - - - - - - - - - 100 Modified TPE-2-4 - - - 100 - - - - - - Triphenylphosphine 0.25 - - - 0.13 0.5 - - 0.25 - (B) Epoxy-1 10 - - - 10 10 - - 10 - (B) Epoxy-2 - 2.5 1.0 2.5 - - 10 0.5 - 2.5 Content (mass %) of (B) in the composition 8.3 2.1 0.8 2.1 7.7 8.4 8.5 0.4 8.8 2.3 Content (mass %) of reactant (C) in composition 32 49 twenty three 49 56 27 82 11 13 twenty four C/(B+C) 0.79 0.96 0.97 0.96 0.88 0.76 0.91 0.96 0.60 0.91

<Preparation of dispersion composition> [Example 7] [Comparative Example 7] As the matrix resin (E), using the same PC/ABS used in the above-mentioned Example 1, and blending as shown in Table 10, a dispersion composition was prepared by the same procedure as the above-mentioned Example 1.

[Examples 8 to 10] [Comparative Example 8] As the matrix resin (E), the following polybutylene terephthalate (PBT) was used, blended as shown in Table 11, and a biaxial extruder (“ZSK26Mc” manufactured by Coperion Corporation) was used. Melt kneading was performed under the conditions of a barrel temperature of 250° C. and a screw rotation number of 300 rpm, and dispersion compositions of Examples 8 to 10 and Comparative Example 8 were produced. ＜Resin＞ ・PBT: "Toraycon 1401" (manufactured by Toray Co., Ltd.)

[Examples 11 to 13] [Comparative Example 9] As the matrix resin (E), the same PPS resin used in the above-mentioned Example 3 was used, and the blends shown in Table 12 were carried out in the same procedure as that of the above-mentioned Example 3 to prepare Examples 11 to 13 and Comparative Example 9. The dispersion composition. ・Glass fiber (GF): "ECS03T-717H/PW" (manufactured by Nippon Electric Glass Co., Ltd.)

[Examples 14 to 17] [Comparative Example 10] The following liquid crystal polymer (LCP) was used and blended as shown in Table 13, using a biaxial extruder (“ZSK26Mc” manufactured by Coperion Corporation), and the temperature of the barrel was 300°C and the number of screw rotations was 300rpm. Melt kneading was performed to prepare dispersion compositions of Examples 14 to 17 and Comparative Example 10. Here, in Examples 14, 16, 17 and Comparative Example 1, LCP was the matrix resin (E), and in Example 15, LCP was the domain resin (F). ＜Resin＞ ・LCP: "Laperos A130" (manufactured by POLYPLASTICS Co., Ltd.)

[Evaluation of physical properties] The above-mentioned physical property evaluation procedure of the composition thus obtained is shown below. (Stretching test) The resin composition was injection-molded with an injection molding machine "SE100DU-C250" (manufactured by Sumitomo Heavy Industries, Ltd.) to produce an ISO multifunctional test piece (type A). Using the above-mentioned test piece, tensile strength (MPa), tensile elongation at break (%), and tensile modulus of elasticity (GPa) were measured in accordance with JIS K7161-1 (2014) (ISO 527-1:2012).

(Bending test) The resin composition was injection-molded with an injection molding machine "SE100DU-C250" (manufactured by Sumitomo Heavy Industries, Ltd.) to produce an ISO multifunctional test piece (A-shape), which was cut into a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. Using the above-mentioned test piece, according to JIS K7171 (2016) (ISO 178:2010), the bending strength (MPa) and the bending elastic modulus (GPa) were measured.

(Impact resistance test) Using an injection molding machine "SE100DU-C250" (manufactured by Sumitomo Heavy Industries, Ltd.), the resin composition was injection-molded to produce an ISO multifunctional test piece (type A), which was cut into a length of 80 mm and a width of 80 mm. 10mm, thickness 4mm. After the above-mentioned test piece was notched, the impact strength (kJ/m ² ) by the Charpy impact test was measured in accordance with JIS K7111 (2012) (ISO 179:2010).

[Table 10] Example 7 Comparative Example 7 Blending ratio (parts by mass) PC/ABS 90 90 D-6 10 - TPE-2 - 10 Containing of reactant (C) Y N Volume Average Dispersion Diameter (μm) 2 5 Tensile strength (MPa) 36.6 26.3 Tensile elongation at break (%) 3.8 2.5 Tensile modulus of elasticity (GPa) 380 304 Impact Strength[23℃] (kJ/m ² ) 5.3 2.8 Impact Strength[0℃] (kJ/m ² ) 5.0 2.5

[Table 11] Example 8 Example 9 Example 10 Comparative Example 8 Blending ratio (parts by mass) PBT 63 63 63 63 D-7 7 - - - D-8 - 7 - - D-9 - - 7 - TPE-2 - - - 7 GF 30 30 30 30 Containing of reactant (C) Y Y Y N Volume Average Dispersion Diameter (μm) <1 <1 <1 3 Bending strength (MPa) 146 146 146 150 Flexural modulus of elasticity (GPa) 6.6 6.7 6.7 6.7 Impact Strength[23℃] (kJ/m ² ) 9.1 9.0 9.1 7.2 Impact Strength[0℃] (kJ/m ² ) 9.0 8.9 8.9 6.5

