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

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

[Technical Field]

[0001] The present invention relates to a resin composition, a resin modifier, a dispersion composition, an automotive component, and a method for producing a resin composition. [Background technology]

[0002] It is already known that some block copolymers having a polymer block containing structural units derived from an aromatic vinyl compound and a polymer block containing structural units derived from a conjugated diene compound, and their hydrogenated products, have vibration-damping properties and have been used as vibration-damping materials. Furthermore, some of the block copolymers and their hydrogenated products can have physical properties such as sound insulation, heat resistance, impact resistance, and adhesiveness in addition to vibration-damping properties, and are therefore thought to be useful in a variety of applications. For example, hydrogenated block copolymers of styrene compounds and conjugated diene compounds such as isoprene and butadiene have been disclosed, in which the peak temperature of tan δ and the amount of vinyl bonds have been specified in order to improve mechanical properties such as vibration damping, flexibility, heat resistance, tensile strength, and impact resistance (see, for example, Patent Documents 1 to 4). Furthermore, by adding the hydrogenated block copolymer to, for example, a polyamide resin, the vibration-damping properties of the polyamide resin can be improved.

[0003] As a method for improving the compatibility between non-polar materials such as styrene-based elastomers and olefin-based elastomers and polar resins, for example, a method of modifying the elastomer with maleic anhydride (hereinafter sometimes referred to as MAh modification) is known (see, for example, Patent Document 5). However, the types of polar resins that can be compatible with maleic anhydride-modified elastomers are limited, and the compatibility improvement effect with resins such as polyphenylene sulfide (PPS), polycarbonate (PC), and polybutylene terephthalate (PBT) is not necessarily sufficient.

[0004] Another method for increasing the compatibility of non-polar materials with polar resins is to add a small amount of a compatibilizer that is reactive with polar resins and highly compatible with non-polar materials. For example, Patent Document 6 describes a method of obtaining an oxazoline-modified polyolefin by kneading an oxazoline-based polymer with an oxazoline-based polymer, such as MAh polypropylene (a maleic acid-modified product of polypropylene (PP)) or a carboxylic acid-modified polyethylene, in an extruder, and then describes the use of the oxazoline-modified polyolefin as a compatibilizer for polyethylene (PE) and polyolefin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-284830 [Patent Document 2] International Publication No. 2000 / 015680 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-117879 [Patent Document 4] Japanese Patent Application Laid-Open No. 2010-053319 [Patent Document 5] Japanese Patent Application Publication No. 61-076518 [Patent Document 6] Japanese Patent Application Laid-Open No. 2012-102231 Summary of the Invention [Problem to be solved by the invention]

[0006] Epoxy and oxazoline groups exhibit high reactivity with the resins listed above, even though MAh conversion of elastomers does not sufficiently improve compatibility. Therefore, if these functional groups could be introduced into elastomers, it would be possible to improve compatibility, but no practical method for doing so had previously been proposed. Patent Document 6 describes the use of oxazoline-modified polyolefin as a compatibilizer for PE and polyolefin, but does not describe the use of elastomer as a substance to be made compatible. Furthermore, since compatibilizers do not form new covalent bonds in elastomers, the use of compatibilizers has not been an advantageous method for further improving the compatibility of elastomers with polar resins or for improving compatibility with a wider variety of resins. When the above-mentioned block copolymer or its hydrogenated product, or the olefin-based elastomer is added to another resin such as a polar resin to prepare a dispersion composition, if the compatibility of the dispersed component with the other resin is low, there is a problem in that the processability, moldability, and mechanical properties such as vibration damping and impact resistance of the obtained dispersion composition cannot be sufficiently improved.

[0007] Therefore, an object of the present invention is to provide a resin composition that exhibits high compatibility with many types of resins. Another object of the present invention is to provide a dispersion composition that has good moldability and excellent mechanical properties such as high vibration damping over a wide temperature range. [Means for solving the problem]

[0008] As a result of intensive research to solve the above problems, the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows.

[0009] [1] A resin composition containing a reaction product (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 (i) a block copolymer having a polymer block (A-1) mainly composed of structural units derived from an aromatic vinyl compound and a polymer block (A-2) mainly composed of structural units derived from a conjugated diene compound, each of which has a functional group capable of reacting with an oxazoline group or an epoxy group, (ii) a hydrogenated product of the block copolymer, or (iii) an olefin-based elastomer. [II] The reactive compound (B) has, per molecule, two or more groups of one or more types selected from the group consisting of oxazoline groups and epoxy groups. [2] A resin modifier comprising the resin composition. [3] A dispersion composition containing the above resin composition as a first resin composition (D) and further containing a matrix resin (E), in which the first resin composition (D) is dispersed in the matrix resin (E). [4] An automotive component containing the dispersion composition. [5] A method for producing the above resin composition, comprising mixing the modified elastomer (A) and the reactive compound (B) in a molten state to react them to produce a reaction product (C). [6] A method for producing the above-mentioned resin composition, comprising adding a radical initiator and at least one of a carboxy group-containing compound and an acid anhydride to a molten block copolymer, a hydrogenated product of the block copolymer, or an olefinic elastomer, and then adding a reactive compound (B) to introduce at least one of a carboxy group and a group derived from the acid anhydride into the block copolymer, the hydrogenated product of the block copolymer, or the olefinic elastomer, and reacting the reactive compound (B). [7] A method for producing the above-mentioned resin composition, comprising adding at least one of a carboxy group-containing compound and an acid anhydride to a block copolymer, a hydrogenated product of the block copolymer, or an olefinic elastomer in a molten state, introducing at least one of a carboxy group and a group derived from the acid anhydride into the block copolymer, the hydrogenated product of the block copolymer, or the olefinic elastomer, and then adding a reactive compound (B) to react the block copolymer, the hydrogenated product of the block copolymer, or the olefinic elastomer into which at least one of a carboxy group and a group derived from the acid anhydride has been introduced. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a resin composition that exhibits high compatibility with many types of resins, and also to provide a dispersion composition that has good moldability and excellent mechanical properties such as high vibration damping over a wide temperature range. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 2 is a cross-sectional view showing an example of a core-shell structure. [Figure 2] FIG. 10 is a cross-sectional view showing another example of a core-shell structure. [Figure 3] 1 is an enlarged cross-sectional photograph showing an example of a core-shell structure. [Figure 4] FIG. 4 is an enlarged partial photograph of FIG. 3. DETAILED DESCRIPTION OF THE INVENTION

[0012] In this specification, preferred definitions can be selected arbitrarily, and combinations of preferred definitions can be considered more preferred. In this specification, the expression "XX to YY" means "XX or more and YY or less." In this specification, for preferred numerical ranges (e.g., ranges of content, etc.), the lower and upper limits described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." In this specification, the term "unit" (where "" indicates a monomer) means "a structural unit derived from", for example, "propylene unit" means "a structural unit derived from propylene". In this specification, for example, "(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 is a weight average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). In this specification, the phrase "B mainly composed of A" means that B contains A in an amount of at least more than 50 mass %.

[0013] [Resin composition] The resin composition according to an embodiment of the present invention (hereinafter sometimes referred to as the resin composition of the present embodiment) is a resin composition containing a reaction product (C) of a modified elastomer (A) and a reactive compound (B), and satisfies the following conditions [I] to [II]. [I] The modified elastomer (A) is the following (i), (ii), or (iii), each of which has a functional group capable of reacting with an oxazoline group or an epoxy group: (i) A block copolymer having a polymer block (A-1) mainly composed of structural units derived from an aromatic vinyl compound and a polymer block (A-2) mainly composed of structural units derived from a conjugated diene compound. (ii) A hydrogenated product of the above block copolymer (iii) Olefin-based elastomer [II] The reactive compound (B) has, per molecule, two or more groups of one or more types selected from the group consisting of oxazoline groups and epoxy groups. In this specification, the above resin composition may be referred to as "first resin composition (D)" or "resin composition (D)".

[0014] The reactant (C) contained in the resin composition (D) is produced as a reaction product in which the modified site of the modified elastomer (A) reacts with the reactive compound (B) to form a covalent bond between them. The resin composition (D) may be composed of only the reactant (C), or may contain components other than the reactant (C). The resin composition (D) may further contain at least one of a modified elastomer (A) and a reactive compound (B) as a component other than the reactant (C). The resin composition (D) may contain an elastomer before modification (hereinafter, sometimes referred to as elastomer (A0)). Details of the reactant (C) will be described later.

[0015] The amount of reactant (C) in resin composition (D) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total mass of resin composition (D), from the viewpoint of improving compatibility with matrix resin (E) or domain resin (F), which will be described later. 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% by mass or less, and may be 90% by mass or less, 80% by mass or less, or even 70% by mass or less. In other words, the amount of reactant (C) in resin composition (D) is preferably 1 to 100% by mass, based on the total mass of resin composition (D). The unmodified elastomer (A0), modified elastomer (A), and reactive compound (B) may be contained in resin composition (D) as components other than reactant (C). Here, A0M represents the content of the unmodified elastomer (A0), AM represents the content of the modified elastomer (A), and BM represents the content of the reactive compound (B). From the viewpoint of improving compatibility with matrix resin (E) or domain resin (F), A0M preferably accounts for 70% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less of the total mass of resin composition (D). From the same viewpoint, AM preferably accounts for 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less of the total mass of resin composition (D). From the same viewpoint, BM preferably accounts for 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less of the total mass of resin composition (D). 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 50 mass %. Furthermore, based on the total mass of resin composition (D), AM is preferably 70 mass% or less and BM is 20 mass% or less, more preferably 50 mass% or less and BM is 20 mass% or less, and even more preferably 50 mass% or less and BM is 20 mass% or less. In other words, the AM and BM in resin composition (D) are preferably 0 to 70 mass% and 0 to 20 mass%. Furthermore, when the content of the reactive compound (B) contained in the resin composition (D) is B mass % and the content of the reactant (C) is C mass %, from the viewpoint of improving compatibility with the matrix resin (E) or the domain resin (F), the value of C / (B+C) is preferably 0.1 to 1.0, more preferably 0.3 to 1.0, and even more preferably 0.5 to 1.0.

[0016] In resin composition (D), when the above condition [II] is satisfied, reactant (C) has high compatibility with various types of resins, even with types of resins that are difficult to be compatible with unmodified elastomers or general modified elastomers (e.g., MAh elastomers). Therefore, for example, when reactant (C) is added to and mixed with matrix resin (E) described below, reactant (C) is dispersed in matrix resin (E) with the moiety derived from reactive compound (B) of resin composition (D) interposed between reactant (C) and matrix resin (E). This results in the formation of a core-shell structure consisting of a shell mainly composed of moieties derived from reactive compound (B) and a core mainly composed of reactant (C). In addition, the reactive compound (B) portion of the reactant (C) that is highly compatible with the matrix resin (E) tends to be positioned on the outside, so that the reactant (C) is dispersed in the matrix resin (E) in the form of fine dots. In this way, even if the elastomer (A0) is poorly compatible with the matrix resin (E) as it is, it can be finely and uniformly dispersed in the matrix resin (E) by being modified and becoming the reaction product (C), which is thought to be the reason why the elastomer (A0) exhibits high compatibility with many types of resins.

[0017] Furthermore, when the domain resin (F) described below is added to and mixed with the reactant (C), the domain resin (F) is dispersed in the matrix of the resin composition (D) in a state where the moiety derived from the reactive compound (B) in the resin composition (D) is interposed between the reactant (C) and the domain resin (F). Then, a core-shell structure is formed with a shell mainly composed of the moiety derived from the reactive compound (B) and a core mainly composed of the domain resin (F). Furthermore, the portion of the reactive compound (B) in the reactant (C) that is highly compatible with the domain resin (F) tends to be positioned on the domain resin (F) side, and therefore the domain resin (F) tends to be dispersed in the form of fine dots in the matrix of the resin composition (D). In this way, even if an elastomer (A0) that is not easily compatible with the domain resin (F) is used as it is, by modifying the elastomer (A0) and making it into the reaction product (C), the domain resin (F) can be dispersed finely and uniformly in the matrix of the resin composition (D).

[0018] Furthermore, 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 to before the addition, and the property-improving effects of the reactive compound (B) and the elastomer (A0) are more likely to be exhibited. In the resin composition (D) according to the embodiment of the present invention, the above-mentioned condition [I] is satisfied, and therefore, in the matrix resin (E) after adding the resin composition (D), the mechanical properties such as vibration damping and impact resistance can be improved compared to before the addition. Moreover, since the domain resin (F) is easily dispersed in the reactant (C) contained in the resin composition (D), the physical properties of the domain resin (F) can be easily exhibited while the elongation characteristics and flexibility of the resin composition (D) are ensured.

[0019] From the viewpoint of enhancing the effect of improving the mechanical properties of the matrix resin (E) after the addition of the resin composition (D) or the resin composition (D) after the addition of the domain resin (F), the content of resin components contained in the resin composition (D) other than the reactant (C), the modified elastomer (A), the reactive compound (B), and the elastomer (A0) is preferably 0 to 50 mass%, more preferably 0 to 30 mass%, even more preferably 0 to 20 mass%, still more preferably 0 to 10 mass%, and most preferably 0 to 5 mass%.

[0020] The components constituting the resin composition of the present embodiment will be described below. In addition, the use of the resin composition, the dispersion composition, the use of the dispersion composition, and the method for producing the dispersion composition will also be described.

[0021] <Modified elastomer (A)> The modified elastomer (A) is, as specified in the above condition [I], (i) a block copolymer having a polymer block (A-1) mainly composed of structural units derived from an aromatic vinyl compound (hereinafter sometimes abbreviated as "aromatic vinyl compound units") and a polymer block (A-2) mainly composed of structural units derived from a conjugated diene compound (hereinafter sometimes abbreviated as "conjugated diene units"), each of which has a functional group capable of reacting with an oxazoline group or an epoxy group, (ii) a hydrogenated product of the block copolymer, or (iii) an olefin-based elastomer. From the viewpoint of mechanical properties such as vibration damping and impact resistance, the modified elastomer (A) is preferably the block copolymer having the functional group or a hydrogenated product of the block copolymer having the functional group, and more preferably a modified product of the block copolymer or a modified product of a hydrogenated product of the block copolymer. The block copolymer and the hydrogenated product thereof will be described in detail later.

[0022] Examples of the functional group possessed by the compound having a functional group capable of reacting with an oxazoline group or an epoxy group (hereinafter referred to as reactive compound (a)) used to modify the elastomer (A0) and introduce the functional group include an alkoxysilyl group, a carboxy group, an amino group, a hydroxy group, a phenolic hydroxyl group, a group derived from an acid anhydride, an ester group, and a mercapto group. Two or more of these groups may be contained. Preferably, the functional group is one or more functional groups selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and a group derived from an acid anhydride. More preferably, from the viewpoint of reactivity with the oxazoline group or the epoxy group, the functional group is one or more functional groups selected from the group consisting of a carboxy group and a group derived from an acid anhydride. From the viewpoint of facilitating reactive extrusion and making it suitable for industrialization, a particularly preferred functional group capable of reacting with an oxazoline group or an epoxy group is at least one group selected from the group consisting of a group derived from maleic anhydride, a group derived from succinic anhydride, a group derived from phthalic anhydride, and a carboxy group, and particularly at least one group selected from the group consisting of a group derived from maleic anhydride and a carboxy group. In this specification, a phenolic hydroxyl group means a hydroxyl group that substitutes a hydrogen atom on an aromatic ring. Here, the "group derived from maleic anhydride" refers to at least one of a group having a structure in which one of the carbon atoms constituting the double bond of the ring of maleic anhydride becomes a bond, and a group having a structure in which one O of the two CO atoms in maleic anhydride becomes a bond. The "group derived from succinic anhydride" refers to a group having a structure in which one O of the two CO atoms in succinic anhydride becomes a bond. The "group derived from phthalic anhydride" refers to a group having a structure in which one O of the two CO atoms in phthalic anhydride becomes a bond.

