TWI818643B - Resin composition, method for producing resin composition, and molded article - Google Patents

Abstract

A resin composition comprising: Component (I): resin with polar groups (except component (II)); Component (II): at least one modified conjugated diene polymer, which has a polar group bonded to a block polymer, and the above block polymer has: From the polymer block (A) mainly composed of vinyl aromatic monomer units, the polymer block (B) mainly composed of conjugated diene monomer units, and the vinyl aromatic monomer units and conjugated At least two types of polymer blocks in the random polymer block (C) of the diene monomer unit, the above-mentioned polar groups are selected from anhydride group, hydroxyl group, carboxyl group, dicarboxyl group, epoxy group, and oxetanyl group and at least one of the group consisting of amine groups; and The above-mentioned resin composition has a continuous phase (A) of the component (I), and a dispersed phase (B) containing the component (II) dispersed in the continuous phase (A). The number average dispersed particle size of the dispersed phase (B) is: Below 1.5 μm, The mass ratio of ingredient (I): ingredient (II) = 50/50~99/1.

Description

Resin composition, method for producing resin composition, and molded article

The present invention relates to a resin composition, a method for producing the resin composition, and a molded article.

It is known that conjugated diene polymers exhibit various characteristics by adjusting the ratio of 1,2-bonds, the ratio of blocks constituting the conjugated diene polymer, the arrangement of the blocks, the degree of hydrogenation, and the like. In addition, in order to provide more characteristics, conjugated diene-based polymers (hereinafter referred to as modified conjugated diene polymers) having affinity groups that can generate molecular forces with other materials or reactive groups that can form chemical bonds have been proposed. vinyl polymers). For example, Patent Document 1 proposes an amine-modified conjugated diene polymer obtained by reacting an amine group-containing compound with the terminal end of a conjugated diene polymer.

On the other hand, resins having polar groups (hereinafter sometimes referred to as polar resins) are generally excellent in rigidity, chemical resistance, heat resistance, etc., but are hard and brittle, so various modifiers have been studied in the past. Modified conjugated diene polymers have excellent compatibility with polar resins due to molecular forces such as reactions or hydrogen bonds caused by the modified groups, and therefore can be widely used as modifiers for polar resins. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2014-210848

[Problem to be solved by the invention]

In recent years, as automobiles, home appliances, communication equipment, etc. become more advanced and IoT becomes more popular, the lightweight and electrical components of each component are promoted. Heat resistance, chemical resistance, flame retardancy, mechanical properties, etc. The demand for polar resins with excellent strength, dimensional stability, electrical insulation, and dielectric properties is increasing. On the other hand, electronic materials are required to be able to withstand impacts during manufacturing and use. In addition, safety awareness in automobile parts is gradually increasing, and it is necessary to improve the impact resistance and toughness of hard and brittle polar resins, which has become an issue. . For example, in Patent Document 1, regarding the toughness improvement of polyphenylene sulfide resin (hereinafter, sometimes referred to as "PPS"), a resin composition containing a modified conjugated diene polymer having better toughness than PPS is proposed. . However, according to the research of the present inventors, the resin composition disclosed in Patent Document 1 has the following problem: the toughness is not sufficient and there is room for improvement.

Therefore, in the present invention, in view of the above-mentioned problems of the prior art, an object is to provide a resin composition excellent in impact resistance and toughness. [Technical means to solve problems]

The present inventors conducted diligent research in order to solve the above-mentioned prior art problems, and found that the above-mentioned prior art problems can be solved by the following resin composition, which contains a resin having a polar group ( Component (I)), and a modified conjugated diene polymer having a specific polar group (component (II)), which is specified as: a dispersed phase (B) containing the modified conjugated diene polymer ) has a specific number average dispersed particle diameter, and the above-mentioned resin having a polar group (component (I)) and the above-mentioned modified conjugated diene polymer (component (II)) have a specific mass ratio. That is, the present invention is as follows.

[1] A resin composition comprising: Component (I): a resin having a polar group (except component (II) below); Component (II): at least one modified conjugated diene polymer, the The modified conjugated diene-based polymer is one in which a polar group is bonded to a block polymer, and the block polymer has: A polymer block (A) selected from the group consisting of polymer blocks containing vinyl aromatic monomer units as the main body. , at least 2 of the polymer block (B) mainly composed of conjugated diene monomer units, and the random polymer block (C) of vinyl aromatic monomer units and conjugated diene monomer units. A polymer block, the above-mentioned polar group is at least one selected from the group consisting of anhydride group, hydroxyl group, carboxyl group, dicarboxyl group, epoxy group, oxetanyl group and amine group; the above-mentioned resin composition has the above-mentioned components The continuous phase (A) of (I), and the dispersed phase (B) containing the above-mentioned component (II) dispersed in the above-mentioned continuous phase (A), the number average dispersed particle size of the above-mentioned dispersed phase (B) is 1.5 μm or less , the mass ratio of the above component (I) to the above component (II) is component (I): component (II) = 50/50~99/1. [2] The resin composition of [1] above, further comprising component (III): a polymer having a polar group reactive with the component (I) and/or component (II) (the component (I) above) , except (II)); The mass ratio of the above-mentioned component (II) to the above-mentioned component (III) is component (II): component (III) = 1/99~99/1. [3] The resin composition of [1] above, wherein the component (I) is selected from the group consisting of polyphenylene sulfide resin, polyethylene terephthalate resin, and polybutylene terephthalate resin. , and at least one resin in the group consisting of epoxy resin. [4] The resin composition of [2] above, wherein the component (I) is selected from the group consisting of polyphenylene sulfide resin, polyethylene terephthalate resin, and polybutylene terephthalate resin. , and at least one resin in the group consisting of epoxy resin. [5] The resin composition according to any one of the above [1] to [4], wherein the above component (II) contains a hydrogenated modified conjugate derived from the hydrogenation of an aliphatic double bond of a conjugated diene compound. Diene polymer. [6] The resin composition according to any one of [1] to [5] above, wherein the component (I) is a polyphenylene sulfide resin. [7] The resin composition according to any one of the above [1] to [6], wherein the above component (II) contains a modification bonded with at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group. Conjugated diene polymer. [8] The resin composition according to any one of the above [2] to [7], wherein the above component (III) has a group selected from the group consisting of epoxy group, oxazolinyl group, and oxetanyl group Polymers containing at least one polar group. [9] The resin composition according to any one of [2] to [8] above, wherein the component (III) is an olefin elastomer having an epoxy group. [10] The resin composition according to any one of [5] to [9] above, wherein the hydrogenation rate of the hydrogenation-modified conjugated diene polymer is 90% or less. [11] The resin composition according to any one of the above [1] to [10], wherein the content of vinyl aromatic monomer units in the above component (II) is 40 mass % or less. [12] The resin composition according to any one of the above [2] to [11], wherein the component (III) is a copolymer of a polymerizable monomer having an epoxy group and an unsaturated hydrocarbon compound having a ring. Oxygen-based elastomer. [13] The resin composition according to any one of the above [2] to [12], wherein the above component (III) is a polymerizable monomer having an epoxy group, an unsaturated hydrocarbon compound, and a (meth)acrylate. and/or copolymers of vinyl acetate. [14] A method for producing a resin composition, which has the following steps: A modified conjugated diene polymer (component (II)) containing a polymer selected from the group consisting of polymers containing vinyl aromatic monomer units as a main body Block (A), polymer block (B) composed mainly of conjugated diene monomer units, and random polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units ), and at least 1 polar group selected from the group consisting of hydroxyl and carboxyl groups; a resin (component (I)) having a polar group, which is selected from polyphenylene sulfide At least one kind from the group consisting of ether resin, polyethylene terephthalate resin, and polybutylene terephthalate resin; and an olefin elastomer (component (III)), which has At least one polar group selected from the group consisting of an epoxy group, an oxetanyl group, and an oxetanyl group; the above-mentioned resin having a polar group (component (I)) and the above-mentioned modified conjugated diene The mass ratio of the polymer (component (II)) is resin having a polar group: modified conjugated diene polymer = 50/50 to 99/1, and the above modified conjugated diene polymer and The mass ratio of the above-mentioned olefin-based elastomer having a polar group is set to modified conjugated diene-based polymer: olefin-based elastomer having a polar group = 1/99 to 99/1, and is kneaded to obtain a resin composition. The steps; and making the above-mentioned resin composition have a continuous phase (A) of the above-mentioned resin having a polar group (component (I)), and a polymer containing the above-mentioned modified conjugated diene dispersed in the above-mentioned continuous phase (A) The step is to reduce the number average dispersed particle diameter of the dispersed phase (B) to 1.5 μm or less. [15] A molded article, which is a molded article of the following resin composition, the resin composition containing: a resin (component (I)) having a polar group , which is selected from the group consisting of polyphenylene sulfide resin, polyterephthalene At least one of the group consisting of ethylene formate-based resin and polybutylene terephthalate-based resin; a modified conjugated diene-based polymer (component (II)) having an ethylene content selected from the group consisting of Polymer block (A) based on vinyl aromatic monomer units, polymer block (B) based on conjugated diene monomer units, vinyl aromatic monomer units and conjugated diene monomers At least two types of polymer blocks in the random polymer block (C) of the unit; and an olefin elastomer having an epoxy group (component (III)); the above-mentioned modified conjugated diene polymer (component (II)) It has at least one polar group selected from the group consisting of hydroxyl group and carboxyl group, and the above-mentioned molded article satisfies the following conditions (I-1) to (II-1): <Condition (I-1)> By molding The tensile elongation at break of a short strip test piece with a width of 10 mm, a length of 170 mm, and a thickness of 2 mm is at room temperature and at a tensile speed of 5 mm/min of 25% or more, <Condition (II- 1) The Charpy impact value of a short strip test piece of about 80 mm long, 10 mm wide and 4 mm thick obtained from the molded body in the Charpy impact test at -30°C is 15 kJ/m ² . [Effects of the invention]

According to the present invention, a resin composition excellent in impact resistance and toughness can be provided.

Hereinafter, the mode for implementing the present invention (hereinafter, referred to as “this embodiment”) will be described in detail. The following embodiments are examples for illustrating the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate changes within the scope of the gist of the invention.

[Resin composition] The resin composition of this embodiment includes: Component (I): resin with polar groups (except component (II) below); and Component (II): at least one modified conjugated diene polymer, which has a polar group bonded to a block polymer, and the block polymer has a component selected from the group consisting of Polymer block (A) containing vinyl aromatic monomer units as the main body, The polymer block (B) containing conjugated diene monomer units as the main body, and At least two polymer blocks in the random polymer block (C) of a vinyl aromatic monomer unit and a conjugated diene monomer unit, and the above-mentioned polar groups are selected from an acid anhydride group, a hydroxyl group, a carboxyl group, and a dicarboxylic group. At least one of the group consisting of , epoxy group, oxetanyl group and amine group. The above-mentioned resin composition has a continuous phase (A) of the above-mentioned component (I), and a dispersed phase (B) containing the above-mentioned component (II) dispersed in the above-mentioned continuous phase (A), and the number of the above-mentioned dispersed phase (B) is average. The dispersed particle size is 1.5 μm or less. The mass ratio of the above-mentioned component (I) to the above-mentioned component (II) is component (I): component (II)=50/50~99/1. By having the above-mentioned structure, a resin composition excellent in impact resistance and toughness is obtained.

(Component (I): resin with polar groups (except component (II) below)) The resin composition of this embodiment contains a resin having a polar group (hereinafter, may be described as polar resin (I), component (I)).

Generally speaking, from the viewpoint of entropy and enthalpy, resins with excellent rigidity have polar groups in the main chain. The polar resin (I) used in the resin composition of this embodiment is not limited to the following, and examples thereof include: acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene Methylene-styrene copolymer resin (MBS); polyvinyl chloride resin; polyvinyl acetate resin and its hydrolyzate; polymers of acrylic acid and its esters or amides; polyacrylate resin; as acrylonitrile and/or Nitrile resins of copolymers of methacrylonitrile polymers and other copolymerizable monomers containing more than 50% by mass of such acrylonitrile monomers; polyamide resins; polyester resins, thermoplastic polyamine-based Formate resin, polycarbonate polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate; thermoplastic polystyrene such as polyether styrene or polyallyl styrene; Polyoxymethylene resin; poly(2,6-dimethyl-1,4-phenylene) ether and other polyphenylene ether resins; polyphenylene sulfide resin; polyarylate resin; polyetherketone polymer or Copolymer; polyketone resin; Fluorine resin; polyethylene terephthalate resin; polyoxybenzyl polymer, polyimide resin; polyethylene terephthalate resin; polybutylene terephthalate Resin; epoxy resin, etc.