[Table 12] Example 11 Example 12 Example 13 Comparative Example 9 Blending ratio (parts by mass) PPS 65 65 65 70 D-7 5 - - - D-8 - 5 - - D-9 - - 5 - GF 30 30 30 30 Containing of reactant (C) Y Y Y N Volume Average Dispersion Diameter (μm) <1 <1 <1 - Tensile strength (MPa) 151 157 157 174 Tensile elongation at break (%) 2.3 2.4 2.5 2.1 Tensile modulus of elasticity (GPa) 10.9 11 11.1 11.8 Bending strength (MPa) 241 243 245 267 Flexural modulus of elasticity (GPa) 9.9 9.8 9.8 10.6 Impact Strength[23℃] (kJ/m ² ) 15.2 14.8 15.0 10.9 Impact Strength[0℃] (kJ/m ² ) 14.9 14.4 14.7 9.5

[Table 13] Example 14 Example 15 Example 16 Example 17 Comparative Example 10 Blending ratio (parts by mass) LCP 70 50 70 70 70 D-7 30 50 - - - D-8 - - 30 - - D-9 - - - 30 - TPE-2 - - - - 30 Containing of reactant (C) Y Y Y Y N Tensile strength (MPa) 10.1 15.9 9.6 10.0 9.2 Tensile elongation at break (%) 39 166 48 40 3 Tensile modulus of elasticity (GPa) 27 10 27 27 135

As can be seen from Table 10, in the molded article of the dispersion composition of Example 7 comprising the resin composition D-6 obtained by melt-kneading the modified TPE-2-1 and the epoxy resin, the phase with PC/ABS was It has high capacitance and can make its dispersion diameter very small. On the other hand, in the molded article used for the dispersion composition of Comparative Example 7 not containing the reactant (C), the dispersion diameter was larger than that of Example 7, and the dispersion became non-uniform. As a result, Example 7 including D-6 was excellent in tensile properties and impact strength.

Similarly, as can be seen from Table 11 and Table 12, the resin compositions D-7 to D-9 have high compatibility with PBT or PPS, and can be dispersed in a molded article containing these dispersion compositions The diameter becomes very small. Therefore, these molded systems improve impact strength without significantly lowering the modulus of elasticity.

In addition, it can be seen from Table 13 that the resin compositions D-7 to D-9 have high compatibility with LCP, and the molded articles of Examples 14 to 17 containing 30 to 50 wt % of them are compared with those containing TPE- In the molded article of Comparative Example 10 of 2, the tensile elongation at break was greatly improved, and it became a composition rich in flexibility. [Possibility of Industrial Use]

Since the resin composition of the present invention exhibits high compatibility with many kinds of resins, it can be used as a resin modifier for resins used in a wide range of fields such as automobiles, electrical products, and building materials. In addition, the dispersion composition of the present invention has good formability and good mechanical properties such as high vibration damping properties in a wide temperature range, and can be used for pellets, compacts, vibration damping materials, sound insulation materials, phase Containers, sole materials, floor boards, adhesives, adhesives, laminates, fibers and auto parts, etc.

10,11: Core-Shell Structure 10a, 11a: nucleus 10b, 11b: Shell 11b, 11c, 11d: Area 20: Matrix

FIG. 1 is a schematic cross-sectional view showing an example of a core-shell structure. FIG. 2 is a schematic cross-sectional view showing another example of the core-shell structure. FIG. 3 is an enlarged cross-sectional photograph showing an example of a core-shell structure. FIG. 4 is a partially enlarged photograph of FIG. 3 .

none.

Claims (26)

A resin composition comprising a reactant (C) of a modified elastomer (A) and a reactive compound (B), the resin composition satisfying the following conditions [I] to [II]: [ I] The modified elastomer (A) is a

(i) of functional groups reacted with oxazoline group or epoxy group has a polymer block (A-1) mainly derived from a structural unit derived from an aromatic vinyl compound and a structure derived from a conjugated diene compound A block copolymer of the polymer block (A-2) whose unit is the main body, (ii) a hydrogenated product of the block copolymer, or (iii) an olefin-based elastomer; [II] The reactive compound (B) is each 1 molecule has 2 or more selected from including