[0023] The modified elastomer (A) has one or more of the above functional groups in the molecule. From the viewpoint of easily ensuring 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 above functional groups in the molecule. Furthermore, there are no particular restrictions on the position of the functional group in the modified elastomer (A), but from the viewpoint of easily controlling fluidity, it is preferable to have the above functional group at the molecular terminal, and more preferably to have the above functional group only at the molecular terminal. The number of the functional groups in the modified elastomer (A) can be controlled, for example, by adjusting the amount of radical initiator added in the production method of the modified elastomer (A) described below. Furthermore, the presence of the functional groups at the molecular terminals of the modified elastomer (A) can be achieved, for example, by introducing a specific group such as a hydroxyl group into the terminal when producing the elastomer (A0) and then reacting the group with the reactive compound (a), as described below.

[0024] It is desirable that the functional groups of the modified elastomer (A) used to prepare the reactant (C) are not bonded to other substances such as the reactive compound (B).

[0025] From the viewpoint of further improving mechanical properties such as vibration damping and impact resistance, the block copolymer is preferably a block copolymer having a block (A-1) containing more than 70 mol % of aromatic vinyl monomer units and a block (A-2) containing 30 mol % or more of a conjugated diene monomer, or a modified product of a hydrogenated product thereof.

[0026] The aromatic vinyl compound units in the polymer block (A-1) are more preferably 80 mol % or more, even more preferably 90 mol % or more, and even more preferably 95 mol % or more, and particularly preferably substantially 100 mol %. In other words, the aromatic vinyl compound units in the polymer block (A-1) are preferably 80 to 100 mol %. From the viewpoint of exhibiting excellent vibration-damping properties, the conjugated diene units in the polymer block (A-2) are preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, and particularly preferably substantially 100 mol %. In other words, the conjugated diene units in the polymer block (A-2) are preferably 50 to 100 mol %.

[0027] The modified elastomer (A) is more preferably a modified product of a hydrogenated block copolymer having a polymer block (A-1) and a polymer block (A-2). The modified elastomer (A) is particularly preferably a hydrogenated product of a block copolymer having a polymer block (A-1) and a polymer block (A-2), and is a modified product of the hydrogenated product having a hydrogenation rate of 50 to 99 mol%. When the modified elastomer (A) is a modified product of a hydrogenated block copolymer having a polymer block (A-1) and a polymer block (A-2), the upper limit of the content of the polymer block (A-1) in the modified elastomer (A) is preferably 35% by mass or less, more preferably 22% by mass or less, even 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 block copolymer having a polymer block (A-1) and a polymer block (A-2), the hydrogenation rate of the polymer block (A-2) is preferably 88 mol% or more, more preferably 93 mol% or more. When the modified elastomer (A) is a modified product of a hydrogenated block copolymer having a polymer block (A-1) and a polymer block (A-2), the weight average molecular weight of the modified elastomer (A) is preferably 15,000 to 400,000, more preferably 20,000 to 300,000, even more preferably 25,000 to 250,000, particularly preferably 30,000 to 200,000, and most preferably 40,000 to 180,000. The weight average molecular weight of the modified elastomer (A) can be adjusted, for example, by the amount of polymerization initiator used during polymerization.

[0028] When the modified elastomer (A) is a modified product of an olefin-based elastomer, examples of the olefin-based elastomer include acid-modified ethylene-α-olefin copolymers such as Tafmer MA8510, MA9015, MD715, MH7010, MH7020, MH5010, MH5020, and MH5040 (manufactured by Mitsui Chemicals, Inc.).

[0029] From the viewpoint of reactivity with the reactive compound (B), the modified elastomer (A) is preferably a product modified with a compound having at least one group selected from a carboxy group and a group derived from an acid anhydride, and the amount of modification, expressed in phr as parts by mass per 100 parts by mass of the modified product, is 0.01 to 1.0 phr, more preferably 0.02 to 0.5 phr, and even more preferably 0.03 to 0.3 phr. In this specification, the modification amount is a value measured by acid value titration, and more specifically, is measured by the method described in the Examples. The degree of modification in the modified elastomer (A) can be adjusted by adjusting the proportion and type of the modifier used.

[0030] The glass transition temperature of the modified elastomer (A) is preferably from -100 to -30°C, more preferably from -80 to -40°C, and even more preferably from -70 to -50°C, from the viewpoint of improving heat shock resistance. The glass transition temperature of the modified elastomer (A) is preferably from -30 to +40°C, more preferably from -15 to +30°C, and even more preferably from -10 to +25°C, from the viewpoint of improving vibration damping properties. In this specification, the glass transition temperature is a value measured using a differential scanning calorimeter (DSC) measuring device, and specifically, is measured by the method described in the examples. The glass transition temperature of the modified elastomer (A) can be adjusted, for example, by the content of 3,4-bonds and 1,2-bonds in the conjugated diene.

[0031] The modified elastomer (A) preferably has a structure represented by the following formula (X) or the structure of a hydrogenated product thereof (hereinafter, this may be referred to as an alicyclic skeleton (X)). [ka] (In the above formula (X), R 1 ~R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and 1 ~R 3 may be the same or different.) When a block copolymer or a hydrogenated product thereof is used as the elastomer (A0), the alicyclic skeleton (X) is preferably contained in a polymer block containing a structural unit derived from a conjugated diene compound, which is a constituent element of the elastomer (A0). Details of the alicyclic skeleton (X) will be described later. The block copolymer or its hydrogenated product used as the elastomer (A0) will be described in detail later.

[0032] <Reactive Compound (B)> As specified in the above condition [II], the reactive compound (B) has two or more groups per molecule of one or more types selected from the group consisting of oxazoline groups and epoxy groups. The oxazoline groups or epoxy groups react with the modified sites of the modified elastomer (A) to produce a reaction product (C). Examples of the reactive compound (B) include resins and low-molecular-weight compounds having two or more groups per molecule of one or more types selected from the group consisting of oxazoline groups and epoxy groups.

[0033] When the reactive compound (B) is a resin, it is preferably an epoxy resin or a thermoplastic resin having one or more skeletons selected from the group consisting of polystyrene, polyacrylic acid esters, polymethacrylic acid esters, and polyolefins, and having two or more groups per molecule selected from the group consisting of oxazoline groups and epoxy groups. Resins as the reactive compound (B) include homopolymers having only one skeleton from the above group, copolymers having two or more skeletons from the above group, and copolymers having one or more skeletons from the above group and another skeleton, such as copolymers of styrene and (meth)acrylic acid esters, such as methyl acrylate / polystyrene random copolymers.

[0034] The reactive compound (B) may be a low molecular weight compound having two or more groups selected from the group consisting of oxazoline groups and epoxy groups in one molecule. The molecular weight of the low molecular weight compound is, for example, 50 to 1,000, preferably 100 to 500, more preferably 130 to 350, and particularly preferably 150 to 300.

[0035] Examples of low molecular weight compounds containing two or more oxazoline groups in one molecule include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, and 2,2'-bis-4-benzyl-2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane. Examples of suitable compounds include 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine, 2,2'-isopropylidenebis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2'-methylenebis(4-phenyl-2-oxazoline). Among these compounds, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is preferred.

[0036] 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, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, and 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, which are compounds having two epoxy groups in one molecule; compounds having three epoxy rings in the molecule, such as N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane;

[0037] Examples of the polyacrylic acid ester constituting the skeleton of the reactive compound (B) include homopolymers of monomers such as methyl acrylate, butyl acrylate, and glycidyl acrylate, and copolymers with other monomers.

[0038] Examples of the polymethacrylate ester constituting the skeleton of the reactive compound (B) include homopolymers of monomers such as polymethyl methacrylate and polyglycidyl methacrylate, and copolymers with other monomers.

[0039] Examples of polyolefins 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; polypropylenes such as homopolypropylene, block polypropylene, and random polypropylene; α-olefin homopolymers or copolymers; and copolymers of propylene and / or ethylene with α-olefins. Examples of the α-olefins include α-olefins having 20 or less carbon atoms, such as 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, and 1-eicosene, and these may be used alone or in combination.

[0040] 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 as the reactive compound (B), a small amount is generally required to achieve high compatibility with the reactant (C), compared with other reactive compounds (B). Note that when a reactive compound (B) different from the epoxy group-containing resin having the specific molecular weight is used, the amount used tends to be large, but this has the advantage of making it easier to uniformly disperse the reactant (C) in the matrix resin (E) and the domain resin (F) in the reactant (C), making it easier to stabilize the feed amount during continuous production such as extrusion molding.

[0041] Hereinafter, the oxazoline group-containing styrene copolymer, epoxy resin, epoxy group-containing graft copolymer, epoxy group-containing acrylic copolymer, and epoxy group-containing styrene copolymer that can be used as the reactive compound (B) will be described.

[0042] (Oxazoline group-containing styrene copolymer) The oxazoline group-containing styrene copolymer is a copolymer containing structural units derived from styrene and structural units derived from an oxazoline group-containing olefin such as isopropenyloxazoline. The content of structural units derived from oxazoline group-containing olefin in this oxazoline group-containing styrene copolymer is not particularly limited, but from the viewpoint of compatibilizing effect, when the mass of the copolymer is taken as 100 mass%, it is preferably 2 to 50 mass%, more preferably 10 to 45 mass%, and particularly preferably 15 to 40 mass%. The total content of the structural units derived from styrene and the structural units derived from the oxazoline group-containing olefin relative to the total mass of the oxazoline group-containing styrene-based copolymer is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 85 to 100 mass%, and most preferably 100 mass%. The presence or absence of structural units derived from oxazoline group-containing olefins and the content thereof are measured by NMR. Commercially available oxazoline group-containing styrene copolymers include "Epocross RPS-1005" and "Epocross PX-3-RP-5" manufactured by Nippon Shokubai Co., Ltd., which are copolymers of styrene and 2-isopropenyl-2-oxazoline.

[0043] (Epoxy Resin) The epoxy resin is not particularly limited as long as it is a resin having two or more epoxy groups in its structure, and examples thereof include novolac epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin, alicyclic epoxy resin, nitrogen-containing ring epoxy resins such as triglycidyl isocyanurate and hydantoin epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, aliphatic epoxy resin, tetrafunctional epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, dicyclocyclic epoxy resin, and naphthalene epoxy resin. Preferred are novolac epoxy resins having three or more epoxy groups such as phenol novolac epoxy resin and cresol novolac epoxy resin, tetrafunctional epoxy resin, and glycidyl amine epoxy resin, and particularly preferred are tetrafunctional epoxy resins and glycidyl amine epoxy resin.

[0044] (epoxy group-containing graft copolymer) The epoxy group-containing graft copolymer is a graft copolymer in which a polymer having an epoxy group is introduced as a side chain into a main chain derived from a polyolefin or an acrylonitrile-styrene copolymer. There are no particular restrictions on the mass proportion of the portion derived from the epoxy group-containing polymer in this epoxy group-containing graft copolymer. However, from the viewpoint of easily ensuring good compatibilization, when the mass of the graft copolymer is taken as 100% by mass, it is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 30% by mass. The presence or absence of an epoxy group-containing polymer moiety in the epoxy group-containing graft copolymer and its content are measured by NMR. Commercially available epoxy group-containing graft copolymers include the Modiper A4000 series, such as Modiper A4100, A4300, and A4400 manufactured by NOF Corporation, which are graft copolymers having a polyolefin main chain and a vinyl polymer such as polystyrene as a side chain.

[0045] (Epoxy group-containing acrylic copolymer, epoxy group-containing styrene 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, while the epoxy group-containing styrene copolymer is a copolymer of a polymerizable unsaturated compound having an epoxy group and a styrene polymerizable unsaturated compound. The content of structural units derived from polymerizable unsaturated compounds having epoxy groups in these epoxy group-containing copolymers is not particularly limited, but from the viewpoint of compatibilizing effect, when the mass of the copolymer 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%. The presence or absence of structural units derived from a polymerizable unsaturated compound having an epoxy group and the content thereof are measured by NMR. Commercially available epoxy group-containing acrylic copolymers or epoxy group-containing styrene copolymers include the Marproof G series, such as Marproof (registered trademark) G-0105SA, G-0130SP, G-0150M, G-0250SP, and G-1005S manufactured by NOF Corporation.

[0046] The reactive compound (B) used to prepare the reactant (C) preferably has no other substance such as the modified elastomer (A) bonded to one or more groups selected from the group consisting of an oxazoline group and an epoxy group.

[0047] By using the above-mentioned compound as the reactive compound (B), the total content of epoxy groups and oxazoline groups in the reactive compound (B) can be adjusted to a predetermined value. Specifically, when parts by mass per 100 parts by mass of the reactive compound (B) are expressed in phr, the total content of epoxy groups and oxazoline groups in the reactive compound (B) is preferably 0.1 to 30 phr, more preferably 0.5 to 25 phr, and even more preferably 1.0 to 20 phr. The total content of epoxy groups and oxazoline groups in the reactive compound (B) can be adjusted by selecting the proportions and types of raw material monomers used to prepare the reactive compound (B), controlling the reaction conditions, etc.

[0048] <Reactant (C)> As described above, the reaction product (C) is produced as a reaction product in which the modified site of the modified elastomer (A) reacts with the oxazoline group or epoxy group of the reactive compound (B) to form a covalent bond therebetween. The reactant (C) preferably contains at least one of the structures represented by the following formulas (1) to (4). [ka]

[0049] The above formula (1) represents a structure formed by the bond between a carboxy group in the modified elastomer (A) and an oxazoline group in the reactive compound (B). The above formulas (2) and (3) represent structures formed by the reaction between a carboxy group in the modified elastomer (A) and an epoxy group in the reactive compound (B). The above formula (4) represents a structure formed by the bond between a group derived from an acid anhydride in the modified elastomer (A) and an oxazoline group in the reactive compound (B).

[0050] [Resin modifier] The resin modifier according to an embodiment of the present invention includes a resin composition (D). The resin modifier is a modifier that is added to a resin to be modified to improve the processability, moldability, mechanical properties, etc. of the resin. The resin modifier may consist of resin composition (D) alone or may contain components other than resin composition (D), such as processing aids, reinforcing agents, fillers, plasticizers, open-cell agents, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, lubricants, antistatic agents, antibacterial agents, mildew inhibitors, dispersants, colorants, foaming agents, foaming aids, flame retardants, water repellents, waterproofing agents, electrical conductivity imparting agents, thermal conductivity imparting agents, electromagnetic wave shielding agents, fluorescent agents, and crystal nucleating agents. The content of resin composition (D) in the resin modifier is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total mass of the resin modifier, from the viewpoint of ensuring sufficient compatibility. There is no particular upper limit and it may be 100% by mass, but from the viewpoint of ensuring good productivity, it can be, for example, 99.8% by mass or less. In other words, the content of resin composition (D) in the resin modifier is preferably 80 to 100% by mass.