The preferred polar resin (I) varies depending on the characteristics required for the resin composition of the present embodiment. From the viewpoint of rigidity, polyethylene terephthalate-based resin or polyterephthalate resin is preferred. Butylene glycol resin, epoxy resin, and polyphenylene sulfide resin are preferred from the viewpoint of chemical resistance, and epoxy resin and polyphenylene sulfide resin are preferred from the viewpoint of heat resistance. Polyphenylene sulfide resin is preferred.

The polyethylene terephthalate resin only needs to belong to the category called polyethylene terephthalate resin, and it is more preferable that the polyethylene terephthalate resin is composed of a glycol component of at least 90 mol% of ethylene glycol. A thermoplastic resin obtained by polymerization of a dicarboxylic acid component consisting of at least 90 mol% of terephthalic acid.

The polybutylene terephthalate resin only needs to belong to the category called polybutylene terephthalate resin, and it can be made by using terephthalic acid or its derivatives as two of the main components. A polymer obtained by a common polymerization method such as polycondensation reaction between a carboxylic acid and a glycol containing 1,4-butanediol or its derivatives as the main component. The repeating unit of butylene terephthalate is preferably 90 mol%. or above, more preferably 95 mol% or above.

The epoxy resin only needs to belong to the category called epoxy resin. From the viewpoint of rigidity, it is preferable to have two or more epoxy groups in one molecule. One type of epoxy resin can be used alone, or two or more types can be used in combination. The epoxy resin is not limited to the following, and examples thereof include dixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol S type epoxy resin, Phenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol Type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, joint Benzene epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane epoxy resin, cyclohexanedimethanol epoxy resin, naphthyl ether Type epoxy resin, trimethylol type epoxy resin, and tetraphenylethane type epoxy resin, etc.

The polyphenylene sulfide-based resin only needs to belong to the category called polyphenylene sulfide resin. From the viewpoint of heat resistance, it is preferable that it contains 70 mol% or more of p-phenylene sulfide units as its structural unit. More preferably, it contains more than 90 mol% of p-phenylene sulfide units as its structural unit. Furthermore, as other structural units, for example, o-phenylene sulfide unit, m-phenylene sulfide unit, phenylene sulfide unit, phenylene sulfide trine unit, phenylene sulfide ketone unit, diphenyl sulfide unit, substituent-containing Phenyl sulfide units, phenyl sulfide units with branched structures, etc. From the viewpoint of the rigidity of the resin composition of the present embodiment, the molecular weight of the polyphenylene sulfide-based resin is preferably 5,000 or more, and more preferably 10,000 or more. The polyphenylene sulfide resin may be linear, cross-linked or branched. In addition, the polyphenylene sulfide-based resin may have a polar group such as a thiol group or a carboxyl group in the terminal or main chain of the polymer structure. The production method of the polyphenylene sulfide-based resin is not particularly limited, and an example thereof is a production method in which an alkali metal sulfide and a dihalogenated aromatic compound are reacted in a polymerization solvent.

(Component (II): modified conjugated diene polymer) The resin composition of this embodiment contains at least one modified conjugated diene polymer (hereinafter, sometimes described as modified conjugated diene polymer (II), component (II)). The conjugated diene polymer is one in which a polar group is bonded to a block polymer having a polymer block (A) containing a vinyl aromatic monomer unit as a main body, and a conjugated diene polymer At least two polymer blocks (B) consisting of a polymer block (B) composed of a diene monomer unit and a random polymer block (C) composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit. Paragraph, the above-mentioned polar group is at least one selected from the group consisting of anhydride group, hydroxyl group, carboxyl group, dicarboxyl group, epoxy group, oxetanyl group, and amine group. By having the modified conjugated diene polymer (II) having the above-mentioned polar group and having affinity and/or reactivity with the above-mentioned polar resin (I), the resin composition of the present embodiment can be improved. Toughness and impact resistance.

The above-mentioned affinity means that at least one intermolecular force selected from the group consisting of ionic interactions, hydrogen bonds, dipolar interactions, and Van der Waals forces can be generated between each component. The above-mentioned reactivity means that the polar groups of each component maintain covalent bonding with each other. Included in the following definition: When polar groups react with each other, if, for example, the OH of a carboxyl group is detached, the original polar group will change or disappear, and when a covalent bond is formed thereby, the polar groups show "reactivity" with each other. .

By allowing the modified conjugated diene polymer (II) to have an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an oxazoline group, an epoxy group, an oxetanyl group, and an amine group. At least one polar group among them has excellent affinity and/or reactivity with the above-mentioned polar resin (I), so the above-mentioned polar resin (component (I)) and the modified conjugated diene polymer (component (II) ) improves the compatibility, the number average dispersed particle size of the dispersed phase (B) containing component (II) in the continuous layer (A) containing component (I) becomes 1.5 μm or less, and the interface between the components can be strengthened, This helps improve impact resistance and toughness.

The preferred polar group of the modified conjugated diene polymer (II) also varies depending on the type of the polar resin (I) or the characteristics required for the resin composition of this embodiment. For example, when the polar resin (I) is a polyphenylene sulfide resin, the affinity of the epoxy group, oxazoline group, and amine group with the thiol group and carboxyl group present at the terminal of the polyphenylene sulfide resin And/or it has excellent reactivity, so it is preferred as the polar group of the modified conjugated diene polymer (II). Moreover, when the component (I) is an epoxy resin, the carboxyl group, the acid anhydride group, the hydroxyl group, and the dicarboxylic group have excellent affinity and/or reactivity with the epoxy group of the component (I). In this way, by providing each component (I) and (II) with an affinity group and/or a reactive group that exhibits affinity and/or reactivity between the components, the interface between the components can be strengthened and contribute to improving the Toughness and impact resistance of the resin composition of this embodiment. Furthermore, effects such as improvement in tracking resistance and suppression of physical property degradation (thermal cycle characteristics) when alternately exposed to high to low temperatures are also expected. These properties can be improved by controlling the compatibility state by adjusting the affinity or reactivity between the components.

For example, when the polar resin of the component (I) is a polyethylene terephthalate resin or a polybutylene terephthalate resin, the epoxy group, the amine group of the component (II) and the poly(p-butylene terephthalate) resin Ethylene phthalate resin and polybutylene terephthalate resin have excellent affinity and/or reactivity with the carboxyl groups present at the terminals, so each component exhibits affinity and reactivity between the components. /or reactive affinity groups and/or reactive groups can strengthen the interface between components and help improve the toughness and impact resistance of the resin composition. Furthermore, as the component (II), two types of modified conjugated diene polymers in which different polar groups derived from the above-mentioned polar groups are respectively bonded can also be used. From the viewpoint of the above compatibility, when using two types of modified conjugated diene polymers (II) each bonded with different polar groups, it is preferable to use one type of modified conjugated diene. The polymer is bonded with a polar group that is reactive with another modified conjugated diene polymer and the above-mentioned polar resin (I). For example, when the polar resin of the component (I) is a polyphenylene sulfide-based resin, a polyethylene terephthalate-based resin, or a polybutylene terephthalate-based resin, the component (II) may be It is preferable to use modified conjugated diene polymers bonded with epoxy groups and modified conjugated diene polymers bonded with carboxyl groups and/or hydroxyl groups. For example, when the polar resin of component (I) is an epoxy resin, the carboxyl group, hydroxyl group, and amino group have excellent affinity and/or reactivity with the epoxy group of the epoxy resin, so the polar resin can be used A modified conjugated diene-based polymer is preferably used as component (II). In this way, by providing each component with an affinity group and/or a reactive group that exhibits affinity and/or reactivity between the components, the interface between the components can be strengthened and contribute to improving the resin composition of the present embodiment. Toughness and impact resistance.

Generally, in a resin composition, the same components tend to agglomerate with each other to form a phase. However, in the resin composition of this embodiment, by having the above component (II) have a polar group, the above component (I) The affinity and/or reactivity of these components are improved, and the compatibility of these components is improved, so that the number average dispersed particle diameter of the following dispersed phase (B) is 1.5 μm or less, which helps to express the resin composition of this embodiment. impact resistance and toughness. From the viewpoint of compatibility with the polar resin (I), the amount of polar groups contained in the modified conjugated diene polymer (II) is preferably 0.3 mоl/chain or more, more preferably 0.5 mоl/ chain or more, and more preferably 0.6 mоl/chain or more. If the amount of polar groups in the modified conjugated diene polymer (II) is 0.3 mol/chain or more, the polymer chain having the above-mentioned affinity group or reactive group is compatible with the above-mentioned component (I) and does not have The polymer chains of the affinity group or the reactive group are compatible with the above-mentioned component (I) and the polymer chains are condensed as described above, whereby the number average dispersed particle size of the dispersed phase (B) can be set to 1.5 μm. below, preferably 1.3 μm or below. As long as the polar groups contained in component (I) and component (II) respectively have the required affinity and/or reactivity, the ease of compatibility and aggregation are better than the structure of the resin or the type of polar groups, The combination of polar groups between components has a greater impact on the frequency (amount) of polar groups in the polymer chain. Therefore, the number average dispersed particle diameter of the dispersed phase (B) can be controlled to a desired value by appropriately setting the amount of polar groups of component (II). In addition, if the affinity group or reactive group of component (II) is excessive, gelation or the like may occur in the resin composition of this embodiment, so it is preferably 30 mol/chain or less. Furthermore, the "chain" mentioned here refers to one molecule of polymer, and polymer structures branched through chemical bonds are also counted as one molecular chain. The amount of the polar group of the modified conjugated diene polymer (II) can be adjusted by adjusting the reaction conditions used to form the compounds, such as the addition of the compound, during the production steps of the modified conjugated diene polymer. The amount, reaction temperature, reaction time, etc. are controlled within the above numerical range.

The modified conjugated diene polymer (component (II)) has two or more types of polymer blocks selected from the group consisting of the following polymer blocks (A) to (C). (A) A polymer block containing vinyl aromatic monomer units as a main component (hereinafter, may be referred to as polymer block (A)). (B) A polymer block mainly composed of conjugated diene monomer units (hereinafter, may be described as polymer block (B)). (C) A random polymer block of a vinyl aromatic monomer unit and a conjugated diene monomer unit (hereinafter, sometimes referred to as a random polymer block (C) or a polymer block (C)) .

In the above (A), the polymer block containing vinyl aromatic monomer units as a main component has a content of vinyl aromatic monomer units of 80 mass % or more. The vinyl aromatic compound used to form the vinyl aromatic monomer unit is not limited to the following, and examples thereof include: styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1 , 1-stilbene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. Among these, from the viewpoint of availability and productivity, styrene, α-methylstyrene, and 4-methylstyrene are preferred, and styrene is more preferred. The polymer block containing vinyl aromatic monomer units as the main component (A) may be composed of one type of vinyl aromatic monomer unit or two or more types of vinyl aromatic monomer units. From the viewpoint of the strength of the molded article of the resin composition of the present embodiment, (A) the content of the vinyl aromatic monomer units contained in the polymer block containing the vinyl aromatic monomer units as the main body is set to It is 80 mass % or more, preferably 90 mass % or more, more preferably 95 mass % or more, and still more preferably 100 mass % (no other compounds are intentionally added).