One or more groups of the group of an oxazoline group and an epoxy group. The resin composition of claim 1, wherein the content of the reactant (C) is 1 to 100% by mass relative to the total mass of the resin composition. The resin composition according to claim 1 or 2, further comprising at least one of the modified elastomer (A) and the reactive compound (B). The resin composition of claim 3, wherein relative to the total mass of the resin composition, the content of the modified elastomer (A) is 70% by mass or less, and the content of the reactive compound (B) is 20% by mass the following. The resin composition of any one of claims 1 to 4, wherein the content of the reactive compound (B) contained in the resin composition is regarded as B mass %, and the content of the reactant (C) is regarded as C mass %, the value of C/(B+C) is 0.1 to 1.0. The resin composition according to any one of Claims 1 to 5, wherein the modified elastomer (A) is a modified product derived from a compound having at least one of a carboxyl group and a group derived from an acid anhydride, and is expressed in phr The modified mass is 0.01 to 1.0 phr in terms of mass parts relative to 100 mass parts of the modified substance. The resin composition of claim 6, wherein the reactant (C) comprises at least one of the structures represented by the following formulae (1) to (4);

. The resin composition according to any one of claims 1 to 7, wherein the glass transition temperature of the modified elastomer (A) is -100 to -30°C. The resin composition according to any one of claims 1 to 7, wherein the glass transition temperature of the modified elastomer (A) is -30 to +40°C. The resin composition according to any one of claims 1 to 9, wherein the modified elastomer (A) has a polymer block (A-1) derived from an aromatic vinyl compound and a conjugated diene compound derived The modified product of the hydrogenated product of the block copolymer of the polymer block (A-2). The resin composition of claim 10, wherein the content of the polymer block (A-1) in the modified elastomer (A) is 35% by mass or less. The resin composition of claim 10 or 11, wherein the hydrogenation rate of the polymer block (A-2) is 88 mol% or more. The resin composition according to any one of claims 10 to 12, wherein the weight average molecular weight of the modified elastomer (A) is 15,000-400,000. The resin composition according to any one of claims 1 to 13, wherein the modified elastomer (A) is a molecular terminal having a

Functional groups that react with oxazolinyl or epoxy groups. The resin composition according to any one of claims 1 to 14, wherein the reactive compound (B) has at least one selected from the group consisting of polystyrene, polyacrylate, polymethacrylate and polyolefin skeleton, and each molecule has 2 or more selected from the group consisting of

A thermoplastic resin based on one or more groups of an oxazoline group and an epoxy group. The resin composition according to any one of claims 1 to 15, wherein when expressed in phr relative to 100 parts by mass of the reactive compound (B), the epoxy group of the reactive compound (B) and

The total content of oxazoline groups is 0.1 to 30 phr. The resin composition according to any one of claims 1 to 16, wherein, in addition to the reactant (C), the modified elastomer (A), the reactive compound (B), and the elastomer (A0), the resin composition contained The content is 0 to 50% by mass. A resin modifier comprising the resin composition according to any one of claims 1 to 17. A dispersion composition containing the resin composition according to any one of claims 1 to 18 as the first resin composition (D), and further containing a matrix resin (E), the first resin composition (D) is a Disperse in matrix resin (E). The dispersion composition of claim 19, wherein the matrix resin (E) is selected from the group consisting of polyamide resin, polyester resin, polyacetal resin, polyphenylene sulfide resin, polyphenylene ether resin, polyarylate At least one resin selected from the group of resin, polyether resin, epoxy resin, styrene-based resin, and polycarbonate resin. If the dispersion composition of claim 19 or 20, wherein the mass of the first resin composition (D) in the dispersion composition is regarded as D, and the mass of the matrix resin (E) is regarded as E, D/ E is in the range of 1/99 to 50/50. An automotive component containing the dispersion composition according to any one of claims 19 to 21. A method for producing a resin composition, which is the method for producing a resin composition according to any one of claims 1 to 17, wherein Reactant (C) is produced|generated by mixing the modified elastomer (A) and the reactive compound (B) in a molten state, and making both react. A method for producing a resin composition, which is the method for producing a resin composition according to any one of claims 1 to 17, wherein To the block copolymer in the molten state, the hydrogenated product of the block copolymer, or the olefin-based elastomer, a radical initiator, at least one of a carboxyl group-containing compound and an acid anhydride are added, and then a reactive compound ( B) At least one of a carboxyl group and an acid anhydride-derived group is introduced into the block copolymer, the hydrogenated product of the block copolymer, or the olefin-based elastomer, and the reactive compound (B) is reacted. A method for producing a resin composition, which is the method for producing a resin composition according to any one of claims 1 to 17, wherein Add at least one of a carboxyl group-containing compound and an acid anhydride to a block copolymer in a molten state, a hydrogenated product of the block copolymer, or an olefin-based elastomer, and add at least one of a carboxyl group-containing compound and an acid anhydride to the block copolymer, the block copolymer Into the hydride or the olefin-based elastomer, at least one of a carboxyl group and a group derived from an acid anhydride is introduced, and then a reactive compound (B) is added, so that the reactive compound (B) is introduced into the carboxyl group and the source. The block copolymer, the hydrogenated product of the block copolymer, or the olefin-based elastomer is reacted from at least one of the acid anhydride groups. The method for producing a resin composition according to any one of claims 23 to 25, wherein the content of the reactive compound (B) contained in the resin composition is regarded as B mass %, and the content of the reactant (C) is regarded as The reaction ratio represented by C/(B+C) is 0.1 to 1.0 in the case of C mass %.

Images