[0051] [Dispersion composition] <First Dispersion Composition (M1)> A first dispersion composition according to an embodiment of the present invention (hereinafter, sometimes referred to as dispersion composition (M1)) contains the above-described resin composition as a first resin composition (D) and further contains a matrix resin (E). The first resin composition (D) is dispersed in the matrix resin (E).

[0052] 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, for example, melt-kneading the resin composition (D) and the matrix resin (E), a dispersion composition in which the resin composition (D) is very finely dispersed in the matrix resin (E) can be obtained. Therefore, the dispersion composition (M1) has superior processability and moldability compared to the matrix resin (E) alone. In addition, since the reactant (C) is easily dispersed in the matrix resin (E), the dispersion composition (M1) or the molded article of the dispersion composition (M1) has a good appearance. In addition, in the molded article of the dispersion composition (M1) or the dispersion composition (M1), the characteristics resulting from the reactive compound (B) and the elastomer (A0) used as raw materials are likely to appear. Since the dispersion composition (M1) according to the embodiment of the present invention contains the resin composition (D) that satisfies the above condition [I], the mechanical properties such as vibration damping properties and impact resistance can be enhanced in the molded article of the first dispersion composition (M1) or the dispersion composition (M1). Further, by appropriately selecting the type of the modified elastomer (A) and the reactive compound (B) for obtaining the reactant (C), the type of the matrix resin (E), etc., the physical properties such as tensile strength, elongation properties, and heat shock resistance of the dispersion composition (M1) and its molded article can be made excellent.

[0053] <Core-shell structure> A preferred embodiment of the dispersion composition (M1) is a dispersion composition having a core-shell structure in which the reactant (C) is dispersed in the matrix resin (E) and the dispersion diameter D(C) of the reactant (C) and the dispersion diameter D(B) of the component mainly composed of the site derived from the reactive compound (B) existing along the periphery of the reactant (C) satisfy the relationship D(C) < D(B). Further, a preferred embodiment of the dispersion composition (M1) is a dispersion composition that can develop a core-shell structure satisfying the relationship D(C) < D(B) in the molded article of the dispersion composition. Here, the dispersion diameter refers to the volume-average dispersion diameter of the major axis of the core-shell structure, and is specifically measured by the procedure described in the Examples below. The core-shell structure also includes those that contain one or more domains composed of components different from the reactant (C) within a shell primarily composed of a moiety derived from the reactive compound (B). Examples of such domains include domains composed of the reactive compound (B), the modified elastomer (A), a polymer or elastomer before modification, the matrix resin (E), a reaction product of the reactant (C) and the matrix resin (E), and a reaction product of the reactive compound (B) and the matrix resin (E). The presence of a core-shell structure containing a domain composed of a component different from the reactant (C) facilitates improved impact resistance.

[0054] Fig. 1 is a cross-sectional schematic diagram showing an example of a core-shell structure in a molded article of the dispersion composition (M1) according to this embodiment. As shown in Fig. 1, a core-shell structure 10 exists in a matrix 20 made of a matrix resin (E). The core-shell structure 10 includes a core 10a mainly composed of the reactant (C) and a shell 10b mainly composed of a portion derived from the reactive compound (B). FIG. 2 is a cross-sectional schematic diagram showing another example of a core-shell structure in a molded article of the dispersion composition (M1) according to this embodiment. As shown in FIG. 2, the core-shell structure 11 includes a core 11a mainly composed of the reactant (C), a shell 11b mainly composed of a portion derived from the reactive compound (B), and multiple domains distributed in the form of islands in the core 11a. Examples of the multiple domains include a domain 11b of the reactive compound (B), a domain 11c of the modified elastomer (A), and a domain 11d of the polymer or elastomer before modification, as shown in FIG. 2. The core 11a may also include a domain of the matrix resin (E), a domain of the reaction product of the reactant (C) and the matrix resin (E), or a domain of the reaction product of the reactive compound (B) and the matrix resin (E). FIG. 3 is an enlarged cross-sectional photograph taken with a transmission electron microscope (TEM) showing an example of a core-shell structure, and FIG. 4 is a partially enlarged photograph of the same. As shown in FIGS. 3 and 4, a core-shell structure is formed in a matrix 20 formed from a matrix resin (E), including a shell 11b mainly composed of a portion derived from the reactive compound (B) and a core 11a mainly composed of the reactant (C). Furthermore, the core in FIGS. 3 and 4 contains multiple domains 11b-11d, including domains of the reactive compound (B). The numerous tiny dots inside the core are due to the dyeing of specific portions of the modified elastomer (A).

[0055] The volume average dispersion diameter (major axis) of the core-shell structure in the dispersion composition (M1) or a molded product of the dispersion composition (M1) is preferably 0.01 to 10 μm, more preferably 0.03 to 8 μm, and even more preferably 0.05 to 6 μm. The dispersion diameter D(C) of the reactant (C) is substantially the same as the volume average dispersion diameter of the 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, and even more preferably 0.03 to 4 μm. The volume average dispersion diameter (minor axis) of the core-shell structure is equal to or smaller than the above volume average dispersion diameter (major axis), and is preferably 0.005 to 8 μm, more preferably 0.015 to 6 μm, and even more preferably 0.02 to 5 μm. When the volume average dispersed diameter of the core-shell structure is within the above range, the dispersibility of the core-shell structure in the matrix resin (E) can be improved, and the mechanical properties of the dispersion composition (M1) or a molded article of the dispersion composition (M1) can be improved.

[0056] <Matrix resin (E)> The matrix resin (E) is a component that serves as a base material in which the first resin composition (D) is dispersed. Examples of the matrix resin (E) include polar resins, styrene-based resins, and epoxy resins. Polar resins refer to resins that have polar groups such as carboxyl groups, sulfonic acid groups, hydroxyl groups, and cyano groups; resins that have ether bonds, ester bonds, amide bonds, sulfide bonds, and the like within the resin; and resins that contain at least one of oxygen, nitrogen, sulfur, and halogen within the molecule; and are resins that are electronically polarized within the molecule and have thermoplastic properties. The polar resin is preferably a resin having a polar group such as a sulfonic acid group or a cyano group, a resin having an ether bond, an ester bond, an amide bond, a sulfide bond, or the like in the resin, or a resin containing at least one of oxygen, nitrogen, sulfur, and a halogen in the molecule, and more preferably a resin containing at least one of an ether bond, an ester bond, and an amide bond in the resin. Preferred polar resins are at least one selected from the group consisting of polyamide resins such as nylon 6, nylon 66, nylon 610, nylon 9, nylon 6 / 66, nylon 66 / 610, nylon 6 / 11, nylon 6 / 12, nylon 12, nylon 46, and amorphous nylon; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and liquid crystal polymers (LCPs); polyacetal resins such as polyoxymethylene homopolymers and polyoxymethylene copolymers; polyphenylene sulfide (PPS) resin, polyphenylene ether resin, polyarylate resin, polyethersulfone resin, polyurethane resin, polyvinyl alcohol resin, polycarbonate (PC) resin, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, polyether ketone, polyether ether ketone, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, vinylon, triacetyl cellulose, xylene resin, acrylic resin, and polyester-based thermoplastic elastomers. More preferably, it is at least one selected from the group consisting of polyamide resin, polyester resin, polyacetal resin, polyphenylene sulfide resin, polyurethane resin, polyvinyl alcohol resin, polycarbonate resin, and polyester-based thermoplastic elastomer.

[0057] The polyester-based thermoplastic elastomer used as the polar resin can be obtained, for example, by using (i) an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, (ii) an aromatic dicarboxylic acid or an alkyl ester thereof, and (iii) a polyalkylene ether glycol as raw materials, and subjecting the resulting oligomer to an esterification reaction or transesterification reaction, followed by a polycondensation reaction. An example of a commercially available polyester thermoplastic elastomer is Hytrel 3046 (registered trademark) manufactured by DuPont-Toray Co., Ltd.

[0058] Particularly preferred matrix resin (E) is at least one resin selected from the group consisting of polyamide resin, polyester resin, polyacetal resin, polyphenylene sulfide resin, polyphenylene ether resin, polyarylate resin, polyether sulfone resin, epoxy resin, styrene-based resin, and polycarbonate resin. Examples of the styrene-based resin include atactic polystyrene, syndiotactic polystyrene (SPS), ABS resin, AS resin, and ACS resin.

[0059] At least one of the glass transition temperature and melting point of the matrix resin (E) is preferably 80° C. or higher, more preferably 100° C. or higher, and even more preferably 150° C. or higher. The glass transition temperature and melting point are measured with a DSC measuring device. When at least one of the glass transition temperature and the melting point is within the above range, the mechanical properties of the dispersion composition tend to be good.

[0060] <Proportion of components in dispersion composition> When the mass of the resin composition (D) contained in the dispersion composition (M1) is D and the mass of the matrix resin (E) is E, the D / E ratio is preferably 1 / 99 to 50 / 50, more preferably 3 / 97 to 30 / 70, and even more preferably 5 / 95 to 20 / 80. By ensuring that D / E is within the above range, it is possible to improve physical properties such as vibration damping while suppressing a significant decrease in the mechanical properties of the matrix resin. The dispersion composition (M1) may further contain an elastomer (A0) in addition to the resin composition (D) and the matrix resin (E). From the viewpoint of mechanical properties, the content of the elastomer (A0) is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and even more preferably 1 to 5% by mass, based on the total mass of the dispersion composition (M1).

[0061] <Second Dispersion Composition (M2)> A dispersion composition according to a second embodiment of the present invention (hereinafter sometimes referred to as dispersion composition (M2)) contains the above-mentioned resin composition as a first resin composition (D) and further contains a domain resin (F). The domain resin (F) is dispersed in a matrix formed by the first resin composition (D). The domain resin (F) is not particularly limited, but the resins exemplified above as the matrix resin (E) are preferably used. The glass transition temperature and melting point of the domain resin (F) are preferably the same as those described for the matrix resin (E).

[0062] In addition, in the dispersion composition (M2) in which the above-mentioned domain resin (F) is dispersed in a matrix formed by the first resin composition (D), when the mass of the resin composition (D) is D and the mass of the domain resin (F) is F, D / F is preferably 99 / 1 to 20 / 80, more preferably 90 / 10 to 20 / 80, and even more preferably 70 / 30 to 30 / 70. When D / F is within the above range, the mechanical properties such as flexibility and tensile strength are well balanced, and physical properties such as vibration damping can be improved.

[0063] <Additives> The dispersion composition may contain various additives within the range that does not impair the effects of the present invention. Examples of additives include inorganic fillers such as talc, clay, mica, calcium silicate, glass, hollow glass spheres, glass fiber, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc borate, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, graphite, carbon fiber, activated carbon, hollow carbon spheres, calcium titanate, lead zirconate titanate, silicon carbide, and mica; and organic fillers such as wood flour and starch. Further examples of the additives include tackifying resins, plasticizers, fillers, crosslinking agents (isocyanate-based crosslinking agents, epoxy-based crosslinking agents, metal chelate-based crosslinking agents, aziridine-based crosslinking agents, amine resins, etc.), heat stabilizers, light stabilizers, ultraviolet absorbers, infrared absorbers, antioxidants, lubricants, colorants, antistatic agents, flame retardants, water repellents, waterproofing agents, hydrophilicity-imparting agents, electrical conductivity-imparting agents, thermal conductivity-imparting agents, electromagnetic wave shielding agents, translucency adjusters, fluorescent agents, sliding properties-imparting agents, transparency-imparting agents, antiblocking agents, metal deactivators, antibacterial agents, crystal nucleating agents, crack inhibitors, antiozonants, rodent repellents, dispersants, thickeners, light resistance agents, weather resistance agents, copper damage inhibitors, reinforcing agents, antifungal agents, and macrocyclic molecules (cyclodextrin, calixarene, cucurbituril, etc.). The above additives can be used alone or in combination of two or more. The content of the additives in the dispersion composition is not limited and can be adjusted appropriately depending on the type of additive and the intended use of the dispersion composition. When the dispersion composition contains the additives, the content of the additives may be, for example, 50% by mass or less, 45% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less, or 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, or 5% by mass or more, relative to 100% by mass of the total amount of the dispersion composition. In other words, the content of the additives in the dispersion composition is preferably 0.01 to 50% by mass.

[0064] [Block copolymer or its hydrogenated product] The constituents, usage ratios, properties, etc. of a block copolymer or its hydrogenated product that can be used as the elastomer (A0) are explained below. Since the elastomer (A0) is the substance before modification of the modified elastomer (A), it naturally also has the polymer block (A-1) and polymer block (A-2) that the modified elastomer (A) has. Therefore, the following explanation of the polymer block (A-1) and polymer block (A-2) applies to both the elastomer (A0) and the modified elastomer (A). (Configuration of polymer block (A-1)) From the viewpoint of mechanical properties such as vibration damping and impact resistance, the polymer block (A-1) constituting the block copolymer preferably has a structural unit derived from an aromatic vinyl compound used as a monomer. The polymer block (A-1) preferably contains structural units derived from aromatic vinyl compounds (hereinafter sometimes abbreviated as "aromatic vinyl compound units") in an amount of more than 70 mol% in the polymer block (A-1), and from the viewpoint of mechanical properties such as impact resistance, more preferably 80 mol% or more, even more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably substantially 100 mol%. In other words, the content of aromatic vinyl compound units in the polymer block (A-1) is preferably more than 70 mol% and 100 mol% or less.

[0065] Examples of the aromatic vinyl compounds include 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-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro Examples of aromatic vinyl compounds include m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, vinylnaphthalene, and N-vinylcarbazole. These aromatic vinyl compounds may be used alone or in combination of two or more. Among these, from the viewpoint of the balance between production costs and physical properties, styrene, α-methylstyrene, p-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

[0066] As long as the object and effect of the present invention are not hindered, the polymer block (A-1) may contain structural units derived from unsaturated monomers other than aromatic vinyl compounds (hereinafter, sometimes abbreviated as "other unsaturated monomer units"), but the content of these units in the polymer block (A-1) is preferably 30 mol% or less, more preferably less than 20 mol%, even more preferably less than 15 mol%, still more preferably less than 10 mol%, even more preferably less than 5 mol%, and particularly preferably 0 mol%. In other words, the content of these other unsaturated monomer units in the polymer block (A-1) is preferably 0 to 30 mol%. Examples of the other unsaturated monomer include at least one selected from the group consisting of butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, etc. When the polymer block (A-1) contains the other unsaturated monomer units, the bonding form is not particularly limited and may be either random or tapered.

[0067] The block copolymer may have at least one polymer block (A-1). When the block copolymer has two or more polymer blocks (A-1), the polymer blocks (A-1) may be the same or different. In this specification, "different polymer blocks" means that the polymer blocks differ in at least one of the monomer units constituting the polymer blocks, the weight-average molecular weight, the stereoregularity, and, if multiple monomer units are present, the ratio of the monomer units and the copolymerization form (random, gradient, block).