In the above (B), the polymer block containing conjugated diene monomer units as the main component is one in which the content of the conjugated diene monomer units is 80% by mass or more. As the conjugated diene compound used to form the conjugated diene monomer unit, a diene having one pair of conjugated double bonds can be used. The diene is not limited to the following, and examples thereof include: 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl -1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene. Among these, from the viewpoint of availability and productivity, 1,3-butadiene and isoprene are preferably exemplified. (B) The polymer block mainly composed of conjugated diene monomer units may be composed of one type of conjugated diene monomer unit, or may be composed of two or more types of conjugated diene monomer units. From the viewpoint of the impact resistance of the resin composition of the present embodiment, (B) the content of the conjugated diene monomer units contained in the polymer block containing the conjugated diene monomer units as the main component is: 80 mass% or more, preferably 90 mass% or more, more preferably 95 mass% or more, further preferably 100 mass% (no other compounds are intentionally added).

Ethylene used to form the vinyl aromatic monomer units and conjugated diene monomer units contained in the random polymer block of the above (C) conjugated diene monomer units and vinyl aromatic monomer units The aromatic compound and the conjugated diene compound may be compounds that can be used in the above-mentioned polymer block (A) and polymer block (B). The distribution state of the vinyl aromatic monomer units in the random polymer block (C) is not particularly limited, and the vinyl aromatic monomer units in the random polymer block (C) may be uniformly distributed. , or it can also be distributed in a cone shape. In addition, there may be portions in which a plurality of vinyl aromatic monomer units are uniformly distributed and/or portions in which the vinyl aromatic monomer units are distributed in a conical shape, and there may also be segments in which the content of a plurality of vinyl aromatic monomer units is different. The mass ratio of vinyl aromatic monomer units and conjugated diene monomer units in the random copolymer block (C) is preferably vinyl aromatic monomer unit/conjugated diene monomer unit = 75/25 ~25/75, more preferably 70/30 ~ 30/70, further more preferably 65/35 ~ 35/65. The modified conjugated diene polymer (II) used in the resin composition of this embodiment may also be polymerized with other compounds copolymerizable with the conjugated diene compound and the vinyl aromatic compound.

The structure of the modified conjugated diene polymer (component (II)) is not particularly limited, and examples thereof include those having a structure represented by the following formula. In addition, in the following formula, description of a polar group is abbreviate|omitted. (bc) _n , c-(bc) _n , b-(cb) _n , (bc) _m -X, (cb) _m -X, [(bc) _n ] _m -X, [(cb) _n ] _m -X, [c-(bc) _n ] _m -X, [b-(cb) _n ] _m -X, [(bc) _n -b] _m -X, [(cb) _n -c] _m -X , (ab) _n , b-(ab) _n , a-(ba) _n , (ab) _m -X, (ba) _m -X, [(ab) _n ] _m -X, [(ba) _n ] _m -X, [b-(ab) _n ] _m -X, [a-(ba) _n ] _m -X, [(ab) _n -a] _m -X, [(ba) _n -b] _m - X, (ac) _n , c-(ac) _n , a-(ca) _n , (ac) _m -X, (ca) _m -X, [(ac) _n ] _m -X, [(ca) _n ] _m -X, [c-(ac) _n ] _m -X, [a-(ca) _n ] _m -X, [(ac) _n -a] _m -X, [(ca) _n -c] _m -X、 c-(ba) _n 、c-(ab) _n 、 c-(aba) _n 、c-(bab) _n 、 ac-(ba) _n 、ac-(ab) _n 、 ac-(ba) _n -b, [(abc) _n ] _m -X, [a-(bc) _n ] _m -X, [(ab) _n -c] _m -X, [(aba) _n -c] _m -X, [(bab) _n -c] _m -X, [(cba) _n ] _m -X, [c-(ba)n] _m -X, [c-(aba) _n ] _m -X, [c-( bab) _n ] _m -X a-(bc) _n , a-(cb) _n , a-(cbc) _n , a-(bcb) _n , ca-(bc) _n , ca-(cb) _n , ca -(bc) _n -b, [(cba) _n ] _m -X, [c-(ba) _n ] _m -X, [(cb) _n -a] _m -X, [(cbc) _n -a] _m -X, [(bcb) _n -a] _m -X, [(abc) _n ] _m -X, [a-(bc) _n ] _m -X, [a-(cbc) _n ] _m -X, [a-(bcb) _n ] _m -X b-(ac) _n , b-(ca) _n , b-(cac) _n , b-(aca) _n , cb-(ac) _n , cb-(ca ) _n , cb-(ac) _n -a, [(cab) _n ] _m -X, [c-(ab) _n ] _m -X, [(ca) _n -b] _m -X, [(cac) _n -b] _m -X, [(bcb) _n -b] _m -X, [(bac) _n ] _m -X, [b-(ac) _n ] _m -X, [b-(cac) _n ] _m -X, [b-(aca) _n ] _m -X In addition, in each of the above general formulas, a represents the above polymer block (A), b represents the above polymer block (B), and c represents the above Polymer block (C). n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X represents a residue of a coupling agent or a residue of a polyfunctional initiator. The modified conjugated diene polymer (component (II)) is preferably a polymer with a basic block structure, especially a polymer represented by the structural formula of ab, aba, and abab.

From the viewpoint of mechanical strength, impact resistance, abrasion resistance, compatibility, and moldability of the resin composition of the present embodiment, the weight average molecular weight of the modified conjugated diene polymer (component (II)) (Mw) (hereinafter also referred to as "Mw") is preferably 0.5 million to 600,000, more preferably 30,000 to 400,000, and still more preferably 50,000 to 300,000. The weight average molecular weight (Mw) of the modified conjugated diene polymer (component (II)) is based on a calibration curve calculated by measuring a commercially available standard polystyrene (using the peak molecular weight of the standard polystyrene). (Production) Calculate the weight average molecular weight (Mw) obtained by measuring the molecular weight of the peak of the chromatogram obtained by gel permeation chromatography (GPC). The molecular weight distribution of the conjugated diene polymer before modification can also be determined by measurement by GPC. Molecular weight distribution is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). The molecular weight distribution of a single peak of the modified conjugated diene polymer (component (II)) measured by GPC is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.0 or less, still more preferably 2.5 or less.

The modified conjugated diene polymer (component (II)) contains vinyl aromatic monomer units. Generally speaking, impact resistance and toughness are imparted by dispersing a specific polymer in a polar resin with high rigidity because when impact or extension is applied, the interface between the polar resin and the dispersed polymer particle component Or the polymer particles themselves create voids, and the matrix resin shears and yields from the polymer particles, thereby causing stress relaxation. Since the polymer block (A) mainly composed of vinyl aromatic monomer units is amorphous, it tends to promote the above-mentioned shear yield. Therefore, from the viewpoint of promoting the above shear yield and expressing impact resistance and toughness, the lower limit of the content of vinyl aromatic monomer units in the modified conjugated diene polymer (component (II)) is lower than Preferably, it is 1 mass % or more, More preferably, it is 3 mass % or more, Still more preferably, it is 5 mass % or more, Still more preferably, it is 8 mass % or more. By setting the content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) to 1 mass % or more, the ethylene content of the modified conjugated diene polymer (II) The amorphous portion of the aromatic monomer unit agglomerates and promotes the above-mentioned shear yield tendency. However, when voids are generated at the interface between the above-mentioned highly rigid polar resin and the dispersed polymer particle components or the polymer particles themselves, it is important that the rigidity difference between the polar resin serving as the matrix and the dispersed phase is relatively large. From this point of view, the interface between the polar resin (component (I)) and the dispersed polymer particle component (component (II)) or the polymer particles themselves creates voids and exhibits impact resistance and toughness. In other words, the upper limit of the vinyl aromatic monomer units of the modified conjugated diene polymer (component (II)) is preferably 90 mass% or less, more preferably 85 mass% or less, and still more preferably 80 mass% the following. By setting the amount of vinyl aromatic monomer units of component (II) to 90% by mass or less, the rigidity difference between the dispersed phase and the matrix becomes larger, which may further create voids at the interface or the polymer particles themselves. In this embodiment, In resin compositions, impact resistance and toughness tend to be improved. When a polyphenylene sulfide-based resin is used as the polar resin of the component (I), from the viewpoint of impact resistance at low temperatures, the ethylene of the modified conjugated diene-based polymer (component (II)) The content of the base aromatic monomer unit is preferably 40 mass% or less, more preferably 35 mass% or less, still more preferably 30 mass% or less, still more preferably 27 mass% or less. The content of vinyl aromatic monomer units in the modified conjugated diene polymer (component (II)) can be measured by the method described in the following Examples. The content of vinyl aromatic monomer units in the modified conjugated diene polymer (component (II)) can be controlled within the above numerical range by adjusting the amount of monomer added during polymer production.

In the modified conjugated diene polymer (II), from the viewpoint of productivity, the lower limit of the content of the polymer block (A) is preferably 1 mass % or more, more preferably 3 mass % % or more, and more preferably 5 mass% or more. From the viewpoint of impact resistance and toughness performance, the upper limit of the content of the polymer block (A) is preferably 95 mass% or less, more preferably 90 mass% or less, and still more preferably 80 mass% or less. When a polyphenylene sulfide-based resin is used as the polar resin (I), from the viewpoint of impact resistance performance at low temperatures, the polymer block (II) in the modified conjugated diene-based polymer (II) The content of A) is preferably 40 mass% or less, more preferably 35 mass% or less, still more preferably 30 mass% or less, still more preferably 27 mass% or less. Furthermore, the content of the polymer block (B) in the modified conjugated diene polymer (II) is preferably 0% by mass or more, and more preferably 10% by mass from the viewpoint of impact resistance and toughness. % or more and less than 90 mass%. When a polyphenylene sulfide-based resin is used as the polar resin (I), from the viewpoint of impact resistance performance at low temperatures, the polymer block (II) in the modified conjugated diene-based polymer (II) The content of B) is preferably 60 mass% or more, more preferably 65 mass% or more, further preferably 70 mass% or more, still more preferably 73 mass% or more. Furthermore, the content of the polymer block (C) in the modified conjugated diene polymer (II) is preferably 0 mass % or more from the viewpoint of compatibility with the polyphenylene sulfide resin. , more preferably 10 mass% or more and 90 mass% or less.

In the modified conjugated diene polymer (II), the vinyl bond amount is preferably 0 mol% or more, more preferably 5 mol% or more, based on 100 mol% of the total conjugated diene monomer units. The so-called "vinyl bond amount" refers to the 1,4-bond (cis and trans) and 1,2-bond (wherein , when incorporated into a polymer with 3,4-bonds, refers to the total amount of 1,2-bonds (mol%) of the total amount of 1,2-bonds and 3,4-bonds) . The vinyl bond amount of the modified conjugated diene polymer (II) can be measured using a nuclear magnetic resonance device (NMR) or the like. Specifically, it can be measured using the method described in the following Examples. The above-mentioned vinyl bond amount can be controlled to the above-mentioned numerical range by using a Lewis base, such as a compound such as an ether or an amine, as a vinyl bond amount adjuster (hereinafter referred to as a vinylating agent).

The modified conjugated diene polymer (II) may include a hydrogenated modified conjugated diene polymer in which an aliphatic double bond derived from a conjugated diene compound is hydrogenated. Thereby, the heat resistance of the resin composition of this embodiment can be improved. The hydrogenation rate of the aliphatic double bond derived from the conjugated diene compound is determined by the thermally unstable 1,2-bond portion (wherein, when incorporated into the polymer with a 3,4-bond) In terms of improving heat resistance by hydrogenation (including a 1,2-bond part and a 3,4-bond part), it is preferably 10% or more, more preferably 20% or more, and still more preferably 30% or more. In addition, when using a polyphenylene sulfide-based resin as the polar resin (I) which is particularly excellent in rigidity, chemical resistance, and heat resistance, the amount of the dispersed phase (B) in the resin composition of this embodiment is From the viewpoint of further improving toughness and impact resistance by setting the average dispersed particle size to 1.5 μm or less, the hydrogenation rate is preferably 90% or less, more preferably 83% or less, and still more preferably 80% or less. The hydrogenation rate of the modified conjugated diene polymer (II) can be measured using a nuclear magnetic resonance device (NMR) or the like. Specifically, it can be measured using the method described in the Examples. In addition, the hydrogenation rate can be controlled within the above numerical range by adjusting the amount of hydrogen that reacts during the hydrogenation reaction, for example.

<Production method of modified conjugated diene polymer (component (II))> The modified conjugated diene polymer (II) used in the resin composition of this embodiment is not limited to the following. For example, it can be produced by using an organic alkali metal compound as a polymerization starter in an organic solvent. The polymer is polymerized with a conjugated diene compound and a vinyl aromatic compound to obtain a block polymer, and then a modification reaction is carried out. The modified conjugated diene polymer (II) may be hydrogenated. The hydrogenation reaction and the modification reaction are not limited to this order and may be reversed. As the mode of polymerization, it may be batch polymerization, continuous polymerization, or a combination thereof. From the viewpoint of fixing the size of the dispersed phase in the resin composition, which affects impact resistance and toughness, a batch polymerization method in which the molecular weight distribution is narrowed is preferred.

The polymerization temperature is generally 0 to 180°C, preferably 20 to 160°C, and more preferably 30 to 150°C. The polymerization time varies depending on the target polymer, but is usually within 48 hours, preferably 0.1 to 10 hours. From the viewpoint of obtaining a conjugated diene polymer with a narrow molecular weight distribution and high strength, the time is more preferably 0.5 to 5 hours. The atmosphere of the polymerization system is not particularly limited as long as the pressure range is sufficient to maintain the nitrogen and solvent in the liquid phase. Preferably, there are no impurities in the polymerization system that can deactivate the polymerization initiator and active polymer, such as water, oxygen, carbon dioxide, etc.

The organic solvent is not limited to the following, and examples thereof include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane and cycloheptane; , methylcyclopentane and other alicyclic hydrocarbons; benzene, xylene, toluene, ethylbenzene and other aromatic hydrocarbons.

The organic alkali metal compound used as the polymerization initiator is preferably an organic lithium compound. Examples of the organolithium compound include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds. The organolithium compound is not limited to the following, and examples thereof include: ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, second butyl lithium, third butyl lithium, and n-pentyl lithium. Lithium, n-hexyllithium, benzyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isopropenyldilithium, and piperidine lithium, etc. When an organic lithium compound containing nitrogen (N) such as lithium piperidine is used as a polymerization initiator, an amine-modified conjugated diene polymer having an atomic group of X=0 in NHx is obtained. Only one type of these polymerization initiators may be used alone, or two or more types may be used in combination. Among these, n-butyllithium, di-butyllithium, and piperidinium lithium are preferred from the viewpoint of polymerization activity.

The amount of organic alkali metal compound used as a polymerization initiator depends on the molecular weight of the target modified conjugated diene polymer. Generally speaking, it is preferably 0.01 to 1.5 phm (relative to the mass per 100 parts by mass of the monomer). parts), more preferably, it is in the range of 0.02 to 0.3 phm, and still more preferably, it is in the range of 0.05 to 0.2 phm.

The vinyl bond amount of the conjugated diene-based polymer (component (II)) can be modified by using a Lewis base, such as an ether, an amine or other compound, as a vinyl bond amount adjuster (hereinafter referred to as a vinylating agent). to control. In addition, the amount of vinyl bonds can be controlled by adjusting the amount of vinylizing agent used.

The vinylating agent is not limited to the following, and examples thereof include ether compounds, tertiary amine compounds, and the like.

Examples of the ether compound include linear ether compounds and cyclic ether compounds. Examples of linear ether compounds include, but are not limited to, dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Diethylene glycol dialkyl ether compounds; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether and other dialkyl ether compounds of diethylene glycol. In addition, the cyclic ether compound is not limited to the following, and examples thereof include tetrahydrofuran, dihexane, 2,5-dimethyloxolane, and 2,2,5,5-tetramethyloxyxane. Heterocyclopentane, 2,2-bis(2-tetrahydrofuryl)propane, alkyl ether of furanmethanol, etc.

The tertiary amine compound is not limited to the following, and examples thereof include: trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N -Methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane , trimethylaminoethylpiperidine, N,N,N',N",N"-pentamethylethylidenetriamine, N,N'-dioctyl-p-phenylenediamine, pyridine, tetrakis Methylpropanediamine, bis[2-(N,N-dimethylamino)ethyl]ether, etc. Only one type of these may be used alone, or two or more types may be used in combination. As the tertiary amine compound, a compound having two amines is preferred. Furthermore, among them, those having a structure showing symmetry in the molecule are more preferred, and N,N,N',N'-tetramethylethylenediamine, bis[2-(N,N -Dimethylamino)ethyl]ether or 1,2-dipiperidinylethane.

The modified conjugated diene polymer (II) used in the resin composition of this embodiment can be obtained by using a conjugated diene in the coexistence of the above-mentioned vinylating agent, an organic lithium compound, and an alkali metal alkoxide. It is produced by polymerizing compounds and vinyl aromatic compounds. Here, the alkali metal alkoxide is a compound represented by the general formula MOR (in the formula, M is an alkali metal and R is an alkyl group). By allowing the alkali metal alkoxide to coexist in the polymerization step, the effect of controlling the vinyl bond amount, molecular weight distribution, polymerization speed, block ratio, etc. is obtained.

The alkali metal as the alkali metal alkoxide is preferably sodium or potassium from the viewpoint of higher vinyl bond amount, narrower molecular weight distribution, higher polymerization speed, and higher block ratio. The alkali metal alkoxide is not limited to the following, and examples thereof include sodium alkoxide, lithium alkoxide, and potassium alkoxide having an alkyl group having 2 to 12 carbon atoms, and those having an alkyl group having 3 to 6 carbon atoms are preferred. The sodium alkoxide or potassium alkoxide of the alkyl group is preferably sodium tert-butoxide, sodium tert-pentoxide, potassium tert-butoxide, or potassium tert-pentoxide. Among these, sodium tert-butoxide and sodium tert-pentoxide which are sodium alkoxides are more preferred.

The modified conjugated diene polymer (II) may also be hydrogenated, and the polymer block containing the conjugated diene monomer unit may also be a hydrogenated product. The method of hydrogenation is not particularly limited. For example, the conjugated diene polymer obtained in the above polymerization step can be hydrogenated by supplying hydrogen to it in the presence of a hydrogenation catalyst, thereby obtaining conjugated diene monomer units. Hydrogenated conjugated diene polymers formed by hydrogenation of double bond residues. The hydrogenation rate can be controlled, for example, by the amount of catalyst during hydrogenation. The hydrogenation speed can be controlled, for example, by adjusting the catalyst amount, hydrogen supply amount, pressure and temperature during hydrogenation. The hydrogenation reaction step is preferably carried out in sequence after the formation reaction of the conjugated diene polymer before hydrogenation is stopped.

The modified conjugated diene polymer (II) is bonded with at least one polarity selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an epoxy group, an oxetanyl group, and an amine group. base. From the viewpoint of affinity and/or reactivity with the polar resin (I) and the polymer (component (III)) having a specific polar group described below, a hydroxyl group or a carboxyl group is more preferred. Furthermore, the polar group bonded to the modified conjugated diene polymer (II) is at least one selected from the group consisting of a hydroxyl group and a carboxyl group, and a thermoplastic resin is used as the component (I), and When a molten resin composition is injected into a mold by injection molding and then cooled to obtain an arbitrary molded body, the fluidity of the resin composition tends to be improved and the processability is improved. The method of introducing the polar group into the conjugated diene polymer is not particularly limited. Examples include: a method of introducing a polymerization initiator having a specific polar group; a method of introducing a polymer having a specific polar group; A method of polymerizing unsaturated monomers to obtain modified conjugated diene polymers; a method of adding a modifier with a polar group to the active terminal of the polymer, etc. In the modified conjugated diene polymer (II), the position for introducing each polar group is not particularly limited. For example, it can be the end of the conjugated diene polymer, or it can be block or random. The cone is arranged on part of the main chain. From the viewpoint of affinity and/or reactivity with the polar resin (component (I)) and the polymer (component (III)) having a specific polar group described below, and further the processability of the above-mentioned resin composition, it is more Preferably, it is the terminal end of the conjugated diene polymer.

The "modifier" is not limited to the following, and examples thereof include: maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carboxylic acid, Acid, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid and other aliphatic carboxylic acids; terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, Aromatic carboxylic acids such as trimellitic acid and pyromellitic acid. Examples include maleic anhydride, itaconic anhydride, pyromellitic dianhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, and pyromellitic anhydride. Carboxylic dianhydride, 5-(2,5-dioxotetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, ε-caprolactam, etc.

Another method for introducing a polar group into a conjugated diene polymer may include, for example, a method in which an organic alkali metal compound such as an organic lithium compound is reacted with a conjugated diene polymer (metalization reaction), And the modifier having a polar group and the polymer to which the organic alkali metal is added are subjected to an addition reaction.

Furthermore, as another method of introducing a polar group, for example, a method of directly grafting and adding an atomic group having a polar group to an unmodified conjugated diene polymer can be used. Examples of the graft addition method include: a method of reacting a radical initiator, a conjugated diene polymer, and the above-mentioned modifier in a solution; or initiating radicals. A method of reacting an agent, a conjugated diene polymer, and the above-mentioned modifier under heating and melting; or a compound that does not contain a free radical initiator and contains a conjugated diene polymer, and the above-mentioned modifier is reacted in Methods of reaction under heating and melting, etc.

As a method for reacting each component when introducing a polar group into a polymer, for example, general-purpose methods such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a bidirectional kneader, and a multi-screw extruder can be used. A mixer is a method of melting and kneading the ingredients. From the viewpoint of cost and production stability, a method using a single, twin or multi-screw extruder is preferred, and a method using a twin-screw extruder is preferred. During the reaction step, each component can be dry-blended and put in at once, each component can be fed separately, and the same component can also be added in stages. From the perspective of uniformly adding the modifier to the polymer, the rotation speed of the screw is preferably 50 to 400 rpm, and more preferably 100 to 350 rpm to suppress the deterioration of the polymer due to shearing. From the viewpoint of uniform addition, 150 to 300 rpm is preferred. The kneading temperature is a temperature at which the conjugated diene polymer melts and radicals are generated from the radical initiator, and is preferably 100°C to 350°C. From the viewpoint of controlling the introduction amount of polar groups or suppressing deterioration of the polymer due to heat, 120°C to 300°C is preferred, and 150°C to 250°C is more preferred. In order to inhibit the deactivation of free radical active species due to oxygen, melting and kneading can also be carried out under inert gases such as nitrogen.

The above-mentioned free radical initiator is not limited to the following, and examples thereof include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, diyl peroxide, peroxyester, and peroxygen. Dicarbonates. The radical initiator preferably has a half-life temperature of 1 minute in the kneading temperature range. More preferably, those with a half-life temperature of 1 minute are within the range of 150°C to 250°C. Examples include: 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy) base) cyclohexane, 2,2-bis(4,4-di-(tert-butylperoxy)cyclohexyl)propane, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxide Maleic acid, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butylperoxylauric acid, peroxymonocarbonate O,O-tert-butyl-O-iso Propyl ester, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy) Hexane, tert-butyl peracetate, 2,2-di-(tert-butylperoxy)butane, tert-butyl peroxybenzoate, 4,4-di-(tert-butylperoxy)butane n-butyloxy)valerate, di(2-tert-butylperoxyisopropyl)benzene, dicumyl peroxide, di-tert-hexyl peroxide, 2,5-dimethyl-2 ,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, p-methane hydroperoxide, 2,5-dimethyl-2 , 5-di(tertiary butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide. In particular, from the viewpoint of compatibility with the conjugated diene polymer used in the modification step, di(2-tert-butylperoxyisopropyl)benzene and dibenzoperoxide are preferred. Cumene, di-tert-hexyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, dibutyl peroxide -Tertiary butyl, 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexyne-3. More preferably, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 2,5-dimethyl-2,5-di(tert-butylperoxy) )Hexyne-3.