[0068] (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 the weight-average molecular weight of at least one polymer block (A-1) among the polymer blocks (A-1) contained in the block copolymer is preferably 3,000 to 60,000, more preferably 4,000 to 50,000. Having at least one polymer block (A-1) with a weight-average molecular weight within the above range in the block copolymer can contribute to further improvement of vibration damping properties. Meanwhile, in an embodiment where 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. The weight average molecular weight is a weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC).

[0069] (Content of polymer block (A-1)) The content of polymer block (A-1) in the block copolymer is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 16% by mass or less, and particularly preferably 14% by mass or less. A content of 50% by mass or less can provide a block copolymer or a hydrogenated product thereof with appropriate flexibility and excellent vibration damping properties without a decrease in tan δ peak top intensity. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 6% by mass or more. A content of 1% by mass or more can provide a block copolymer or a hydrogenated product thereof with mechanical properties such as impact resistance, and handleability such as moldability and coatability that are suitable for various applications of the dispersion composition. In other words, the content of polymer block (A-1) in the block copolymer is preferably 1 to 50% by mass. In one preferred embodiment of the present invention, the modified elastomer (A) has the functional group only at its molecular terminal. In this case, the upper limit of the content of 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, and even more preferably 32% by mass or less. The lower limit of the content of polymer block (A-1) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more. When the content of polymer block (A-1) is within this range, the resin composition of the present invention is likely to exhibit a well-balanced vibration damping property, impact resistance, and mechanical strength, which is preferred. The content of the polymer block (A-1) in the block copolymer is 1 The values ​​were determined by H-NMR measurement, and more specifically, the values ​​were measured according to the method described in the Examples.

[0070] (Configuration 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 containing one or more alicyclic skeletons (X) represented by the following formula (X) in the main chain (hereinafter, sometimes abbreviated as "alicyclic skeleton-containing units"). The polymer block (A-2) may also contain a structural unit derived from a conjugated diene compound that does not contain an alicyclic skeleton (X) (hereinafter, sometimes abbreviated as "conjugated diene units"). From the viewpoint of exhibiting excellent vibration-damping properties, the total content of the alicyclic skeleton-containing units and the conjugated diene units in the polymer block (A-2) is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably substantially 100 mol%. In other words, the total content of the alicyclic skeleton-containing units and the conjugated diene units in the polymer block (A-2) is preferably 50 to 100 mol%. When the block copolymer has two or more polymer blocks (A-2), the polymer blocks (A-2) may be the same or different.

[0071] [ka]

[0072] In the above formula (X), R 1 ~R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and 1 ~R 3 may be the same or different. The number of carbon atoms in the hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 (i.e., a methyl group). The hydrocarbon group may be a straight-chain or branched-chain, saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and the formation of the alicyclic skeleton (X), R 1 ~R 3 are particularly preferably each independently a hydrogen atom or a methyl group. When the block copolymer is hydrogenated, the vinyl group in the formula (X) may be hydrogenated to form a hydrogenated product. Therefore, the alicyclic skeleton (X) in the hydrogenated product also includes a skeleton in which the vinyl group in the formula (X) is hydrogenated.

[0073] 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 using the method described below. Depending on the conjugated diene compound used, at least one type of alicyclic skeleton (X) is contained in the main chain of the alicyclic skeleton-containing unit. By incorporating the alicyclic skeleton (X) into the main chain of the structural unit contained in the polymer block (A-2), molecular motion is reduced, thereby increasing the glass transition temperature and improving the peak-top intensity of tan δ around room temperature, thereby enabling the development of excellent vibration damping properties.

[0074] Examples of the conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 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. Among these, butadiene, isoprene, or a combination of butadiene and isoprene is preferred.

[0075] When butadiene and isoprene are used in combination, there are no particular restrictions on the blending ratio [isoprene / butadiene] (mass ratio), but it is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, even more preferably 40 / 60 to 70 / 30, and particularly preferably 45 / 55 to 65 / 35. When expressed as a molar ratio, the blending ratio [isoprene / butadiene] is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, even more preferably 40 / 60 to 70 / 30, and particularly preferably 45 / 55 to 55 / 45.

[0076] As a specific example, an alicyclic skeleton (X) that is mainly produced 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 the conjugated diene compound, an alicyclic skeleton (X) having the combination of the following substituents (i) is produced. That is, in this case, the alicyclic skeleton (X) is R 1 ~R 3 and R are simultaneously hydrogen atoms. Therefore, as a preferred embodiment of the block copolymer or its hydrogenated product, the polymer block (A-2) is 1 ~R 3 and (X) are simultaneously hydrogen atoms.

[0077] When isoprene is used alone as the conjugated diene compound, two types of alicyclic skeletons (X) having the following combinations of substituents (v) and (vi) are mainly produced. Furthermore, when butadiene and isoprene are used in combination as the conjugated diene compound, six types of alicyclic skeletons (X) having the following combinations of substituents (i) to (vi) are mainly produced. (i) :R 1 = hydrogen atom, R 2 = hydrogen atom, R 3 = hydrogen atoms (ii) :R 1 = hydrogen atom, R 2 = methyl group, R 3 = hydrogen atoms (iii) :R 1 = hydrogen atom, R 2 = hydrogen atom, R 3 = methyl group (iv) :R 1 = methyl group, R 2 = hydrogen atom, R 3 = hydrogen atoms (v) :R 1 = methyl group, R 2 = methyl group, R 3 = hydrogen atoms (vi) :R 1 = methyl group, R 2 = hydrogen atom, R 3 = methyl group

[0078] In the above formula (X), the presence of a hydrocarbon group as a substituent reduces molecular motion and further improves vibration damping properties. From the viewpoint of this, at least one alicyclic skeleton (X) in the polymer block (A-2) is 1 ~R 3 It is preferable that at least one of the groups is an alicyclic skeleton (X') which is a hydrocarbon group having 1 to 11 carbon atoms. Among these, it is more preferable that the hydrocarbon group in the alicyclic skeleton (X') is a methyl group, from the viewpoint of enabling efficient production of the alicyclic skeleton from the conjugated diene compound and achieving a balance of mechanical properties such as vibration damping and impact resistance. Especially R 1 ~R 3each independently represents a hydrogen atom or a methyl group, and R 1 ~R 3 and (ii) are each an alicyclic skeleton that is not a hydrogen atom at the same time. That is, the polymer block (A-2) more preferably has a structural unit that includes, in the main chain, one or more of the alicyclic skeletons having the combinations of the substituents (ii) to (vi) above.

[0079] (Amount of vinyl bond in polymer block (A-2)) When the structural units constituting the polymer block (A-2) are any of an isoprene unit, a butadiene unit, and a mixed unit of isoprene and butadiene, the bonding form of each of the isoprene and butadiene other than the bonding form forming the alicyclic skeleton (X) can be a 1,2-bond or a 1,4-bond in the case of butadiene, and a 1,2-bond, a 3,4-bond, or a 1,4-bond in the case of isoprene.

[0080] In the block copolymer and its hydrogenated product, the total content of 3,4-bond units and 1,2-bond units in the polymer block (A-2) (hereinafter sometimes simply referred to as "vinyl bond content") is preferably 55 to 95 mol%, more preferably 63 to 95 mol%, and even more preferably 70 to 95 mol%. Within the above range, excellent vibration damping properties can be exhibited. On the other hand, in an embodiment where impact resistance is particularly important, the vinyl bond content is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, even more preferably 3 to 20 mol%, and particularly preferably 3 to 10 mol%. Here, the vinyl bond content can be determined according to the method described in the Examples. 1 This is a value calculated by H-NMR measurement. When the polymer block (A-2) is composed of only butadiene, the above-mentioned "content of 3,4-bond units and 1,2-bond units" is to be read as "content of 1,2-bond units".

[0081] (Alicyclic skeleton (X) content of polymer block (A-2)) From the viewpoint of vibration damping properties, it is sufficient for the polymer block (A-2) to contain a structural unit containing an alicyclic skeleton (X) in the main chain. However, from the viewpoint of exhibiting better vibration damping effects and easily suppressing a decrease in resin strength even at high temperatures, the polymer block (A-2) preferably contains 1 mol% or more of the alicyclic skeleton (X), more preferably 1.1 mol% or more, even more preferably 1.4 mol% or more, even more preferably 1.8 mol% or more, even more preferably 4 mol% or more, even more preferably 10 mol% or more, and particularly preferably 13 mol% or more. 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 does not impair the effects of the present invention. From the viewpoint of productivity, however, it is preferably 40 mol% or less, and may be 30 mol% or less, 20 mol% or less, or even 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 vibration-damping properties, the polymer block (A-2) preferably contains the alicyclic skeleton (X') in an amount of 1 mol% or more, more preferably 1.3 mol% or more, and even 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%.

[0082] More specifically, when isoprene is used as the conjugated diene compound, when butadiene is used, or when butadiene and isoprene are used in combination, the alicyclic skeleton content in each case is as follows: When isoprene is used as the conjugated diene compound, if one or more alicyclic skeletons (X') having the combination of the substituents (v) and (vi) are present in the polymer block (A-2), the total content thereof is preferably 1 mol% or more, more preferably 1.5 mol% or more, from the viewpoint of easily achieving a superior vibration-damping effect, and from the viewpoint of obtaining a superior vibration-damping effect over a wide temperature range, even more preferably 2 mol% or more, even more preferably 3 mol% or more, and particularly preferably 4 mol% or more. Furthermore, when isoprene is used, 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 isoprene is used, the content of the alicyclic skeleton (X') having the combination of the substituents (v) and (vi) in the polymer block (A-2) is preferably 1 to 40 mol%.

[0083] When butadiene is used as the conjugated diene compound, the content of the alicyclic skeleton (X) in the polymer block (A-2) is preferably 5 mol% or more, from the viewpoint of easily exhibiting superior vibration-damping properties, more preferably 10 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, still more preferably 25 mol% or more, and particularly preferably 30 mol% or more. Furthermore, when butadiene is used, the upper limit of the content is the same as the upper limit of the content of the alicyclic skeleton (X). In other words, when butadiene is used, the content of the alicyclic skeleton (X) in the polymer block (A-2) is preferably 5 to 40 mol%.

[0084] When butadiene and isoprene are used in combination as the conjugated diene compound, if one or more alicyclic skeletons (X') having a combination of the substituents (ii), (iii), (v), and (vi) are present in the polymer block (A-2), the total content thereof is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 5 mol% or more, even more preferably 8 mol% or more, and even more preferably 13 mol% or more, from the viewpoint of easily exhibiting superior vibration-damping effects. 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, the total content of the alicyclic skeletons (X') having a combination of the substituents (ii), (iii), (v), and (vi) in the polymer block (A-2) is preferably 1 to 40 mol%. Furthermore, when butadiene and isoprene are used in combination as the conjugated diene compound, if one or more alicyclic skeletons (X) having a combination of the substituents (i) to (vi) are present in the polymer block (A-2), the total content thereof is preferably 1 mol% or more, more preferably 5 mol% or more, from the viewpoint of easily achieving superior vibration-damping effects. 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 skeletons (X) having a combination of the substituents (i) to (vi) in the polymer block (A-2) is preferably 1 to 40 mol%.

[0085] The content of the alicyclic skeleton (X) (including (X')) contained in the block copolymer or its hydrogenated product is 13 It is a value determined from the integral value derived from the alicyclic skeleton (X) in the polymer block (A-2) by C-NMR measurement, and more specifically, it is a value measured according to the method described in the Examples.

[0086] Furthermore, when the hydrogenation rate of the polymer block (A-2) of the block copolymer or its hydrogenated product is 0 mol % or more and less than 50 mol %, the molar ratio of the vinyl groups bonded to the alicyclic skeleton (X) to the vinyl groups bonded to the main chain can be specified. For example, in the alicyclic skeleton (X') having a combination of the substituents (ii), (iii), (v), and (vi), the carbon atom (a) of the vinyl group terminal bonded to the alicyclic skeleton (X') is 13 The chemical shift in C-NMR appears around 107 to 110 ppm, which corresponds to the carbon atom at the end of the vinyl group attached to the main chain ((b) in the following chemical formula). 13 The chemical shift in C-NMR appears around 110 to 116 ppm. When the hydrogenation rate is 0 to 40 mol%, 13 The peak area ratio measured by C-NMR [peak area at chemical shift values ​​of 107 to 110 ppm] / [peak area at chemical shift values ​​of 110 to 116 ppm] is usually in the range of 0.01 to 3.00, and from the viewpoint of achieving better vibration damping properties, the area ratio is preferably 0.01 to 1.50, more preferably 0.01 to 1.00, even more preferably 0.01 to 0.50, and still more preferably 0.01 to 0.20.

[0087] [ka]

[0088] In addition, for hydrogenated products, 13 In C-NMR measurement, peaks derived from carbon atoms on the alicyclic skeleton (X) are hardly observed, but the substituent R 3 is a hydrocarbon group having 1 to 11 carbon atoms, and the R 3 A peak derived from a carbon atom on the alicyclic skeleton (X) bonded to a branched alkyl group derived from a vinyl group having the formula: can be observed. As a result, when the hydrogenation rate of the polymer block (A-2) of the hydrogenated product is 50 to 99 mol %, the above R 3It is also possible to specify the molar ratio of the carbon atoms on the alicyclic skeleton (X) bonded to the branched alkyl group derived from the vinyl group and the carbon atoms on the main chain bonded to the branched alkyl group derived from the vinyl group.

[0089] For example, in the alicyclic skeleton (X) having a combination of the substituents (iii) and (vi), the carbon atom (c) of the alicyclic skeleton (X) that is bonded to the isoprene group is 13 The chemical shift in C-NMR appears around 50.0 to 52.0 ppm, which corresponds to the carbon atom on the main chain that bonds to the isoprene group ((d) in the chemical formula below). 13 The chemical shift in C-NMR appears around 43.0 to 45.0 ppm. When the hydrogenation rate is 40 to 99 mol%, 13 The peak area ratio measured by C-NMR [peak area at chemical shift values ​​of 50.0 to 52.0 ppm] / [peak area at chemical shift values ​​of 43.0 to 45.0 ppm] is usually in the range of 0.01 to 3.00, and from the viewpoint of making it easier to exhibit better vibration damping properties, the area ratio is preferably in the range of 0.01 to 1.50, more preferably in the range of 0.01 to 1.00, even more preferably in the range of 0.01 to 0.50, and still more preferably in the range of 0.01 to 0.25. More specifically, the peak area ratio can be measured according to the method described in the Examples.

[0090] [ka]

[0091] On the other hand, in an embodiment where 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 %, even more preferably 0 to 5 mol %, and particularly preferably substantially 0 mol %.

[0092] (Weight-average molecular weight of polymer block (A-2)) From the viewpoint of vibration damping properties, the total weight average molecular weight of the polymer blocks (A-2) in the block copolymer before hydrogenation is preferably 15,000 to 800,000, more preferably 50,000 to 700,000, even 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 where 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, even more preferably 30,000 to 300,000, particularly preferably 30,000 to 200,000, and most preferably 35,000 to 150,000.