As another method of introducing a polar group into a conjugated diene polymer, for example, the primary modified conjugated diene polymer obtained by the above method is introduced by reacting it with an atomic group having a specific polar group. The second modification. Examples of combinations of polar groups include: amine group and dicarboxylic acid anhydride group, isocyanate group, hydroxyl group, oxetanyl group, and carboxyl group; acid anhydride group and hydroxyl group, tetrazolinyl group, And oxetanyl group; silanol group and hydroxyl group, and carboxyl group; epoxy group and carboxyl group can be enumerated. From the viewpoint of reactivity, the preferred ones are an amine group and a dicarboxylic group, an acid anhydride group, an oxazoline group, and an oxetanyl group; a silanol group and a hydroxyl group, and a dicarboxylic group; an epoxy group and a dicarboxylic group, and more preferably Preferred are amine groups, dicarboxylic groups, and acid anhydride groups.

As a method of primary modification by bonding epoxy groups, acid anhydride groups, and hydroxyl groups to the conjugated diene-based polymer, the above-mentioned method can be exemplified. As the modifier, the above-mentioned modifiers, epoxy-containing polymers, etc. can be exemplified. Based polymeric compounds, etc.

As a method for primary modification by bonding a silanol group to a conjugated diene polymer, the above method can be exemplified. As a modifier, for example: bis-(3-triethoxysilyl group) Propyl)-tetrasulfide, bis-(3-triethoxysilylpropyl)-disulfide, ethoxysiloxane oligomers, epoxy group-containing polymeric compounds, the above-mentioned ring-containing compounds Examples of polymerizable compounds with an oxygen group include hydrolyzates of compounds having an alkoxysilyl group and the like.

An example of a primary modification method by bonding an amine group to a conjugated diene polymer is the above method. Examples of the modifier include: 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylpropamide, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2- Imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone Ketone, 1-methyl-3-(2-methoxyethyl)-2-imidazolidinone, 1-methyl-3-(2-ethoxyethyl)-2-imidazolidinone, 1, 3-Di-(2-ethoxyethyl)-2-imidazolidinone, 1,3-dimethylethylthiourea, N,N'-diethylpropenyl urea, N-methyl-N '-Ethyl acrylurea etc. Furthermore, examples include: 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-Butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone , 1-methyl-2-piperidone, 1,4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-isopropyl-2-piperidone, 1 -Isopropyl-5,5-dimethyl-2-piperidone, etc.

An example of a method for bonding a primary modified conjugated diene polymer to which an amine group is bonded and a secondary modifier is the above method. Examples of the modifier include maleic acid. , oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carboxylic acid, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid and other aliphatic carboxylic acids; terephthalic acid Formic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimellitic acid, trimellitic acid, pyromellitic acid and other aromatic carboxylic acids. Examples include maleic anhydride, itaconic anhydride, pyromellitic dianhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, and pyromellitic anhydride. Carboxylic dianhydride, 5-(2,5-dioxotetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, etc.

The shape of the modified conjugated diene polymer (II) obtained by the above-mentioned production method is not particularly limited, and examples thereof include granular, flake, linear, and flake shapes. In addition, it can also be directly made into a molded product after melting and kneading. By granulating the modified conjugated diene polymer (II), particles of the modified conjugated diene polymer can be produced. As a method of pelletization, for example, the modified conjugated diene polymer is extruded in a linear form from a single-screw or twin-screw extruder, and is immersed in water using a rotary knife installed in front of the die nozzle. Cutting method: Extruding the modified conjugated diene polymer into a linear form from a single-screw or twin-screw extruder, water-cooling or air-cooling, and then cutting it with a wire cutting machine; by Methods such as melt-mixing with an open roller or Banbury mixer, forming it into a sheet using a roller, cutting the sheet into short strips, and then cutting it into cubic pellets using a granulator. . Furthermore, the size and shape of the particles are not particularly limited.

In the modified conjugated diene polymer (II), a particle adhesion preventing agent may be added to the particles to prevent particle adhesion if necessary. The particle adhesion preventing agent is not limited to the following, and examples thereof include: calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylbisstearylamide, talc, Amorphous silica, etc. When using the resin composition of the present embodiment to produce a random polypropylene composition or a tubular molded article or a sheet-shaped molded article containing the same, calcium stearate is preferred from the viewpoint of their transparency. , polyethylene, and polypropylene. A preferable amount of the particle adhesion preventing agent is 500 to 6000 ppm relative to the modified conjugated diene polymer (II). A more preferable amount is 1000 to 5000 ppm relative to the modified conjugated diene polymer (II). The particle adhesion preventing agent is preferably prepared in a state of being attached to the surface of the particles, or may be contained inside the particles to some extent.

(Component (III) is a polymer having a polar group reactive with component (I) and/or component (II) (except component (I) and component (II)) The resin composition of this embodiment may also contain a polymer (excluding component (I) and component (II)) having a polar group reactive with component (I) and/or component (II) (hereinafter, it may be stated is polymer (III), component (III)). Even when the polar group bonded to the modified conjugated diene polymer (II) has low affinity and/or reactivity with the component (I), by including the component (I) and/or the polymer (III) in which the component (II) has a reactive functional polar group is included in the resin composition of this embodiment, and the number average dispersed particle diameter of the dispersed phase (B) can be 1.5 μm or less. tendency. In addition, it is from the perspective of expressing impact resistance and toughness by increasing the difference in rigidity between the polar resin (component (I)) as the matrix and the dispersed phase (component (II), component (III)) and promoting shear yield. Specifically, component (III) is preferably reactive with component (I) and component (II). Component (III) is a non-vinyl aromatic compound that does not contain a polymer block mainly composed of vinyl aromatic monomer units and does not contain a polymer with the same structure as the modified conjugated diene polymer (II). It is a modified polymer. When component (III) contains a vinyl aromatic monomer unit, the reactivity with component (I) and component (II) tends to decrease due to steric hindrance of the aromatic ring.

Component (III) is a polymer having a polar group reactive with the above-mentioned component (I) and/or component (II). The so-called "polymer" refers to a polymer compound with repeating units (also includes repeating units of Oligomers with a lower degree of polymerization (about 2 to 10). From the viewpoint of maintaining sufficient rigidity for practical use of the resin composition of the present embodiment, the lower limit of the molecular weight of component (III) is preferably 1,000 or more, more preferably 2,000 or more. From the viewpoint of the fluidity of the resin composition of the present embodiment, the upper limit of the molecular weight of component (III) is preferably 5 million or less, more preferably 3 million or less, and still more preferably 1 million or less. In addition, the molecular weight of the above-mentioned component (III) can be appropriately set in consideration of the compatibility with the component (I) and the component (II), the fluidity of the resin composition of the present embodiment, and the like. When it is 5 million or less, good fluidity of the resin composition is obtained, and good formability tends to be obtained in actual use.

The "reactivity" of component (III) with component (I) and/or component (II) means that the polar groups of each component have covalent bonding properties with each other. Included in the following definition: when polar groups react with each other, if the OH of a carboxyl group, for example, is released, the original polar group changes or disappears, whereby the polar groups show "reactivity" with each other when a covalent bond is formed. The polar group contained in component (III) may be one polar group that exhibits reactivity with both component (I) and component (II), or may be a plurality of polar groups that react with component (I) and component ((II) respectively. Each of II) shows reactivity. Component (III) may also contain a polar group that is reactive with only one of component (I) and component (II), but in order to increase the affinity with both components, the amount of the following dispersed phase (B) From the viewpoint of having an average dispersed particle size of 1.5 μm or less, preferably 1.3 μm or less, it is preferred to have a polar group showing reactivity with both component (I) and component (II). For example, when component (III) has an epoxy group, component (I) is a polyphenylene sulfide resin, and component (II) is a polymer having carboxyl and/or hydroxyl groups, the epoxy group of component (III) It exhibits reactivity with the carboxyl groups of the polyphenylene sulfide resin of component (I) and the polymer of component (II). Since the polar group contained in component (III) has reactivity with the polar resin (component (I)) and the modified conjugated diene polymer (component (II)), the resin of this embodiment In the composition, toughness and impact resistance can be improved.

(combination of ingredient (I), ingredient (II), and ingredient (III)) Examples of combinations of polar groups of component (II) and component (III) include the following combinations. When component (II) contains an amine group, preferred polar groups included in component (III) include carboxyl group, carbonyl group, epoxy group, hydroxyl group, acid anhydride group, sulfonic acid, and aldehyde group. When component (II) contains an acid anhydride group, examples of preferred polar groups included in component (III) include amine groups, hydroxyl groups, and the like. When component (II) contains a carboxyl group or a dicarboxylic group, preferred polar groups included in component (III) include an amine group, an isocyanato group, and the like. When component (II) has an epoxy group, preferred polar groups included in component (III) include an amino group, a carboxyl group, a dicarboxylic group, a thiol group, an oxazoline group, and an oxyheterocyclic group. Butyl et al. When component (II) contains an oxetanyl group, preferable polar groups contained in component (III) include thiol group, hydroxyl group, amine group, carboxyl group, dicarboxyl group, and the like. When component (II) contains a tetrazoline group, preferred polar groups included in component (III) include thiol group, hydroxyl group, amine group, carboxyl group, dicarboxylic group, and the like. Furthermore, examples of combinations of polar groups included in component (I) and component (III) include: Amino group and carboxyl group, carbonyl group, epoxy group, hydroxyl group, acid anhydride group, sulfonic acid, and aldehyde group; Isocyanate and hydroxyl, carboxyl, and dicarboxylic groups; hydroxyl and acid anhydride groups; Silanol group and hydroxyl group, carboxyl group, and dicarboxylic group; Epoxy group and carboxyl group, dicarboxyl group, thiol group, oxazolinyl group, and oxetanyl group; Halogen group and carboxylic acid group, carboxylate ester group, amine group, phenol group, and thiol group; Alkoxy and hydroxyl, alkoxide, and amine groups; Thiol group and epoxy group, oxetanyl group, and oxetanyl group; wait.

In the resin composition of this embodiment, you can arbitrarily select which polar group of component (I) or component (III) is used to complete the bonding with the polar group of component (II). When a polyphenylene sulfide-based resin, which is a polar resin excellent in rigidity, chemical resistance, and heat resistance, is used as component (I), from the viewpoint of reactivity, the polarity contained in component (II) The group is preferably a carboxyl group, a hydroxyl group, an epoxy group, a tetrazolinyl group, and an oxetanyl group, and more preferably a carboxyl group or a hydroxyl group. In order to have reactivity with component (I) and component (II), as the polar group possessed by component (III), an epoxy group, an oxazolinyl group, and an oxetanyl group are preferred from the viewpoint of reactivity. In particular, epoxy group is more preferred.

When component (III) is a polymer having an epoxy group, examples of the polymer having the epoxy group include polymerization of epoxy group-containing polymerizable compounds such as unsaturated compounds containing an epoxy group. and copolymers of epoxy group-containing polymerizable compounds and at least one other polymerizable compound. The epoxy group-containing polymerizable compound is not limited to the following, and examples of the epoxy group-containing unsaturated compound include, for example, glycidyl methacrylate, glycidyl acrylate, and vinyl glycidyl ether. , glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate, glycidyl itonate, tetraglycidyl m-xylylenediamine, tetraglycidyl metaxylylenediamine, Glycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidyl o-methyl Aniline, 4,4'-diglycidyl-diphenylmethylamine, 4,4'-diglycidyl-dibenzylmethylamine, diglycidylaminomethylcyclohexane and other polycyclic oxygen compounds.

Furthermore, examples include: γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, and γ-glycidoxysilane. Propyltriethoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane , γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldibutoxysilane Glyceroxypropylmethyl diphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxysilane Propyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropyl Methyl diisopropoxysilane, bis(γ-glycidoxypropyl)dimethoxysilane, bis(γ-glycidoxypropyl)diethoxysilane.

Furthermore, bis(γ-glycidoxypropyl)dipropoxysilane, bis(γ-glycidoxypropyl)dibutoxysilane, and bis(γ-glycidoxypropyl)dibutoxysilane can be exemplified. ) diphenoxysilane, bis(γ-glycidoxypropyl)methylmethoxysilane, bis(γ-glycidoxypropyl)methylethoxysilane, bis(γ-glycidoxypropyl)methylethoxysilane methylpropyl)methylpropoxysilane, bis(γ-glycidoxypropyl)methylbutoxysilane, bis(γ-glycidoxypropyl), tris(γ-glycidoxypropyl) base) methoxysilane.

Furthermore, examples thereof include: β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane, -(3,4-epoxycyclohexyl)ethyl-tripropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tributoxysilane, β-(3,4-epoxy Cyclohexyl)ethyl-triphenoxysilane.

Moreover, further examples include: β-(3,4-epoxycyclohexyl)propyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldiethoxysilane, β-(3 ,4-epoxycyclohexyl)ethyl-methyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldipropoxysilane, β-(3,4-cyclohexyl) Oxycyclohexyl)ethyl-methyldibutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiphenoxysilane, β-(3,4-epoxycyclohexyl) Ethyl-dimethylmethoxysilane, β-(3,4-epoxycyclohexyl), β-(3,4-epoxycyclohexyl)ethyl-dimethylethoxysilane, β-( 3,4-Epoxycyclohexyl)ethyl-dimethylpropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylbutoxysilane, β-(3,4- Epoxycyclohexyl)ethyl-dimethylphenoxysilane.

Furthermore, examples include: β-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiisopropoxy Silane, N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propanamine, etc.

The compound copolymerizable with the above-mentioned epoxy group-containing polymerizable compound is not limited to the following, and examples thereof include: conjugated diene compounds such as butadiene and isoprene; unsaturated hydrocarbons such as ethylene and propylene; Compounds; cyanide vinyl monomers such as acrylonitrile; vinyl acetate, (meth)acrylate, vinyl alcohol, vinyl acetate, vinyl acetate, etc.

The polymer having an epoxy group (component (III)) is not limited to the following, and examples thereof include: Bondfast (copolymer of ethylene-glycidyl methacrylate, ethylene-vinyl acetate-glycidyl methacrylate) Glyceride copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, manufactured by Sumitomo Chemical Co., Ltd.), ELVALOY ^TM PTW (ethylene-glycidyl methacrylate-butyl acrylate copolymer, Dow Chemical Co., Ltd.), Vylon RF (glycidyl group-containing polyester resin, manufactured by Toyobo Co., Ltd.), ARUFONUG-4000 (epoxy group-containing acrylic resin, manufactured by Toa Gosei Co., Ltd.).

Furthermore, a polymer having an epoxy group as component (III) can also be obtained by performing an addition reaction between an arbitrary polymer and the above-mentioned epoxy group-containing unsaturated compound using a radical reaction or the like. Examples of the optional polymer include polymers of unsaturated hydrocarbon compounds such as ethylene and propylene, copolymers of the above unsaturated hydrocarbon compounds and polymerizable compounds having double bonds, conjugated diene compounds and vinyl aromatic compounds. copolymers, etc. As a method of the addition reaction, there can be exemplified previously known techniques, such as: a manufacturing method in which the reaction is carried out in a solution containing a radical initiator, a polymer, and an epoxy group-containing compound; A manufacturing method in which a radical initiator reacts with a polymer and a compound containing an epoxy group under heating and melting; a manufacturing method in which a radical initiating agent is not included and the polymer and a compound containing an epoxy group react in a heating and melting condition Methods; manufacturing methods of reacting a polymer and a compound containing an epoxy group to form a compound polymer by reacting and bonding with either a polymer and a compound containing an epoxy group, and reacting a compound containing an epoxy group with a solution containing the same or heating and melting it, etc. . Another example is a method of epoxylation by partially oxidizing the diene of a polymer having a carbon bond and/or a copolymer of a polymer having a carbon bond and another polymerizable compound.

From the viewpoint of polymerizability, as the epoxy group-containing polymerizable compound, an epoxy group-containing unsaturated compound is preferred, and glycidyl methacrylate, glycidyl acrylate, and vinyl glycidyl ether are more preferred. , glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate.

By increasing the affinity between the polymer having an epoxy group (component (III)) and the modified conjugated diene-based polymer (component (II)), the dispersion of the resin composition of the present embodiment can easily concentrate stress. Phase (B). From the viewpoint of affinity with the modified conjugated diene polymer (component (II)), the polymer having an epoxy group (component (III)) is more preferably the above-mentioned epoxy group-containing polymerizable compound. A copolymer of a (polymerizable monomer having an epoxy group) and an unsaturated hydrocarbon compound is an elastomer having an epoxy group, and an olefin elastomer having an epoxy group is more preferred. By using the polymer (component (III)) as an olefin-based elastomer having an epoxy group, the toughness and/or resistance due to shear yield due to stress concentration at the resin interface with component (I) can be obtained. The effect of improving the impact resistance and thereby suppressing the elongation of micro cracks and/or cracks generated under stress is obtained. Furthermore, the component (II) and the component (III) inhibit micro cracks and/or cracks. The bridging effect tends to further improve toughness and/or impact resistance. Especially at low temperatures, specifically, in applications used below -30°C, by using component (III) as an olefin elastomer having an epoxy group, the toughness and/or low temperature can be further improved. Impact resistance tendency. Furthermore, improvements in tracking resistance and the effect of suppressing deterioration in physical properties (thermal cycle characteristics) even when exposed alternately from high to low temperatures are expected. These effects can be improved by controlling the compatibility state by adjusting the affinity or reactivity between the components.

In addition, as the polymer having an epoxy group as the component (III), the above-mentioned styrene, acrylonitrile and other cyanated vinyl monomers, vinyl acetate, (meth)acrylate, vinyl alcohol, vinyl acetate, etc. When the polymerizable compound is copolymerized with the above-mentioned unsaturated hydrocarbon compound and the above-mentioned epoxy group-containing polymerizable compound, when the above component (I) is a polyphenylene sulfide-based resin, the affinity with the polyphenylene sulfide-based resin From this viewpoint, it is more preferable to copolymerize (meth)acrylate, vinyl acetate, and vinyl acetate, and even more preferably to copolymerize (meth)acrylate and/or vinyl acetate.

Examples of the unsaturated hydrocarbon compound include ethylene, propylene, and α-olefins having 3 to 8 carbon atoms.

(Ratio of polar resin (I), modified conjugated diene polymer (II) and polymer (III)) Regarding the resin composition of this embodiment, the resin composition of this embodiment exhibits heat resistance, impact resistance, and toughness, and the number average dispersed particle size of the following dispersed phase (B) is 1.5 μm or less. The mass ratio of the polar resin (component (I)) and the modified conjugated diene polymer (component (II)) of the composition is set to component (I):component (II). )=50/50～99/1, preferably 55/45～98/2, more preferably 60/40～95/5.

Moreover, when the resin composition of this embodiment contains the above-mentioned polar resin (component (I)), the modified conjugated diene-based polymer (component (II)), and the above-mentioned polymer (component (III)) , from the viewpoint of making the number average dispersed particle diameter of the dispersed phase (B) 1.5 μm or less, the mass ratio of the above-mentioned component (II) and component (III) is preferably component (II): component (III) = 1/ 99 to 99/1, more preferably 5/95 to 95/5, still more preferably 10/90 to 90/10, still more preferably 15/85 to 85/15.

In addition, from the viewpoint of expressing the heat resistance, impact resistance and toughness of the resin composition of the present embodiment and making the number average dispersed particle diameter of the following dispersed phase (B) 1.5 μm or less, the present embodiment is The mass ratio of the total amount of component (I), component (II) and component (III) of the resin composition is preferably component (I): (component (II) + component (III)) = 50/50 ~ 99/1 , more preferably 60/40 to 97/3, further preferably 65/35 to 95/5.

(dispersed state) The resin composition of this embodiment has a continuous phase (A) of a polar resin (component (I)), and a modified conjugated diene polymer (component (II)) dispersed in the continuous phase (A). The dispersed phase (B). By using the polar resin (component (I)) as the continuous phase (A), excellent heat resistance and rigidity are obtained in the resin composition of this embodiment. In addition, due to the presence of the dispersed phase (B), when stress is applied to the molded article containing the resin composition, the stress is concentrated on the dispersed phase (B) and microcracks are generated, thereby contributing to improvement in impact resistance and toughness.

The dispersed phase (B) only needs to be a phase containing the component (II). When it contains the component (III) which is a polymer having a polar group reactive with the above-mentioned component (II), the dispersed phase (B) may be the component (II). The phase in which the modified conjugated diene polymer is compatible with component (III) may be a state where component (III) is present in a segregated state around component (II), or it may be a state in which component (II) is present in a segregated state around component (II). (III) The surrounding state. Furthermore, the component (III) and the component (I) may be in a compatible state. When only the component (III) is dispersed in the sea containing the polar resin (component (I)), the effect of improving the impact resistance and/or toughness of the resin composition cannot be confirmed. Therefore, as described above, the dispersed phase (B) contains both the component (II) and the component (III) or any one of the component (II) dispersed alone, and thereby the dispersed phase (B) becomes a number-average dispersion. Particle size corresponds to improved impact resistance and/or toughness. Therefore, the resin composition of this embodiment has the continuous phase (A) of the polar resin (component (I)) and the dispersed phase (B) containing the modified conjugated diene polymer (component (II)).

The method for confirming the dispersion state of the continuous phase (A) and the dispersed phase (B) will be described below. <(1) Specification of components contained in the resin composition> First, it is useful to specify the components contained in the resin composition of the present embodiment to measure the number average dispersed particle size of the dispersed phase (B). Generally speaking, the polar resin of component (I) is known to have excellent chemical resistance. When the resin composition contains the above-mentioned component (II) modified conjugated diene polymer and component (III) polymer, when the resin composition is mixed in a solvent that can also dissolve component (III), due to chemical resistance Excellent, it can extract undissolved component (I), unreacted component (II), and component (III). Especially when polyphenylene sulfide-based resin is used as component (I), since there is no solvent that can dissolve the polyphenylene sulfide-based resin below 200°C, it can be dissolved by mixing the solvent with the polyphenylene sulfide-based resin at 50 to 200°C. The resin composition is mixed to extract the undissolved component (I), unreacted component (II), and unreacted component (III).

When the component (II) and the component (III) are included, examples of the solvent that can dissolve the component (III) include toluene, cyclohexane, xylene, tetrahydrofuran, chloroform, nitroethane, nitrate, ethylpropane, ethylbenzene, etc.; from the viewpoint of solubility, chloroform, nitroethane, nitropropane, ethylbenzene, and toluene are preferred. After extraction, undissolved component (I) is removed by filtration, etc., and the filtrate is used for liquid chromatography, whereby component (II) and component (III) can be separated. In addition, when the solubility of component (II) and component (III) is different, the following method can also be adopted: using a solvent that dissolves component (II) but cannot dissolve component (III), and vacuum drying, etc. The solvent of the above filtrate is removed, and the mixture of component (II) and component (III) obtained thereby is mixed again in an appropriate solvent, thereby separating component (II) and component (III). Generally speaking, examples of solvents with relatively high solubility for component (II) include toluene, cyclohexane, and tetrahydrofuran. In addition, the structural unit of the component (III) that cannot be dissolved in the above solvent is a polymer unit of an unsaturated hydrocarbon compound, and particularly examples thereof include ethylene, propylene, and α-olefins having 3 to 8 carbon atoms. Component (II) and component (III) can be identified by nuclear magnetic resonance (NMR), infrared absorption spectrometry (IR), gas chromatography (GS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). ) and so on. In addition, the type and structure of the polar group bonded to component (II) and component (III) can also be identified. In addition, when the resin composition of the present embodiment contains components such as the following additives that are soluble in the solvent in the above-mentioned extraction step, they can be separated into respective components by liquid chromatography or the like using differences in molecular weight and polarity. Components can be identified by the above-mentioned NMR, IR, GS, and TOF-SIMS. When the unreacted amount of component (II) and component (III) and the above-mentioned component (I) is very small and it is difficult to separate component (II) and component (III), it can also be observed by using an atomic force microscope (AFM). The obtained infrared absorption spectrum specifies the structural units of component (II) and component (III) and the types of polar groups bonded to component (II) and component (III). Examples of test pieces used for AFM measurement include precision cross-sections of resin compositions produced using ultramicrotome or the like.