[0093] (Other structural units in polymer block (A-2)) The polymer block (A-2) may contain structural units derived from polymerizable monomers other than the conjugated diene compound, as long as the purpose and effects of the present invention are not hindered. In this case, the content of structural units derived from polymerizable monomers other than the conjugated diene compound in the polymer block (A-2) is preferably less than 50 mol%, more preferably less than 30 mol%, even more preferably less than 20 mol%, still more preferably less than 10 mol%, and particularly preferably 0 mol%. In other words, the content of structural units derived from polymerizable monomers other than the conjugated diene compound in the polymer block (A-2) is preferably 0 mol% or more and less than 50 mol%. Preferred examples of the other polymerizable monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, N-vinylcarbazole, vinylnaphthalene, and vinylanthracene, as well as at least one compound selected from the group consisting of methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene. The block copolymer may have at least one polymer block (A-2). When the block copolymer has two or more polymer blocks (A-2), the polymer blocks (A-2) may be the same or different.

[0094] (Bonding Mode between Polymer Block (A-1) and Polymer Block (A-2)) The block copolymer is not limited in the bonding form, as long as the polymer block (A-1) and the polymer block (A-2) are bonded together, and may be linear, branched, radial, or a combination of two or more of these. Among these, the bonding form between the polymer block (A-1) and the polymer block (A-2) is preferably linear. Examples of such a form include a diblock copolymer represented by AB, a triblock copolymer represented by ABA or BAB, a tetrablock copolymer represented by ABAB, a pentablock copolymer represented by ABABA or BABAB, and an (AB)nZ copolymer (where Z represents a coupling agent residue and n represents an integer of 3 or greater), where A represents the polymer block (A-1) and B represents the polymer block (A-2). Among these, a linear triblock copolymer or diblock copolymer is preferred, and an ABA triblock copolymer is preferred from the viewpoints of flexibility, ease of production, and the like. Specific examples of ABA triblock copolymers include styrene-hydrogenated butadiene-styrene copolymer, styrene-hydrogenated isoprene-styrene copolymer, and styrene-hydrogenated butadiene / isoprene-styrene copolymer, etc. That is, the block copolymer preferably contains at least one selected from the group consisting of styrene-hydrogenated butadiene-styrene copolymer, styrene-hydrogenated isoprene-styrene copolymer, and styrene-hydrogenated butadiene / isoprene-styrene copolymer, and more preferably contains styrene-hydrogenated butadiene / isoprene-styrene copolymer.

[0095] Here, in this specification, when polymer blocks of the same type are linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer blocks are treated as a single polymer block. Accordingly, including the above examples, polymer blocks that should strictly be expressed as YZY (Z represents a coupling residue) are expressed as Y as a whole, unless there is a particular need to distinguish them from a single polymer block Y. In this specification, since this type of polymer block containing a coupling agent residue is treated as above, for example, a block copolymer containing a coupling agent residue and that should strictly be expressed as ABZBA (Z represents a coupling agent residue) is expressed as ABA and treated as an example of a triblock copolymer.

[0096] (Content of polymer blocks (A-1) and (A-2)) The block copolymer may contain a polymer block composed of a monomer other than the polymer blocks (A-1) and (A-2) as long as it does not interfere with the objects and effects of the present invention. However, the total content of the polymer blocks (A-1) and (A-2) is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably substantially 100% by mass. A content of 90% by mass or more facilitates the production of a dispersion composition that is more likely to exhibit excellent vibration damping properties. In other words, the total content of the polymer blocks (A-1) and (A-2) in the block copolymer is preferably 90 to 100% by mass.

[0097] (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, determined by gel permeation chromatography in terms of standard polystyrene, is preferably 15,000 to 800,000, more preferably 50,000 to 700,000, even more preferably 60,000 to 600,000, still more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000 to 450,000. If the weight-average molecular weight of the block copolymer and its hydrogenated product is 15,000 or more, heat resistance is enhanced, and if it is 800,000 or less, the handleability of the resulting resin composition is improved. In addition, in an embodiment in which the modified elastomer (A) has the functional groups only at the molecular terminals, 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, even more preferably 25,000 to 100,000, particularly preferably 30,000 to 90,000, and most preferably 40,000 to 80,000. When the weight-average molecular weight (Mw) is within this range, the reactant (C) contained in the resin composition (D) is more easily dispersed in the matrix resin (E), and as a result, excellent impact resistance is more easily exhibited.

[0098] (Tan δ Peak Top Temperature and Intensity of Block Copolymer or Its Hydrogenated Product) The loss tangent (tanδ) of a block copolymer or its hydrogenated product is the ratio of the loss modulus to the storage modulus at a frequency of 1 Hz in dynamic viscoelastic measurements, and the peak-top temperature and strength of tanδ contribute significantly to vibration damping and other physical properties. Here, the peak-top strength of tanδ refers to the value of tanδ when the peak of tanδ is maximum. Furthermore, the peak-top temperature of tanδ refers to the temperature when the peak of tanδ is maximum.

[0099] (Tan δ strength of block copolymer or its hydrogenated product) In this specification, the peak-top temperature and intensity of tan δ of a block copolymer or its hydrogenated product are measured by preparing a monolayer sheet of 1.0 mm in thickness by pressing the block copolymer or its hydrogenated product at 230°C and 10 MPa for 3 minutes, cutting the monolayer sheet into a disk shape, and using this as a test piece. The measurement conditions are in accordance with JIS K 7244-10 (2005): strain 0.1%, frequency 1 Hz, measurement temperature -70 to +100°C, and heating rate 3°C / min. The peak top temperature and tan δ intensity of the block copolymer or its hydrogenated product are values ​​measured in more detail according to the method described in the Examples.

[0100] The block copolymer or its hydrogenated product can have a tan δ peak top intensity of 1.0 or more as measured above. Some have a higher value of 1.5 or more, or even 1.9 or more. The higher the tan δ peak top intensity, the better the physical properties, such as vibration damping, at that temperature. If the tan δ peak top intensity is 1.0 or more, sufficient vibration damping can be obtained in the actual usage environment. Furthermore, from the viewpoint of vibration damping properties, the block copolymer or its hydrogenated product has a tan δ peak top temperature of preferably -50°C or higher, more preferably -40°C or higher, even more preferably -30°C or higher, still more preferably -25°C or higher, and may be 0°C or higher. The upper limit of the tan δ peak top temperature 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 tan δ peak top temperature is, for example, preferably -50 to +50°C, more preferably -40 to +40°C, even more preferably -30 to +30°C, and still more preferably -25 to +25°C. When the tan δ peak top temperature is -50°C or higher or +50°C or lower, sufficient vibration damping properties can be obtained in actual use environments. On the other hand, in an embodiment in which impact resistance is particularly important, the upper limit of the peak top temperature of tan δ is preferably −30° C. or lower, more preferably −35° C. or lower, even more preferably −40° C. or lower, and even more preferably −43° C. or lower. In an 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 tan δ is, for example, preferably −100 to −30° C., more preferably −90 to −35° C., even more preferably −80 to −40° C., and still more preferably −70 to −43° C.

[0101] From the viewpoint of improving impact resistance and heat 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., and even more preferably −70 to −50° C. From the viewpoint of improving vibration damping properties, the glass transition temperature is preferably −30 to +40° C., more preferably −15 to +30° C., and even more preferably −10 to +25° C.

[0102] [Manufacturing method] <Method of producing block copolymer> Examples of methods for producing a block copolymer include a method in which one or more conjugated diene compounds are polymerized as monomers by anionic polymerization to form a polymer block (A-2) having a structural unit containing an alicyclic skeleton (X) in the main chain, and then a monomer for the polymer block (A-1) is added, and if necessary, further monomers for the polymer block (A-1) and a conjugated diene compound are added sequentially to obtain a block copolymer. The anionic polymerization method can be used to generate the alicyclic skeleton (X) using known techniques (see, for example, U.S. Pat. No. 3,966,691). The alicyclic skeleton (X) is formed at the end of the polymer due to monomer depletion, and polymerization can be initiated again from the alicyclic skeleton (X) by sequentially adding additional monomer. Therefore, the presence or absence of the alicyclic skeleton (X) and its content can be controlled by adjusting the sequential addition time of the monomer, the polymerization temperature, the type and amount of catalyst, the combination of the monomer and catalyst, etc. Furthermore, the anionic polymerization method can use an anionic polymerization initiator, a solvent, and, if necessary, a Lewis base.

[0103] In the above method, examples of organolithium compounds that can be used as polymerization initiators for anionic polymerization include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, etc. Examples of dilithium compounds that can be used as polymerization initiators include naphthalenedilithium, dilithiohexylbenzene, etc. Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, and phenyl benzoate. The amounts of these polymerization initiators and coupling agents used are determined appropriately depending on the desired weight-average molecular weight of the block copolymer and its hydrogenated product. Usually, initiators such as alkyllithium compounds and dilithium compounds are preferably used in an amount of 0.01 to 0.2 parts by mass 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 in the polymerization, and when a coupling agent is used, it is preferably used in an amount of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the monomers.

[0104] The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction, and examples thereof include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; aromatic hydrocarbons such as benzene, toluene, and xylene. The polymerization reaction is generally 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.

[0105] Furthermore, by adding a Lewis base as a co-catalyst during polymerization of the conjugated diene compound, the content of the alicyclic skeleton (X) and the contents of 3,4-bonds and 1,2-bonds in the polymer block (A-2) can be increased. Examples of Lewis bases that can be used include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and 2,2-di(2-tetrahydrofuryl)propane (DTHFP); glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether; amines such as triethylamine, N,N,N',N'-tetramethylenediamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholine; and metal salts such as sodium or potassium salts of aliphatic alcohols, such as sodium t-butylate, sodium t-amylate, and sodium isopentylate, or dialkylsodium cyclohexanolate, for example, and sodium or potassium salts of alicyclic alcohols, such as sodium mentholate. These Lewis bases can be used alone or in combination of two or more.

[0106] The amount of Lewis base added is determined by the extent to which the content of the alicyclic skeleton (X) is controlled, and, when the polymer block (A-2) contains structural units derived from isoprene and / or butadiene, the extent to which the vinyl bond content of the isoprene units and / or butadiene units constituting the polymer block (A-2) is controlled. Therefore, although there is no strict limitation on the amount of Lewis base added, it is preferable to use it in the range of usually 0.1 to 1,000 mol, preferably 1 to 100 mol, per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as a polymerization initiator.

[0107] The average feed rate of the conjugated diene compound (hereinafter sometimes referred to as "average diene feed rate") is preferably 150 kg / h or less, more preferably 110 kg / h or less, and even more preferably 55 kg / h or less, per mole of active terminal, from the viewpoint of increasing the content of the alicyclic skeleton (X). It may be 45 kg / h or less, 30 kg / h or less, or 22 kg / h or less. From the viewpoint of increasing productivity, the lower limit is preferably 1 kg / h or more, more preferably 3 kg / h or more, and even more preferably 5 kg / h or more, per mole of active terminal, and may be 7 kg / h or more, 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 mole of active terminal.

[0108] After anionic polymerization using the above-described method, a block copolymer can be obtained by adding an active hydrogen compound such as an alcohol, a carboxylic acid, or water to terminate the polymerization reaction. Alternatively, after anionic polymerization using the above-described method, a cyclic ether compound can be reacted with the living anionic active terminal of the resulting block copolymer, and then an active hydrogen compound such as an alcohol, a carboxylic acid, or water can be added to terminate the polymerization reaction, thereby obtaining a block copolymer having a hydroxy group introduced at the molecular terminal. The cyclic ether compound is not particularly limited, but preferred examples include ethylene oxide, propylene oxide, butylene oxide, and oxetane. Among these, ethylene oxide and oxetane are preferred, and ethylene oxide is more preferred, from the viewpoint of the reactivity of the hydroxy group introduced at the terminal.

[0109] <Method of producing hydrogenated products> When the block copolymer obtained by the above-mentioned production method is converted 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 hydrogenation reaction hydrogenates the carbon-carbon double bonds derived from the conjugated diene compound in the polymer block (A-2) of the block copolymer, thereby producing a hydrogenated product of the block copolymer. The hydrogenation reaction can be carried out under a hydrogen pressure of about 0.1 to 20 MPa, preferably 0.5 to 15 MPa, and more preferably 0.5 to 5 MPa, at a reaction temperature of about 20 to 250°C, preferably 50 to 180°C, and more preferably 70 to 180°C, for a reaction time of usually about 0.1 to 100 hours, and preferably 1 to 50 hours. Examples of hydrogenation catalysts include Raney nickel; heterogeneous catalysts in which a metal such as Pt, Pd, Ru, Rh, or Ni is supported on a substrate such as carbon, alumina, or diatomaceous earth; Ziegler catalysts formed by combining a transition metal compound with an alkylaluminum compound, an alkyllithium compound, or the like; and metallocene catalysts.

[0110] The hydrogenated product thus obtained can be obtained by pouring the polymerization reaction liquid into methanol or the like to solidify it, followed by drying under heating or reduced pressure, or by pouring the polymerization reaction liquid into hot water together with steam to remove the solvent by azeotropy (so-called steam stripping), followed by drying under heating or reduced pressure.

[0111] Whether to use the block copolymer or the hydrogenated product can be determined depending on the desired performance in various applications of the resin composition or dispersion composition. Similarly, the hydrogenation rate of the carbon-carbon double bonds in the polymer block (A-2) when forming the hydrogenated product can be determined depending on the desired performance in various applications of the resin composition or dispersion composition. For example, the higher the hydrogenation rate of the hydrogenated product, the more improved the heat resistance and weather resistance of the hydrogenated product can be.

[0112] Therefore, the block copolymer or hydrogenated product thereof may have a hydrogenation rate of the polymer block (A-2) of 0 mol % or more (i.e., including the case where the polymer block (A-2) is unhydrogenated) but less than 50 mol %, or may have a hydrogenated product thereof having a hydrogenation rate of the polymer block (A-2) of 50 to 99.9 mol %, or may have a hydrogenated product having a hydrogenation rate of 50 to 99 mol %. The hydrogenation rate is determined by measuring the content of carbon-carbon double bonds in the structural units derived from the conjugated diene compound and the alicyclic skeleton (X) in the polymer block (A-2) after hydrogenation. 1 The values ​​were determined by H-NMR measurement, and more specifically, the values ​​were measured according to the method described in the Examples.

[0113] <Method for producing modified elastomer (A), reactant (C), and resin composition (D)> The resin composition (D) can be produced by a production method in which the modified elastomer (A) and the reactive compound (B) are mixed in a molten state and reacted with each other to produce the reaction product (C). The modified elastomer (A) may be prepared and then mixed with the reactive compound (B), or the elastomer (A0) may be modified to produce the modified elastomer (A) and simultaneously react with the reactive compound (B). Hereinafter, the former method will be referred to as the first production method, and the latter method will be referred to as the second production method.

[0114] In the first production method, the modified elastomer (A) can be produced, for example, by adding a radical initiator and at least one of a carboxyl group-containing compound and an acid anhydride to a molten block copolymer, a hydrogenated block copolymer, or an olefinic elastomer, and melt-kneading the mixture (reactive extrusion) to introduce at least one of a carboxyl group and an acid anhydride-derived group into the block copolymer, the hydrogenated block copolymer, or the olefinic elastomer to obtain a modified product. Alternatively, a modified elastomer (A) having a hydroxyl group at the molecular end may be produced by using an epoxy group-containing compound, such as ethylene oxide or propylene oxide, as a polymerization terminator. Alternatively, the modified elastomer (A) may be produced by copolymerizing a monomer having at least one of a carboxyl group and an acid anhydride-derived group (e.g., maleic anhydride) with a monomer not having these groups. In this way, by copolymerizing multiple types of monomers, a modified elastomer (A) having a functional group capable of reacting with an oxazoline group or an epoxy group can be obtained at the same time as the copolymerization, similar to the above-mentioned modified product.