<(2) Measurement of dispersed particle size> [(1)AFM (Particle size measurement of soft phase in elastic modulus spectrum)] Generally speaking, the melting point of the polar resin of component (I) is high, and its rigidity is higher than that of component (II) at normal temperatures, especially low temperatures. When it contains component (III), its rigidity is higher than that of component (III). Furthermore, after isolating component (II) and component (III), the structural units of component (II) and component (III) are identified, or the components (including component (II) and component (III)) are isolated. By measuring the rigidity of the mixture), it can be confirmed that the rigidity of component (II) and component (III) is relatively lower than that of component (I). In addition, it can be clarified that the component (I) has higher rigidity than the component (II) and the component (III) based on the infrared absorption spectrum and/or the force curve of the viscoelasticity and elastic modulus obtained by the above-mentioned AMF observation. When the mass ratio of the polar resin (component (I)) in the resin composition of this embodiment is 50 mass % or more, component (I) forms a "sea" in the form of the resin composition. As mentioned above, due to the difference in rigidity between component (I), component (II), and component (III), as long as the "island" portion observed by AFM observation is softer than the "sea" in the elastic modulus map, The part corresponding to the "island" can be specified as component (II) and/or component (III). Therefore, the number average dispersed particle diameter of the dispersed phase (B) can be calculated by calculating the average value of the particle diameters of the soft portions in the elastic modulus spectrum using the method described in the Examples below. Generally speaking, the elastic modulus measurement by AFM observation is to set an upper limit of the force on the probe at the front end of the AFM cantilever and the sample, and press it in in the vertical direction, thereby based on the relationship between the load and the deformation of the sample. And figure it out. Therefore, in order to express the degree of deformation of each dispersed phase relative to the load, the distribution of components with different elastic moduli was observed in the form of images.

Moreover, generally speaking, the melting temperature when mixing component (I), component (II), and optionally component (III) in a molten state is very high. Therefore, there are cases where low molecular weight compounds generated during kneading etc. overflow and a clear elastic modulus map cannot be obtained. In this case, as described in the following examples, it is preferable to perform ultrasonic cleaning in a solvent such as ethanol to remove the above-mentioned low molecular compounds and then use Ultramicrotome, etc. produce precise sections.

[(2) Specification of dispersed phase by dyeing] When the above-mentioned component (II) and component (III) are isolated and the structural units of component (II) and component (III) are identified, the following method can also be used: by component (I), component (II) ) and the structure of component (III), use appropriate heavy metals to oxidize each component, thereby staining and fixing it, and calculate the dispersion using an electron microscope such as a transmission electron microscope (TEM) and a scanning electron microscope (SEM). Number average dispersed particle size of phase (B). Test pieces for electron microscope observation are ultrathin sections of the resin composition produced using a freezing microtome, etc., and may be produced after the above-mentioned staining, or may be stained after production. For example, when the amount of aromatic skeleton of component (I) is less than that of component (II), and when component (III) does not have an aromatic ring skeleton, ruthenium tetroxide can be used as the heavy metal of the dye for component (II). . The dye tends to oxidize the vinyl aromatic monomer unit of component (II) to the greatest extent, and secondly, the aromatic ring skeleton of the polar resin of component (I), but component (III) will not be oxidized. According to the electron microscope observation of the resin composition dyed by the oxidizing agent, an image was obtained in which component (I) was slightly stained, component (II) was stained the most, and component (III) was not stained. Therefore, the following examples can be used. Image analysis software or the like binarizes the image, thereby calculating the number average dispersed particle size of the dispersed phase (B) in the resin composition. In the above-mentioned binary image, when the dispersed phase (B) contains a large number of phases other than circles such as ellipses, it is preferable to increase the measurement range in the above-mentioned AFM observation for binarization to 10 μm. ×10 μm or so. In addition, when the particles of the dispersed phase (B) are at the edge of the image obtained within the above-mentioned visual field range in the above-mentioned visual field, it is preferable to define the value obtained by doubling the particle size of the particles as the implementation value. Calculate the number average dispersed particle diameter of the dispersed phase (B) using the Feret diameter described in the example.

From the viewpoint of further concentrating stress on the dispersed phase (B) and exhibiting sufficient impact resistance and toughness in the resin composition of this embodiment, the number average dispersed particle diameter of the dispersed phase (B) is set to 1.5 μm or less. , preferably 1.3 μm or less, further preferably 1.1 μm or less, still more preferably 1.0 μm or less, still more preferably 0.9 μm or less. The lower limit of the number average dispersed particle diameter of the dispersed phase (B) is not particularly limited, but a number average dispersed particle diameter of 0.01 μm or more tends to make it easier to maintain the rigidity of the resin composition of the present embodiment. As a method of maintaining sufficient rigidity for practical use in the resin composition of the present embodiment, there can also be mentioned a method of adding the following fillers and the like. Generally speaking, by increasing the bonding between component (II) and component ( III) If the amount of polar groups in the dispersed phase (B) causes the average dispersed particle size of the dispersed phase (B) to be less than 0.01 μm, the amount of side reactions in the step of adding the polar groups may increase, resulting in poor impact resistance of the resin composition. The properties and toughness tend to decrease, so the number average dispersed particle size of the dispersed phase (B) is preferably 0.01 μm or more.

The modified conjugated diene polymer (component (II)) is modified by having at least one selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an epoxy group, an oxetanyl group, and an amine group. A polar group that shows higher affinity and/or reactivity with the polar group of the polar resin (component (I)) and the epoxy group of the polymer having an epoxy group (component (III)). The polar groups of component (II) and component (III) have affinity and/or reactivity with the polar resin (component (I)). Therefore, the affinity and/or reactivity with component (I) is determined by the amount of polar groups bonded to component (II) and component (III). As mentioned above, from the viewpoint of improving the reactivity of component (I) with component (II) and component (III) and making the number average dispersed particle diameter of dispersed phase (B) 1.5 μm or less, bonding is modified The amount of polar groups of the conjugated diene polymer (II) is preferably 0.3 mоl/chain or more, more preferably 0.5 mоl/chain or more, and still more preferably 0.6 mоl/chain or more. If the amount of polar groups of component (II) does not reach 0.3 mol/chain, the amount of component (II) that is not reactive with component (I) and component (III) is relative to the amount of component (II) in the resin composition. When the total amount becomes more than 70 mol%, the dispersibility tends to be greatly reduced. As mentioned above, from the viewpoint of making the number average dispersed particle diameter of the dispersed phase (B) 1.5 μm or less, the mass ratio of the component (II) and the component (III) is preferably: component (II): component (III) = 1/99 to 99/1, more preferably 5/95 to 95/5, still more preferably 10/90 to 90/10, still more preferably 15/85 to 85/15. Furthermore, when a polyphenylene sulfide-based resin is used as component (I), the reactivity with the polyphenylene sulfide-based resin, which is a polar resin excellent in terms of rigidity, chemical resistance, and heat resistance, From the viewpoint of the above, it is preferable that the polar group bonded to component (II) is at least one selected from the group consisting of a hydroxyl group and a carboxyl group. The polar group bonded to component (III) is preferably reactive with the polar group of component (I) and the polar group of component (II), and is preferably selected from the group consisting of epoxy group, oxazolinyl group, and At least one of the group consisting of oxetanyl groups, more preferably an epoxy group.

When the component (III) is a polymer having an epoxy group, and when the epoxy-based component (I) is a polyphenylene sulfide resin, the polar groups of the component (I) and the component (II) It has high affinity and/or reactivity, especially with polyphenylene sulfide resin (component (I)). To improve the affinity and/or reactivity between component (III) and the polyphenylene sulfide resin (component (I)) and component (II), the number average dispersed particle size of the dispersed phase (B) is 1.5 μm or less. From a viewpoint, the content of the epoxy group of component (III) is preferably 1.0 mol/chain or more, more preferably 2.0 mol/chain or more, and further preferably 3.0 mol/chain or more.

(additive) From the viewpoint of improving the strength (rigidity) of the molded article, the resin composition of the present embodiment preferably further contains various additives, such as fillers.

In the resin composition of this embodiment, the filler is preferably a fibrous filler. The fibrous filler is not limited to the following, and examples thereof include glass fiber, carbon fiber, cellulose nanofiber, wollastonite, potassium titanate whisker, calcium carbonate whisker, aluminum borate whisker, and magnesium sulfate. Fiber-shaped inorganic fillers such as whiskers, sepiolite, xostolite, and zinc oxide whiskers. Among them, glass fiber, carbon fiber, cellulose nanofiber and wollastonite are preferred in terms of improving the strength (rigidity) and heat resistance of the molded article. The fibrous filler can also be surface-treated with a compound having an affinity group or a reactive group toward the polar resin (component (I)). The fibrous filler may contain only one type or two or more types.

In addition, other additives are not limited to the following, and examples thereof include oil, filler, heat stabilizer, ultraviolet absorber, nucleating agent, antioxidant, weathering agent, light stabilizer, plasticizer, and antistatic agent. , flame retardants, slip agents, anti-adhesive agents, anti-fogging agents, lubricants, pigments, dyes, dispersants, copper poison inhibitors, neutralizers, bubble preventers, welding strength improvers, natural oils, synthetic Additives such as oils and waxes. In addition, other elastomers or thermoplastic resins may be used as additives in any ratio. Only one type of these may be used, or two or more types may be used in combination.

Furthermore, an auxiliary agent that improves the affinity or reactivity between the polar resin (component (I)) and the modified conjugated diene polymer (component (II)) may be added to the resin composition of this embodiment. As the above-mentioned auxiliary agent, an alkoxysilane compound having at least one polar group selected from the group consisting of an epoxy group, an amine group, and an isocyanate group is preferred.

[Production method of resin composition] The manufacturing method of the resin composition of this embodiment is not specifically limited, and a well-known method can be utilized. For example, the following methods are used: using ordinary mixers such as Banbury mixers, single-screw extruders, twin-screw extruders, bidirectional kneaders, and multi-screw extruders to polar resin (component (I)), modified co-extruders, etc. Method of melting and kneading a conjugated diene polymer (component (II)) and a polymer having a polar group reactive with the component (I) and the component (II) (component (III)) to dissolve each component Or the method of removing the solvent by heating after dispersion and mixing. From the viewpoint of controlling the number average dispersed particle size of the dispersed phase (B) to 1.5 μm or less, a method of melting and kneading is preferred. As a manufacturing method of the resin composition of this embodiment, from the viewpoint of productivity and good kneadability, a method of melt-kneading each component using an extruder is preferred. In particular, a multi-screw with two or more axes is used to knead each component and sufficiently apply shear energy, thereby increasing the interface between the polar resin and the modified conjugated diene polymer to form a dispersed phase (B).

The resin temperature during kneading only needs to be a temperature at which the polar resin (I), the modified conjugated diene polymer (II), and the polymer (III) melt, and is preferably 270°C to 450°C. From the viewpoint of suppressing thermal degradation of the polar resin (I), the modified conjugated diene polymer (II), and the polymer (III), the temperature is more preferably 400° C. or lower.

In order to suppress the oxidation of the modified conjugated diene polymer (II), melt-kneading can also be performed under an inert gas such as nitrogen. When an extruder is used to produce the resin composition of this embodiment, the positions and orders of feeding the polar resin (I), the modified conjugated diene polymer (II), and other components are not particularly limited. In addition, when a thermosetting resin is used as the component (I), a component (II) obtained by dissolving a solution thermosetting resin and/or a solid thermosetting resin in an appropriate solvent, and optionally a component (III) may be added. , and optionally the above-mentioned additives are mixed, and then an appropriate hardener is added and mixed again to obtain the resin composition of this embodiment. In addition, before adding the hardener, the solvent in which the component (II) and the component (III) are dissolved may be removed by vacuum drying or other methods. Examples of the solvent include toluene, methyl ethyl ketone, cyclohexane, cyclohexanone, chloroform, tetrahydrofuran, and the like. When an epoxy resin, which is a polar resin excellent in terms of heat resistance, is used as the component (I), the hardener is not particularly limited as long as it has the function of hardening the polar resin (I). Examples thereof include: phenol-based hardeners, naphthol-based hardeners, active ester-based hardeners, benzophenol-based hardeners, cyanate ester-based hardeners, and carbodiimide-based hardeners. One type of hardening agent may be used alone, or two or more types may be used in combination. In addition, a hardening accelerator can also be added if necessary. Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. As a method of molding the resin composition of this embodiment, there is a method of injecting the resin composition into any mold and heating the mold at any time and temperature to obtain a cured product. From the viewpoint of productivity, the temperature of the mold is preferably 30 to 300°C, and more preferably 50 to 250°C. Moreover, from the viewpoint of productivity, the heating time is preferably 1 minute to 5 hours, more preferably 10 minutes to 3 hours.