[0115] Alternatively, in the first production method, an elastomer having hydroxyl groups at its molecular terminals may be produced, and at least one of a carboxyl group-containing compound and an acid anhydride may be added to the elastomer and reacted to obtain a modified elastomer (A) having functional groups reactive with oxazoline or epoxy groups at its molecular terminals. The modified elastomer (A) thus obtained has the functional groups only at its molecular terminals, making it easier to control its flowability. When the modified elastomer (A) having the functional groups at its molecular terminals is obtained in this manner, the elastomer having hydroxyl groups at its molecular terminals can also be considered to be the elastomer before modification to introduce functional groups reactive with oxazoline or epoxy groups, i.e., elastomer (A0).

[0116] When an elastomer having a hydroxy group at the molecular end is represented as "R-OH," for example, the modified elastomer (A) obtained by adding and reacting phthalic anhydride has a structure represented by the following formula (5), the modified elastomer (A) obtained by adding and reacting succinic anhydride has a structure represented by the following formula (6), and the modified elastomer (A) obtained by adding and reacting maleic anhydride has a structure represented by the following formula (7). [ka]

[0117] In the first production method, the modified elastomer (A) is prepared, and then mixed with the reactive compound (B) and, if necessary, a base catalyst to produce the reaction product (C), thereby producing the resin composition (D).

[0118] In the second production method, for example, a radical initiator and at least one of a carboxyl group-containing compound and an acid anhydride are first added to a molten block copolymer, a hydrogenated block copolymer, or an olefinic elastomer, and then a reactive compound (B) is added to introduce at least one of a carboxyl group and an acid anhydride-derived group into the block copolymer, the hydrogenated block copolymer, or the olefinic elastomer, and react the reactive compound (B) to produce resin composition (D). Resin composition (D) can also be produced according to the second production method using an elastomer having a hydroxyl group at the molecular end.

[0119] The first production method has the advantage that the production of the modified elastomer (A) and the production of the reactant (C) can be carried out separately, while the second production method has the advantage that the step of modifying the elastomer (A0) in advance can be omitted, thereby simplifying the production process.

[0120] In both the first and second production methods, there are no particular limitations on the procedure for mixing and reacting the components, and the components can be mixed and reacted using, for example, a kneading device. Any kneading device commonly used in this field can be used. The components can be mixed using a mixer such as a Henschel mixer, V blender, ribbon blender, tumbler blender, or conical blender, or after mixing, can be kneaded using a single-screw or twin-screw extruder, kneader, or the like. The temperature during melt-kneading can be set as appropriate, but is usually 150 to 300°C, and preferably 160 to 250°C.

[0121] In the first and second production methods, the amount of the raw material used to obtain the reaction product (C) is not limited to, but is, for example, 1 to 50 parts by mass of the reactive compound (B) per 100 parts by mass of the elastomer (A0) used to produce the modified elastomer (A).

[0122] In the first and second production methods, usable radical initiators include, for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane. In addition, usable base catalysts in the first and second production methods include triphenylphosphine; amines such as N,N-dimethyl-4-aminopyridine, bipyridine, 4-pyrrolidinopyridine, ethylenediamine, diethylenetriamine, diethylaminopropylamine, and phenylenediamine; and imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

[0123] In the method for producing resin composition (D), when the content of reactive compound (B) contained in resin composition (D) is B mass % and the content of reactant (C) is C mass %, the reaction rate represented by C / (B+C) is preferably 0.1 to 1.0, more preferably 0.3 to 1.0, and even more preferably 0.5 to 1.0, from the viewpoint of improving compatibility with matrix resin (E) or domain resin (F). The reaction rate can be adjusted by controlling the combination of the reactive compound (B) and the modified elastomer (A) and the reaction conditions.

[0124] The resulting resin composition (D) can be formed into an appropriate form depending on the intended use and mode of use, for example, in the form of granules, flakes, or pellets.

[0125] <Method for producing dispersion composition> The dispersion composition can be produced, for example, by heating and mixing the reactant (C), the matrix resin (E) or the domain resin (F), and, if necessary, additives to an appropriate temperature. Melt-kneading the reactant (C) and the matrix resin (E), or melt-kneading the domain resin (F) and the reactant (C), facilitates the formation of a core-shell structure. The melt-kneading procedure is not particularly limited, and the composition can be prepared, for example, using a kneading device. Any kneading device commonly used in this field can be used. The components can be mixed using a mixer such as a Henschel mixer, V-blender, ribbon blender, tumbler blender, or conical blender, or the components can be mixed and then kneaded using a single-screw or twin-screw extruder, kneader, or the like. The temperature during melt-kneading can be set as appropriate, but is usually 150 to 300°C, and preferably 160 to 250°C.

[0126] The resulting dispersion composition can be formed into an appropriate form depending on the application and mode of use, for example, in the form of granules, flakes, or pellets.

[0127] [Characteristics of the dispersion composition] <Volume average dispersed diameter> In the dispersion composition of this embodiment or a molded article of the dispersion composition, the core-shell structure may have a volume average dispersion diameter of 0.01 to 10 μm, or 0.03 to 8 μm, or even 0.05 to 6 μm. When the volume average dispersion diameter of the core-shell structure is within the above numerical range, the dispersibility of the core-shell structure in the matrix resin (E) or in the matrix of the resin composition (D) can be improved, and for example, the mechanical strength of the dispersion composition can be improved. The volume-average dispersion diameter of the core-shell structure can be determined by freeze-fracturing a test piece using liquid nitrogen, etching the cross section, and then vapor-depositing platinum or the like onto the sample, observing the resulting image with an SEM, and calculating the average value of the long diameters of 50 pores removed by etching as the volume-average dispersion diameter. More specifically, this measurement is carried out by the procedure described in the Examples.

[0128] <Loss coefficient> The dispersion composition of this embodiment exhibits good vibration damping properties over a wide temperature range. The good vibration damping properties exhibited by the dispersion composition over a wide temperature range can be achieved by controlling the type of elastomer (A0), the type and content ratio of the monomer used in the modified hydrogenated product, the balance between the vinyl bond amount and the hydrogenation rate, selection of a method for producing the modified hydrogenated product, control of other components of the modified hydrogenated product of the present invention, or adjustment of the combination of the reactant (C) used in the dispersion composition with the matrix resin (E) or domain resin (F) and the content ratio thereof. For example, a test piece 200 mm long, 10 mm wide, and 2 mm thick is molded using the dispersion composition of this embodiment, and a damping test is performed using the central excitation method in accordance with JIS K 7391 (2008). The loss coefficient is measured, and the vibration damping properties can be evaluated as follows: The loss factor at a frequency of 300 Hz and a temperature of 0° C. is preferably 0.008 or more. Furthermore, the loss factor can be set to 0.020 or more, or 0.030 or more. The loss factor at a frequency of 300 Hz and a temperature of 20° C. is preferably 0.008 or more. Furthermore, the loss factor can be set to 0.020 or more, or 0.030 or more. The loss factor at a frequency of 300 Hz and a temperature of 40° C. is preferably 0.008 or more. Furthermore, the loss factor can be set to 0.020 or more, or 0.030 or more. The loss factor at a frequency of 300 Hz and a temperature of 60° C. is preferably 0.008 or more. Furthermore, the loss factor can be set to 0.020 or more, or 0.030 or more. The loss factor at a frequency of 300 Hz and a temperature of 80° C. is preferably 0.008 or more. Furthermore, the loss factor can be set to 0.020 or more, or 0.030 or more. The loss factor at a frequency of 300 Hz and a temperature of 100° C. is preferably 0.008 or more. Furthermore, the loss factor can be set to 0.020 or more, or 0.030 or more.

[0129] [Uses of the dispersion composition] The dispersion composition described above can be used for a variety of purposes. The dispersion composition of the present embodiment has excellent vibration-damping properties and can be used in various applications. Therefore, the present invention also provides a vibration-damping material, a film or sheet, an adhesive or pressure-sensitive adhesive, etc., using the dispersion composition of the present invention. The dispersion composition of the present invention can also be used in various adhesive layers of printed wiring boards. Specifically, by using the dispersion composition as an adhesive composition for, for example, a coverlay film, a laminate, a resin-coated copper foil, or a bonding sheet, the dispersion composition can be expected to have high adhesion to substrates such as polyimide, polyester, copper foil, and LCP, as well as solder reflow resistance and low dielectric properties. It is also possible to provide a laminate having an X layer containing the dispersion composition of the present invention and a Y layer laminated on at least one surface of the X layer. A suitable example of such a laminate is laminated glass, and by using the X layer as an interlayer film for laminated glass and the Y layer as glass to produce laminated glass, not only excellent vibration damping properties but also excellent sound insulation properties can be expected. The Y layer may be selected appropriately depending on the intended use, other than the above-mentioned glass layer, and may include, for example, a layer containing a thermoplastic resin other than the hydrogenated block copolymer of the present invention, such as a polyvinyl acetal resin such as polyvinyl butyral (PVB), an ionomer, an ethylene-vinyl acetate copolymer, a urethane resin, or a polyamide resin.

[0130] Other uses include pellets, bales, sound absorbing materials, sound insulating materials, dam rubber, shoe sole materials, flooring materials, weather strips, floor mats, dash insulators, roof linings, door panels, engine head covers, door hole seals, fender liners, catheters, and the like, and the rubber is also useful in these applications. The dispersion composition of the present invention can also be used in a variety of automotive components in the automotive field, for example, cooling parts such as thermostat housings, radiator tanks, radiator hoses, water outlets, water pump housings, and rear joints; intake and exhaust system parts such as intercooler tanks, intercooler cases, turbo duct pipes, EGR cooler cases, resonators, throttle bodies, intake manifolds, and tail pipes; fuel system parts such as fuel delivery pipes, gasoline tanks, quick connectors, canisters, pump modules, fuel pipes, oil strainers, lock nuts, and seals; structural parts such as mount brackets, torque rods, and cylinder head covers; drive system parts such as bearing retainers, gear tensioners, headlamp actuator gears, HVAC gears, sliding door rollers, and clutch peripheral parts; and air brakes. It can also be used for brake system parts such as brake tubes; automotive electrical parts such as wire harness connectors in the engine room, motor parts, sensors, ABS bobbins, combination switches, on-board switches, and electronic control unit (ECU) boxes; and interior and exterior parts such as sliding door dampers, door mirror stays, door mirror brackets, inner mirror stays, roof rails, engine mount brackets, air cleaner inlet pipes, door checkers, plastic chains, emblems, clips, breaker covers, cup holders, airbags, fenders, spoilers, radiator supports, radiator grilles, louvers, air scoops, hood bulges, back doors, fuel sender modules, floor mats, instrument panels, dashboards, dash insulators, dam rubber, weather strips, and tires.

[0131] It can also be used in sealing materials, adhesives, pressure-sensitive adhesives, packing, O-rings, belts, soundproofing materials, etc. in various electrical products in the home appliance field, such as televisions, various recorders such as Blu-ray recorders and HDD recorders, projectors, game consoles, digital cameras, home video recorders, antennas, speakers, electronic dictionaries, IC recorders, fax machines, copy machines, telephones, door phones, rice cookers, microwave ovens, oven ranges, refrigerators, dishwashers, dish dryers, IH cooking heaters, hot plates, vacuum cleaners, washing machines, chargers, sewing machines, irons, dryers, electric bicycles, air purifiers, water purifiers, electric toothbrushes, lighting fixtures, air conditioners, air conditioner outdoor units, dehumidifiers, and humidifiers.It can also be used as a fiber. [Example]

[0132] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0133] The methods for evaluating the physical properties of the hydrogenated products of the block copolymers and the modified elastomers (A) obtained in the production examples described below are shown below. (1) Content of polymer block (A-1) The block copolymer before hydrogenation was dissolved in CDCl3. 1 H-NMR measurement [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C] was performed, and the content of polymer block (A-1) was calculated from the ratio of the peak intensity derived from styrene to the peak intensity derived from diene.

[0134] (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) under the following conditions: In the following Production Examples 1 and 2, before the conjugated diene compound was added, a portion of the reaction solution was sampled from the pressure vessel, and GPC measurement was performed using the sampled reaction solution to determine the Mw of the polymer block (A-1) alone in the same manner. (GPC measurement equipment and measurement conditions) Apparatus: GPC apparatus "HLC-8020" (Tosoh Corporation) Separation columns: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Corporation were connected in series. Eluent: Tetrahydrofuran ·Eluent flow rate: 0.7mL / min Sample concentration: 5mg / 10mL Column temperature: 40℃ Detector: Refractive index (RI) detector Calibration curve: Created using standard polystyrene

[0135] (3) Hydrogenation rate in polymer block (A-2) 1 It was calculated from the ratio of the peak area derived from the residual olefins of isoprene and / or butadiene to the peak area derived from ethylene, propylene and / or butylene by H-NMR measurement. Equipment: Nuclear magnetic resonance spectrometer "ADVANCE 400 Nano bay" (manufactured by Bruker) Solvent: CDCl3

[0136] (4) Amount of vinyl bonds in polymer block (A-2) The block copolymer before hydrogenation was dissolved in CDCl3. 1 H-NMR measurement was performed [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C]. The vinyl bond amount (total content of 3,4-bond units and 1,2-bond units) was calculated from the ratio of the total peak area of ​​structural units derived from isoprene and / or butadiene to the peak area corresponding to the 3,4-bond units and 1,2-bond units in isoprene structural units, the 1,2-bond units in butadiene structural units, or, in the case of structural units derived from a mixture of isoprene and butadiene, the peak area corresponding to each of the above bond units.

[0137] (5) Content of alicyclic skeleton (X) in polymer block (A-2) 600 mg of block copolymer before hydrogenation and 340 mg of Cr(acac) were dissolved in 34 mL of CDCl and quantitatively analyzed using a 10 mm NMR tube. 13 C-NMR measurement (pulse program: zgig, inverse gated 1H decoupling method) [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C] was performed, and the contents of the alicyclic skeletons X, X1, and X2 in the polymer block (A-2) were calculated by the following method. In Table 1, X, X1, and X2 represent the following alicyclic skeletons. X: an alicyclic skeleton having a combination of the following substituents (i) to (vi): X1: an alicyclic skeleton having a combination of the following substituents (i) and (iv): X2: an alicyclic skeleton having a combination of the following substituents (ii), (iii), (v), and (iv) (i) :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 group; (1,2Bd + 3,4Ip) (iv) :R 1 = methyl group, R 2 = hydrogen atom, R 3 = Hydrogen atom; (1,2Ip+Bd) (v) :R 1 = methyl group, 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) Note that Ip represents isoprene and Bd represents butadiene.

[0138] [Calculation method] Each peak and the structure it derives from are shown in Table 1-1. If the integral values ​​of each peak are a to g, the integral values ​​of each structure are as shown in Table 1-2, and the contents of X, X1, and X2 can be calculated as (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), respectively.

[0139] [Table 1]

[0140] (6) 13 C-NMR peak area ratio The hydrogenated product of Production Example 1 was subjected to the above quantitative analysis. 13 C-NMR measurement [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C, solvent: CDCl3] was performed, and the peak area ratio [peak area of ​​chemical shift value 50.0 to 52.0 ppm] / [peak area of ​​chemical shift value 43.0 to 45.0 ppm] was calculated.

[0141] (7) Peak top temperature of tan δ, peak top intensity, maximum width of the temperature range where tan δ is 1.0 or more, tan δ intensity at 20°C and 30°C For the following measurements, a hydrogenated product of the block copolymer was pressurized at 230°C and 10 MPa for 3 minutes to prepare a monolayer sheet having a thickness of 1.0 mm. The monolayer sheet was cut into a disk shape to be used as a test sheet. For the measurements, a strain-controlled dynamic viscoelasticity device "ARES-G2" (manufactured by TA Instruments Japan) with a disk diameter of 8 mm was used as a parallel plate oscillatory rheometer based on JIS K 7244-10 (2005). The gap between the two plates was completely filled with the test sheet, and the test sheet was subjected to vibration at a frequency of 1 Hz with a strain of 0.1% and heated from -70°C to +100°C at a constant rate of 3°C / min. The temperatures of the test sheet and discs were maintained until no changes were observed in the measured values ​​of shear loss modulus and shear storage modulus. The maximum value of the peak strength of tan δ (peak top strength) and the temperature at which this maximum value was obtained (peak top temperature) were determined. The maximum width of the temperature range where tan δ was 1.0 or greater, and the tan δ strengths at 20°C and 30°C were also determined. A larger value indicates better vibration damping properties.

[0142] Next, the methods for evaluating the physical properties of the modified elastomer (A) obtained in the production examples described later will be described below. (8) Amount of modification of modified elastomer (A) The amount of maleic anhydride modification of modified elastomers a-1 to a-3, which correspond to the modified elastomer (A) described below, was measured by the following procedure: 5 g of modified elastomer (A) was dissolved in 180 ml of toluene, 20 ml of ethanol was added, and the solution was titrated with a 0.1 mol / L potassium hydroxide solution, and the amount of modification was calculated using the following formula. Maleic anhydride modification amount (phr) = titration amount x 5.611 / sample amount x 98 x 100 / 56.11 x 1000 On the other hand, the acid anhydride modification amounts of modified TPE-2-1 to modified TPE-2-4 described below are not accurate because modified TPE-2-1, modified TPE-2-2, and modified TPE-2-4 contain basic compounds in the polymer, and the above-mentioned titration cannot be used to determine the exact modification amounts. 1 The acid anhydride modification rate was calculated using H-NMR. Specifically, the integral value (α) of the proton (—CH2—OH) (3.3 ppm) of the carbon bearing the terminal hydroxyl group in the unmodified elastomer (AO) in modified TPE-2-1 to modified TPE-2-4 and the integral value (β) of the proton (—CH2—OOC—) (3.6 to 4.0 ppm) of the carbon bonded to succinic anhydride in the modified elastomer (A) were used to calculate β / (α+β), and this value was taken as the acid anhydride modification rate. The amount of acid anhydride modification was then calculated from the acid anhydride modification rate.

[0143] (9) Glass transition temperature of modified elastomer (A) The glass transition temperatures of the modified elastomers a-1 to a-3 described below, which are the modified elastomer (A), were measured using a DSC measurement device (DSC250 manufactured by TA Instruments Japan Co., Ltd.) Specifically, using the above device, measurements were performed under conditions of a temperature range of -120°C to +350°C and a heating rate of 10°C / min, and the temperature at the inflection point of the baseline shift due to the glass transition was taken as the glass transition temperature.

[0144] [Manufacturing Example 1] (Production of hydrogenated block copolymer (TPE-1)) A pressure vessel that had been purged with nitrogen and dried was charged with 50 kg of cyclohexane as a solvent and 87 g of a cyclohexane solution of 10.5 mass % sec-butyllithium as an anionic polymerization initiator (effective amount of sec-butyllithium added: 9.14 g). After the temperature inside the pressure vessel was raised to 50°C, 1.0 kg of styrene (1) was added and polymerization was carried out for 1 hour. At a vessel temperature of 50°C, 63 g of 2,2-di(2-tetrahydrofuryl)propane (DTHFP) was added as a Lewis base, and a mixed solution of 8.16 kg of isoprene and 6.48 kg of butadiene was added over 5 hours at the average diene feed rate shown in Table 2, followed by polymerization for 2 hours. Further, 1.0 kg of styrene (2) was added and polymerization was carried out for 1 hour. Methanol was added to terminate the reaction, thereby obtaining a reaction liquid containing a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer. A Ziegler hydrogenation catalyst formed from nickel octylate and trimethylaluminum was added to the reaction solution under a hydrogen atmosphere, and the mixture was reacted for 5 hours under conditions of a hydrogen pressure of 1 MPa and 80° C. After allowing the reaction solution to cool and release the pressure, the catalyst was removed by washing with water, and the mixture was dried in vacuo to obtain a hydrogenated product of polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer (hereinafter referred to as TPE-1). The raw materials and the amounts used are shown in Table 2. The results of the physical property evaluation are shown in Table 3.

[0145] [Production Example 2] (Production of hydrogenated block copolymer (TPE-2)) Assuming that the amounts of each raw material used are as shown in Table 2, after reacting ethylene oxide as a terminator and then reacting methanol, a hydrogenated product of a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer having a hydroxy group at the molecular end (hereinafter referred to as TPE-2) was obtained in the same procedure as in Production Example 1. Each raw material and its usage amount were shown in Table 2. Also, the results of the physical property evaluation were shown in Table 3.

[0146] [Table 2]

[0147] [Table 3]

[0148] The hydrogenated product TPE-1 of the block copolymer of Production Example 1 shows that the peak top intensity of tanδ is 1.0 or more, and since the temperature range where tanδ≥1.0 is wide, it can be said that it is suitable for a wide range of applications as a vibration damping material. In particular, it can be seen that the tanδ intensity at 20°C and 30°C is high and the vibration damping property near room temperature is excellent. The hydrogenated product TPE-2 of the block copolymer of Production Example 2 has a glass transition temperature of -55°C and is excellent in impact resistance and heat shock resistance. In addition, for the above TPE-2, there is no temperature range where tanδ≥1 on the lower temperature side than the peak of tanδ.

[0149] <Preparation of Reactant (C) and Resin Composition (D) Using TPE-1> Reactant (C) and resin composition (D) were prepared by the following procedure. The components used for the preparation of resin composition (D) are as follows. (Hydrogenated Block Copolymer) · The above TPE-1 (Modifier) · Maleic anhydride (radical initiator) Peroxide 1: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B-40, manufactured by Nippon Oil & Fats Co., Ltd.) (base catalyst) N,N-dimethyl-4-aminopyridine (Reactive Compound (B)) S-Ox-1: Epocross RPS-1005 manufactured by Nippon Shokubai Co., Ltd. S-GMA-1: NOF Corporation "Marproof G-0130SP" Epoxy-1: DIC Corporation's "EPICLON N-673" (cresol novolac epoxy resin)

[0150] [Manufacturing Examples 3 to 5] (Production of Resin Compositions D-1 and D-2 and Modified Elastomer a-1) Using a twin-screw extruder (Coperion "ZSK26mc" (26 mmφ, L / D=56)), the components were melt-kneaded at a cylinder temperature of 210°C and a screw rotation speed of 300 rpm, in accordance with the formulations shown in Table 4. In this way, TPE-1 was modified, and resin compositions D-1 and D-2 were obtained in which the modified product was covalently bonded to reactive compound (B) (i.e., resin compositions D-1 and D-2 were produced by the second production method described above). In addition, modified elastomer a-1, which is the modified elastomer (A), was obtained by carrying out a modification reaction under the same conditions as above using the same formulation as resin composition D-1 of Production Example 3 shown in Table 4, except that the reactive compound (B) was not added. The glass transition temperature of modified elastomer a-1 was 4°C, and the amount of maleic anhydride modification was 0.15 phr. The reactive compound (B) was side-fed into the extruder. The modified elastomer a-1 was used to measure the glass transition temperature and the amount of maleic anhydride modification of the modified elastomer (A).

[0151] [Manufacturing Examples 6 to 10] (Production of Resin Compositions D-3 to D-5, Modified Elastomers a-2 and a-3) Using a twin-screw extruder (Coperion "ZSK26mc" (26 mmφ, L / D=56)), the components were melt-kneaded at a cylinder temperature of 210°C and a screw rotation speed of 300 rpm, with the formulations shown in Table 5. In this way, TPE-1 was modified, and resin compositions D-3 to D-5 were obtained in which the modified product was covalently bonded to reactive compound (B) (i.e., resin compositions D-3 to D-5 were produced by the second production method described above). In addition, modified elastomers a-2 and a-3, which are modified elastomers (A), were obtained by carrying out a modification reaction under the same conditions as above using the same formulations as in Production Examples 6 and 7 shown in Table 5, except that reactive compound (B) was not added. The glass transition temperature of modified elastomer a-2 was 4°C, and the amount of maleic anhydride modification was 0.13 phr. The glass transition temperature of modified elastomer a-3 was 4°C, and the amount of maleic anhydride modification was 0.2 phr. The reactive compound (B) was side-fed into the extruder. The modified elastomers a-2 and a-3 were used to measure the glass transition temperature and the amount of maleic anhydride modification of the modified elastomer (A).

[0152] [Residual amount of reactive compound (B) in resin composition] In order to confirm the degree of reaction of the reactive compound (B) for resin compositions D-1 to D-5, the obtained resin compositions were reprecipitated to remove unreacted reactive compound (B). The amount of reactive compound (B) remaining in each resin composition was measured based on the change in weight before and after reprecipitation. The results are shown in Tables 4 and 5.

[0153] [Table 4]

[0154] [Table 5]

[0155] <Preparation of Dispersion Composition> [Examples 1 and 2] [Comparative Examples 1 and 2] The matrix resin (E) was a mixture (PC / ABS) of the following polycarbonate resin (PC) and ABS resin (ABS), and the dispersion compositions of Examples 1 and 2 and Comparative Example 1 were prepared by melt-kneading the mixture in the formulation shown in Table 6 using a twin-screw extruder ("ZSK26Mc" manufactured by Coperion) under conditions of a cylinder temperature of 250°C and a screw rotation speed of 300 rpm. The measurement results are shown in Table 6 below. Table 6 also lists measurement data for Comparative Example 2, where only PC / ABS was used. In Table 6, the dispersion composition containing reactant (C) is indicated by the symbol "Y," and the dispersion composition not containing reactant (C) is indicated by the symbol "N." The same applies to Tables 7 and 10 to 13 described below. <Resin> PC / ABS: "Iupilon MB2212R" (Mitsubishi Engineering Plastics Corporation)

[0156] [Examples 3 to 6] [Comparative Examples 3 to 6] The dispersion compositions of Examples 3 to 6 and Comparative Examples 3 to 5 were prepared by melt-kneading the following polyphenylene sulfide (PPS) resin as the matrix resin (E) in the formulation shown in Table 7 using a twin-screw extruder ("ZSK26Mc" manufactured by Coperion) under conditions of a cylinder temperature of 300°C and a screw rotation speed of 300 rpm. Table 7 also lists measurement data for Comparative Example 6, in which only PPS resin was used. For Example 6, the obtained dispersion composition was immersed in toluene, in which the matrix resin (E) is insoluble, and the components eluted in toluene were reprecipitated to obtain components other than the matrix resin (E). GPC analysis of the obtained components confirmed that a component with a molecular weight equal to the combined molecular weight of (A) and (B) was produced, indicating that the reaction product (C) was produced. <Resin> PPS resin: "Torelina A900" (manufactured by Toray Industries, Inc.)

[0157] [Physical property evaluation] The procedures for evaluating the physical properties of the compositions thus obtained are as follows: Note that the volume average dispersed particle diameter was not measured for molded articles in which a core-shell structure was not observed.

[0158] (Loss coefficient at 0℃, 20℃, 40℃, 60℃, 80℃ and 100℃) The resulting composition was injection molded using an injection molding machine ("EC75SX," manufactured by Toshiba Machine Co., Ltd.) to produce a sheet measuring 200 mm long x 40 mm wide x 2 mm thick. This sheet was cut into a piece measuring 200 mm long x 10 mm wide x 2 mm thick, and a contact tip was attached to the center using an adhesive whose main component was α-cyanoacrylate to prepare a sample. Next, the sample was set in a loss factor measurement system (Brüel & Kjær, vibrator type 4809; impedance head type 80001). A contact tip attached to the center of the sample was attached to the tip of the excitation force detector built into the impedance head. Vibrations were applied to the center of the laminate at frequencies ranging from 0 to 8,000 Hz, and the excitation force and acceleration waveform at this point were detected. A damping test was performed using the central excitation method in accordance with JIS K 7391 (2008), and acceleration signals representing the excitation force and acceleration waveform at the center were detected. Measurements were performed on each sample at temperatures of 0°C, 20°C, 40°C, 60°C, 80°C, and 100°C. The mechanical impedance at the excitation point (the center of the sample where vibration was applied) was calculated based on the obtained excitation force and the velocity signal obtained by integrating the acceleration signal. An impedance curve was then created with the horizontal axis representing frequency and the vertical axis representing the mechanical impedance, and the loss factor of the sample at each temperature was calculated from the full width at half maximum of the second peak (2nd mode) counting from the low frequency side. The larger the loss factor, the greater the vibration damping effect. The results are shown in Tables 6 and 7.

[0159] (Formation of core-shell structure) The obtained composition was injection molded using an injection molding machine ("EC75SX", manufactured by Toshiba Machine Co., Ltd.) to prepare a sheet measuring 200 mm in length, 40 mm in width, and 2 mm in thickness. This sheet was cut into a piece measuring 200 mm in length, 10 mm in width, and 2 mm in thickness to prepare a test piece. The cross section of this test piece was observed using a transmission electron microscope (TEM) to confirm the presence or absence of a core-shell structure. After cutting, the test piece was embedded in epoxy resin, ultrathinly sliced ​​to approximately 100 μm, and stained with ruthenium tetroxide for cross-sectional observation. Enlarged cross-sectional photographs of Example 2 observed using TEM are shown in FIGS. 3 and 4.

[0160] (Volume average dispersed diameter) The test piece used for measuring tan δ was freeze-fractured using liquid nitrogen, and the cross section was etched with xylene, followed by platinum deposition to prepare a sample, which was then observed using an SEM. In the obtained image, the average value of the major axes of 50 pores removed by etching was taken as the volume-average dispersed diameter. The results are shown in Tables 6 to 7. The volume-average dispersed diameter was also measured in the same manner for Examples 7 to 13 and Comparative Examples 7 to 9, which will be described later, and the results are shown in Tables 10 to 12.

[0161] (Extrusion processability) In Examples 3 to 6 and Comparative Examples 3 to 5, the strands coming out of the twin-screw extruder were pelletized using a pelletizer (water-cooled pelletizer KM-150N, manufactured by Katsu Seisakusho Co., Ltd.). When pellets were obtained, the result was rated "A," and when pellets were not obtained due to poor cutting of the strands, the result was rated "C." The results are shown in Table 7. For Comparative Example 6, PPS was molded and pelletized using the same procedure, and the extrusion processability was evaluated.

[0162] (Appearance of molded product) The resulting resin composition was injection molded using an injection molding machine ("EC75SX," manufactured by Toshiba Machine Co., Ltd.) to produce a sheet measuring 200 mm in length, 40 mm in width, and 2 mm in thickness. The appearance of this molded product was visually inspected, and if there was any appearance defect such as surface peeling, it was rated "C," and if there was no defect, it was rated "A." The results are shown in Table 7.

[0163]

Table 6

[0164]

Table 7

[0165] From Tables 6 and 7, it can be seen that in the molded products 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 loss factor values at 0°C to 100°C can be increased. Also, it can be seen that the molded products using the dispersion compositions of Examples 3 to 6 exhibit good extrusion moldability and have good appearance. On the other hand, in the molded products using the dispersion composition of Comparative Example 1 that does not contain reactant (C), the dispersion diameter is very large compared to those of the examples, the dispersibility is inferior to the molded products of Examples 1 and 2, and the loss factor from room temperature to low temperature also tends to decrease compared to the molded products of Examples 1 and 2. Also, the molded products using the compositions of Comparative Examples 3 and 5 that do not contain reactant (C) also have a very large dispersion diameter compared to the molded products of Examples 3 to 6 and have poor appearance. In particular, it can be seen that the loss factor of the molded product of Comparative Example 3 at low temperature and high temperature is lower than that of the molded products of Examples 3 to 6. Furthermore, it can be seen that the molded product using the composition of Comparative Example 4 that does not contain reactant (C) does not form a core-shell structure and is also inferior in extrusion processability.

[0166] <Preparation of Reactant (C) and Resin Composition (D) Using TPE-2> Reactant (C) and resin composition (D) were prepared by the following procedure. The components used for the preparation of resin composition (D) are as follows. (Hydrogenated product of block copolymer) ·The above TPE-2 (Modifier) ·Succinic anhydride (Base catalyst) ·N,N-Dimethyl-4-aminopyridine ·4-Pyrrolidinopyridine [[ID=4?]] (Reactive Compound (B)) Epoxy-1: DIC Corporation's "EPICLON N-673" (cresol novolac epoxy resin) Epoxy-2: "TETRAD-C" (tetrafunctional glycidylamine epoxy resin) manufactured by Mitsubishi Gas Chemical Company, Inc.

[0167] [Manufacturing Examples 11 to 14] (Production of Modified TPE-2-1 to Modified TPE-2-4) The raw materials and their amounts shown in Table 8 were melt-kneaded for 10 minutes at 150°C using an MS-type pressure kneader (manufactured by Moriyama Corporation). This resulted in succinic anhydride being bonded to the terminal hydroxyl groups of the hydrogenated block copolymer TPE-2, producing modified elastomers Modified TPE-2-1 to Modified TPE-2-4, which have functional groups at the molecular terminals that can react with oxazoline or epoxy groups.

[0168] [Manufacturing Examples 15-24] The modified TPE-2-1 to modified TPE-2-4 were melt-kneaded for 15 minutes at 150°C using an MS-type pressure kneader (manufactured by Moriyama Corporation) in the same manner as above, using the raw materials and amounts shown in Table 9. This yielded resin compositions D-6 to D-15 in which modified TPE-2-1 to modified TPE-2-4 were covalently bonded to reactive compound (B) (i.e., resin compositions D-6 to D-15 were produced by the first production method described above).

[0169] [Content of reactant (C) in resin composition] For resin compositions D-6 to D-15, the modification rates from the modified TPE-2-1 to modified TPE-2-4 to the reaction product (C) were measured by the following procedure. First, 5 g of the obtained resin composition was completely dissolved in 50 mL of toluene to obtain a solution. Next, 100 mL each of acetone and methanol, which are poor solvents, was added to the solution and stirred. After that, the resulting precipitate was obtained on a nylon mesh ("N-NO.200HD" manufactured by NBC Meshtec Co., Ltd.) by filtration. The obtained precipitate was dried to obtain a resin composition from which the unreacted reactive compound (B) had been removed. 1 g of the resin composition obtained as described above was completely dissolved in 10 mL of THF to obtain a solution. Next, 5 mL of 0.2 N hydrochloric acid was added to the solution and stirred for 30 minutes, allowing the hydrochloric acid to react with the epoxy groups in the resin composition. The excess hydrochloric acid was then titrated with a 0.1 N potassium hydroxide ethanol solution, and the amount of epoxy group modification was calculated using the following formula. The content of reactant (C) in the resin composition was then calculated from the amount of epoxy group modification using the following formula. Amount of epoxy group modification (mol / g) = (blank titer (L) - titer (L)) x 0.1 Content (mass%) of reactant (C) in resin composition = (weight average molecular weight of TPE-2 × epoxy group modification amount (mol / g)) / (number of epoxy groups in one molecule of reactive compound (B) - 1) In addition, for the blank titration, the same procedure was performed without adding modified TPE, and the titration amount was determined. The mass of the reactive compound (B) contained in the resin composition was then calculated from the content of the reactant (C) in the resin composition. Furthermore, the reaction rate, expressed as C / (B+C), was calculated, where B is the content of the reactive compound (B) in the resin composition by mass% and C is the content of the reactant (C) by mass%. The results are shown in Table 9.

[0170] [Table 8]

[0171] [Table 9]

[0172] <Preparation of Dispersion Composition> [Example 7] [Comparative Example 7] Using the same PC / ABS as used in Example 1 above as the matrix resin (E), a dispersion composition was prepared according to the formulation shown in Table 10 in the same manner as in Example 1 above.

[0173] [Examples 8 to 10] [Comparative Example 8] The dispersion compositions of Examples 8 to 10 and Comparative Example 8 were prepared by using the following polybutylene terephthalate (PBT) as the matrix resin (E) and the formulation shown in Table 11, and melt-kneading the mixture using a twin-screw extruder ("ZSK26Mc" manufactured by Coperion) under conditions of a cylinder temperature of 250°C and a screw rotation speed of 300 rpm. <Resin> PBT: "Toraycon 1401" (manufactured by Toray Industries, Inc.)

[0174] [Examples 11 to 13] [Comparative Example 9] The dispersion compositions of Examples 11 to 13 and Comparative Example 9 were prepared using the same PPS resin as used in Example 3 above as the matrix resin (E) and the formulations shown in Table 12 using the same procedure as in Example 3 above. Glass fiber (GF): "ECS03T-717H / PW" (manufactured by Nippon Electric Glass Co., Ltd.)

[0175] [Examples 14 to 17] [Comparative Example 10] The dispersion compositions of Examples 14 to 17 and Comparative Example 10 were prepared by melt-kneading the following liquid crystal polymers (LCPs) in the formulations shown in Table 13 using a twin-screw extruder ("ZSK26Mc" manufactured by Coperion) under conditions of a cylinder temperature of 300°C and a screw rotation speed of 300 rpm. Here, in Examples 14, 16, 17, and Comparative Example 1, the LCP was the matrix resin (E), and in Example 15, the LCP was the domain resin (F). <Resin> LCP: "LAPEROS A130" (manufactured by Polyplastics Co., Ltd.)

[0176] [Physical property evaluation] The procedures for evaluating the physical properties of the composition thus obtained are as follows. (Tensile test) The resin composition was injection molded using an injection molding machine "SE100DU-C250" (manufactured by Sumitomo Heavy Industries, Ltd.) to prepare an ISO multipurpose test piece (type A). Using the above test specimens, the tensile strength (MPa), tensile elongation at break (%), and tensile modulus (GPa) were measured in accordance with JIS K7161-1 (2014) (ISO 527-1:2012).

[0177] (bending test) The resin composition was injection molded using an injection molding machine "SE100DU-C250" (manufactured by Sumitomo Heavy Industries, Ltd.) to prepare an ISO multipurpose test piece (A type), which was then cut to a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. Using the above test pieces, the flexural strength (MPa) and flexural modulus (GPa) were measured in accordance with JIS K7171 (2016) (ISO 178:2010).

[0178] (Impact resistance test) The resin composition was injection molded using an injection molding machine "SE100DU-C250" (manufactured by Sumitomo Heavy Industries, Ltd.) to prepare an ISO multipurpose test piece (A type), which was then cut to a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. After notching the above test pieces, the impact strength (kJ / m) was measured by a Charpy impact test in accordance with JIS K7111 (2012) (ISO 179:2010). 2 ) was measured.

[0179] [Table 10]

[0180] [Table 11]

[0181] [Table 12]

[0182] [Table 13]

[0183] Table 10 shows that the molded article made from the dispersion composition of Example 7, which contains resin composition D-6 obtained by melt-kneading modified TPE-2-1 and an epoxy resin, has high compatibility with PC / ABS and can achieve a very small dispersion diameter. In contrast, the molded article made from the dispersion composition of Comparative Example 7, which does not contain reactant (C), has a larger dispersion diameter and less uniform dispersion than Example 7. As a result, Example 7, which contains D-6, has excellent tensile properties and impact strength.

[0184] Similarly, Tables 11 and 12 show that resin compositions D-7 to D-9 have high compatibility with PBT and PPS, and that the dispersion diameter of molded articles made from dispersion compositions containing these compositions can be made very small. As a result, these molded articles have improved impact strength without significantly reducing the elastic modulus.

[0185] Furthermore, Table 13 shows that 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 these compositions have significantly improved tensile elongation at break compared to the molded article of Comparative Example 10 containing TPE-2, making them highly flexible compositions. [Industrial Applicability]

[0186] The resin composition of the present invention exhibits high compatibility with many types of resins, and can therefore be used as a resin modifier for resins used in a wide range of fields, such as automobiles, electrical appliances, building materials, etc. Furthermore, the dispersion composition of the present invention has good moldability and good mechanical properties, such as high vibration damping over a wide temperature range, and can therefore be used in pellets, bales, vibration damping materials, sound insulation materials, compatibilizers, shoe sole materials, flooring materials, adhesives, pressure-sensitive adhesives, laminates, fibers, and automobile parts, etc. [Explanation of symbols]

[0187] 10, 11: Core-shell structure 10a, 11a: Core 10b, 11b: Shell 11b, 11c, 11d: Domain 20: Matrix

Claims

1. A resin composition comprising a reaction product (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 (i) a block copolymer having a polymer block (A-1) mainly composed of structural units derived from an aromatic vinyl compound and a polymer block (A-2) mainly composed of structural units derived from a conjugated diene compound, each of which has a functional group capable of reacting with an oxazoline group or an epoxy group, or (ii) a hydrogenated product of the block copolymer, wherein the conjugated diene compound contains isoprene. [II] The reactive compound (B) is a thermoplastic resin having one or more skeletons selected from the group consisting of polystyrene, polyacrylic acid ester, polymethacrylic acid ester, and polyolefin, and having two or more groups per molecule selected from the group consisting of oxazoline groups and epoxy groups.

2. 2. The resin composition according to claim 1, wherein the content of the reactant (C) is 1 to 100% by mass based on the total mass of the resin composition.

3. The resin composition according to claim 1 or 2, further comprising at least one of a modified elastomer (A) and a reactive compound (B).

4. The resin composition according to claim 3, wherein 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 or less, based on the total mass of the resin composition.

5. The resin composition according to any one of claims 1 to 4, wherein the content of the reactive compound (B) contained in the resin composition is B mass% and the content of the reactant (C) is C mass%, and the value of C / (B+C) is 0.1 to 1.

0.

6. The resin composition according to any one of claims 1 to 5, wherein the modified elastomer (A) is a compound having at least one group selected from a carboxy group and a group derived from an acid anhydride, and the amount of modification is 0.01 to 1.0 phr, expressed in parts by mass per 100 parts by mass of the modified compound.

7. The resin composition according to claim 6, wherein the reactant (C) contains at least one of the structures represented by the following formulas (1) to (4): 【Chemical 1】

8. The resin composition according to any one of claims 1 to 7, wherein the modified elastomer (A) has a glass transition temperature of -100 to -30°C.

9. The resin composition according to any one of claims 1 to 7, wherein the modified elastomer (A) has a glass transition temperature of -30 to +40°C.

10. The resin composition according to any one of claims 1 to 9, wherein the modified elastomer (A) is a modified product of a hydrogenated 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.

11. The resin composition according to claim 10, wherein the content of the polymer block (A-1) in the modified elastomer (A) is 35% by mass or less.

12. The resin composition according to claim 10 or 11, wherein the hydrogenation rate of the polymer block (A-2) is 88 mol% or more.

13. 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 to 400,000.

14. The resin composition according to any one of claims 1 to 13, wherein the modified elastomer (A) has a functional group capable of reacting with an oxazoline group or an epoxy group at a molecular end.

15. The resin composition according to any one of claims 1 to 14, wherein the total content of the epoxy group and the oxazoline group in the reactive compound (B) is 0.1 to 30 phr, expressed in parts by mass per 100 parts by mass of the reactive compound (B).

16. The resin composition according to any one of claims 1 to 15, wherein the content of resin components contained other than the reactant (C), the modified elastomer (A), the reactive compound (B), and the elastomer (A0) before modification is 0 to 50 mass%.

17. A resin modifier comprising the resin composition according to any one of claims 1 to 16.

18. A dispersion composition comprising the resin composition according to any one of claims 1 to 16 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).

19. 19. The dispersion composition according to claim 18, wherein the matrix resin (E) is at least one resin selected from the group consisting of polyamide resins, polyester resins, polyacetal resins, polyphenylene sulfide resins, polyphenylene ether resins, polyarylate resins, polyethersulfone resins, epoxy resins, styrene-based resins, and polycarbonate resins.

20. 20. The dispersion composition according to claim 18 or 19, wherein, in the dispersion composition, when the mass of the first resin composition (D) is D and the mass of the matrix resin (E) is E, D / E is in the range of 1 / 99 to 50 / 50.

21. An automotive component comprising the dispersion composition according to any one of claims 18 to 20.

22. A method for producing the resin composition according to any one of claims 1 to 16, A method for producing a resin composition, comprising mixing a modified elastomer (A) and a reactive compound (B) in a molten state to react them to produce a reaction product (C).

23. A method for producing the resin composition according to any one of claims 1 to 16, A method for producing a resin composition, comprising adding a radical initiator and at least one of a carboxy group-containing compound and an acid anhydride to a block copolymer or a hydrogenated product of the block copolymer in a molten state, and then adding a reactive compound (B) to introduce at least one of a carboxy group and a group derived from the acid anhydride into the block copolymer or the hydrogenated product of the block copolymer and reacting the reactive compound (B).

24. A method for producing the resin composition according to any one of claims 1 to 16, A method for producing a resin composition, comprising adding at least one of a carboxy group-containing compound and an acid anhydride to a block copolymer or a hydrogenated product of the block copolymer in a molten state, introducing at least one of a carboxy group and a group derived from the acid anhydride into the block copolymer or the hydrogenated product of the block copolymer, and then adding a reactive compound (B) to react the reactive compound (B) with the block copolymer or the hydrogenated product of the block copolymer into which at least one of a carboxy group and a group derived from the acid anhydride has been introduced.

25. The content of the reactive compound (B) contained in the resin composition is B mass%, and the content of the reactant (C) is C mass%, and the reaction rate represented by C / (B+C) is 0.1 to 1.

0. A method for producing a resin composition according to any one of claims 22 to 24.

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