Furthermore, when polyphenylene sulfide-based resin is used as the component (I), the molecular force or chemical bond between the polyphenylene sulfide-based resin and the modified conjugated diene-based polymer (component (II)) forms From this viewpoint, the polyphenylene sulfide-based resin preferably contains a thiol group or a carboxyl group.

In the manufacturing step of the resin composition of this embodiment, its shape is not particularly limited and may be any of granular, flake, linear, flake, etc. shapes.

(Preferred form of manufacturing method of resin composition) As a preferred embodiment of the method for producing the resin composition of the present embodiment, the following method can be exemplified. It has the following steps: for a modified conjugated diene polymer (component (II)), which has a polymer block (A) selected from the group consisting of a vinyl aromatic monomer unit as a main body, a conjugated diene monomer unit At least two types of polymer blocks among the polymer block (B) as the main body unit and the random polymer block (C) of the vinyl aromatic monomer unit and the conjugated diene monomer unit and have At least one polar group selected from the group consisting of hydroxyl and carboxyl groups; a resin (component (I)) having a polar group, which is selected from polyphenylene sulfide resin, polyethylene terephthalate resin At least one kind from the group consisting of resin and polybutylene terephthalate resin; and an olefin elastomer (component (III)) having an epoxy group, an oxazoline group, and an oxygen group. At least one polar group in the group consisting of heterocyclobutyl groups; the mass ratio of the above-mentioned resin having a polar group (component (I)) and the above-mentioned modified conjugated diene polymer (component (II)) is set to It is a resin with a polar group: modified conjugated diene polymer = 50/50 ~ 99/1, and the mass ratio of the above modified conjugated diene polymer to the above olefin elastomer with a polar group is set to It is a modified conjugated diene polymer: an olefin elastomer having a polar group = 1/99 to 99/1 and kneading to obtain a resin composition; and making the above resin composition have the above-mentioned polar group The continuous phase (A) of the resin (component (I)), and the dispersed phase (B) containing the above-mentioned modified conjugated diene polymer (component (II)) dispersed in the above-mentioned continuous phase (A), The step is to adjust the number average dispersed particle size of the dispersed phase (B) to 1.5 μm or less. Through the above-mentioned production method, a resin composition excellent in impact resistance and toughness is obtained.

[molded body] Molding System of the Present Embodiment The above-mentioned molded body of the resin composition of the present embodiment. The molded article of the present embodiment can be formed by using the resin composition of the present embodiment by a conventionally known method, such as extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotation Molding, powder condensation molding, foam molding, lamination molding, calendar molding, blow molding, etc. In addition, processes such as foaming, powdering, stretching, bonding, printing, painting, and plating can also be performed as necessary. By this molding method, it can be practically used as sheets, films, injection molded products of various shapes, hollow molded products, pressure molded products, vacuum molded products, extrusion molded products, foamed molded products, nonwoven fabrics, or fiber-shaped products. Various molded products such as molded products and synthetic leather. These molded products can be used in automotive interior and exterior materials, building materials, toys, home appliance parts, medical equipment, industrial parts, various hoses, various casings, various module boxes, various power control unit parts, other miscellaneous goods, and electronic equipment Such as substrates, casings, sheets, packages, etc. As a use of the molded article of this embodiment, from the viewpoint of stably exhibiting impact resistance and toughness, it is preferably used for non-porous members. The term "porous" here refers to pores that penetrate the material. Bubbles, which are non-penetrated pores produced by foaming, are not porous.

(Preferred form of molded article) In applications requiring higher impact resistance and toughness, the molded article of this embodiment is particularly preferably a molded article of the following resin composition, which resin composition contains: a resin having a polar group (Component (I)), which is at least one selected from the group consisting of polyphenylene sulfide resin, polyethylene terephthalate resin, and polybutylene terephthalate resin; Modified hydrogenated conjugated diene polymer (component (II)), which has a polymer block (A) selected from the group consisting of a vinyl aromatic monomer unit as a main body and a conjugated diene monomer unit as a main body. At least two of the polymer blocks (B), vinyl aromatic monomer units and random polymer blocks (C) of conjugated diene monomer units; and those with epoxy groups Elastomer (component (III)); and the above-mentioned modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of hydroxyl group and carboxyl group, and the above-mentioned molded article satisfies the following conditions (I-1)～(II-1). Applications requiring high impact resistance and toughness include, for example, vehicle conduits for automobiles, industrial piping, connectors, sockets, resistors, relay boxes, switches, bobbins, and capacitors. , variable capacitance boxes, optical pickups, oscillators, various terminal boards, recombiners, plugs, printed circuit boards and other electronic machine-related parts. These are formed bodies used under a wide range of temperature conditions from low temperature to high temperature. <Conditions (I-1)> Tensile elongation at break at normal temperature and at a tensile speed of 5 mm/min in a short strip-shaped test piece with a width of 10 mm, a length of 170 mm, and a thickness of 2 mm obtained from the molded body. The rate is over 25%. <Condition (II-1) In a short strip-shaped test piece of about 80 mm long, 10 mm wide, and 4 mm thick obtained from the molded body, the Charpy impact value in the Charpy impact test at -30°C is 15 kJ/m ² .

The formed body of this embodiment can be processed into a desired shape. For example, a dumbbell-shaped test piece or a short strip-shaped test piece can be produced by cutting a test piece from a portion of the formed body that is close to a plane. The above-mentioned test piece does not have to be completely flat, as long as it is flat enough to measure the tensile elongation at break and viscoelasticity. For example, if it is a cylindrical molded body, it also depends on the diameter of the cylinder, but a measurable test piece can be formed by cutting a test piece in the length direction. In addition, the thickness of the formed body may be thicker than 2 mm. In this case, the elongation at break and the test piece with a thickness of 2 mm can be measured by removing the portion with a thickness of 2 mm or more using a file, etc. and setting it as flat as possible. Viscoelasticity.

From the viewpoint of obtaining excellent impact resistance and toughness, the molded article of this embodiment is preferably a modified conjugated diene polymer (component (II)) dispersed in a polyphenylene sulfide resin or the like having polar groups. The state in the resin (component (I)), the dispersion state of the above-mentioned modified conjugated diene polymer (component (II)) to the above-mentioned resin (component (I)) having a polar group is the modified conjugated The average dispersed particle size of the diene polymer (component (II)) is 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.2 μm or less, still more preferably 1.1 μm or less. The average particle diameter of the modified conjugated diene polymer (component (II)) dispersed in the molded article of this embodiment can be measured by the method described in the following Examples.

In order to improve the strength, the resin composition constituting the molded article of this embodiment may contain 1 to 50 parts by mass of fillers and other additives based on 100 parts by mass of the resin composition, preferably 5 to 30 parts by mass. In addition to toughness and impact resistance, in order to add functions such as flame retardancy and tracking resistance, 1 to 70 parts by mass of other additives such as flame retardants may be included based on 100 parts by mass of the resin composition. In the case of additives, it is preferable that the tensile elongation at break measured under the above conditions is 10% or more and the impact resistance is 10 kJ/m ² or more.

[Analysis method of resin composition] The analysis method of the components of the resin composition of this embodiment is shown below. It is considered that the polarity of the modified conjugated diene polymer (component (II)) used in the resin composition of this embodiment is based on combining the above-mentioned modified conjugated diene polymer (component (II)) with a polar group. When the resin (component (I)) is kneaded, it reacts with the polar group of the component (I), thus helping to reduce the particle size of the dispersed phase (B). However, it is assumed that the modification will remain in the resin composition. The conjugated diene polymer (component (II)) often has polar groups. Furthermore, it is thought that although the polar group of the specific polymer (component (III)) is also reactive with component (I) and/or component (II), unreacted polar groups remain in the resin composition. In order to use the modified conjugated diene-based polymer (component (II)) having at least one selected from the group consisting of hydroxyl group and carboxyl group and the elastomer (component (II)) having an epoxy group in the molded article of the present embodiment, (III)) To perform qualitative analysis, first use polyphenylene as the matrix resin to dissolve the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) and not dissolve it. The resin composition is mixed with a solvent in which thioether resin, polyethylene terephthalate resin, and polybutylene terephthalate resin (component (I), respectively) are dissolved. Extract the conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)). When the matrix resin is a polyphenylene sulfide resin, since there is no solvent that can dissolve the polyphenylene sulfide resin below 200°C, the solvent and the resin composition are mixed under a temperature condition of 50 to 200°C. Mixing can dissolve undissolved polyphenylene sulfide resin (component (I)), unreacted modified conjugated diene polymer (component (II)), and unreacted elastomer with epoxy group (component (II)). Component (III)) is extracted. Examples of the solvent include toluene, cyclohexane, xylene, tetrahydrofuran, chloroform, nitroethane, nitropropane, ethylbenzene, etc.; from the viewpoint of solubility, chloroform, nitro Ethane, nitropropane, ethylbenzene, toluene. After extraction, the undissolved matrix resin is removed by filtration, etc., and the filtrate is used for liquid chromatography, whereby the unreacted modified conjugated diene polymer (component (II)) and the unreacted cyclic polymer can be separated. The oxygen-based elastomer (component (III)) is isolated.

In addition, when the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) have different solubilities, the following method can also be used: use the modified A solvent that dissolves the conjugated diene polymer (component (II)) but cannot dissolve the elastomer (component (III)) having an epoxy group is obtained by removing the solvent from the filtrate by vacuum drying or the like. The mixture of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) is mixed again in an appropriate solvent to remove the unreacted modified copolymer. The conjugated diene polymer (component (II)) and the unreacted elastomer having an epoxy group (component (III)) are separated. Generally speaking, examples of solvents with high solubility for the modified conjugated diene polymer (component (II)) include toluene, cyclohexane, and tetrahydrofuran.

The epoxy groups of modified conjugated diene polymers (component (II)) and elastomers with epoxy groups (component (III)) can be identified by nuclear magnetic resonance (NMR) and infrared absorption spectrometry ( IR), gas chromatography (GS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). When the resin composition contains components such as the following additives that are soluble in the solvent in the above-mentioned extraction step, each component can be separated by liquid chromatography or the like by utilizing differences in molecular weight and polarity, and can be separated by the above-mentioned NMR , IR, GS, and TOF-SIMS for identification.

As an analysis method that does not use a solvent, unreacted modified conjugated diene polymer (component (II)) and unreacted cyclic polymers can also be analyzed based on the infrared absorption spectrum obtained by observation with an atomic force microscope (AFM). The structural unit of the oxygen-based elastomer (component (III)), the type of polar group bonded to the unreacted modified conjugated diene polymer, and the polarity of the unreacted elastomer with epoxy group bonded Base type is specified. Examples of test pieces used for AFM measurement include precision cross-sections of resin compositions produced using ultramicrotome or the like.

In addition, you can also use a scanning transmission X-ray microscope to obtain image stack data, extract spectra based on the characteristic areas of the image stack data, and decompose them as the unique values of the reference spectrum to create a map according to different components. Modified conjugated diene polymer, (component (II)), structural unit of unreacted elastomer having an epoxy group (component (III)), bonded to unreacted modified conjugated diene The polar group type of the polymer and the polar group type bonded to the unreacted elastomer having an epoxy group are specified.

In the resin composition of this embodiment, the resin having a polar group (component (I)), the modified conjugated diene polymer (component (II)), and the elastomer having an epoxy group (component (III) )) The content ratio of the modified conjugated diene polymer (component (II)) in the resin with polar groups (component (I)) can be observed using the above-mentioned AFM, TEM, SEM and other electron microscopes, and the For the dispersion state of the epoxy-based elastomer (component (III)), the obtained image is binarized or tripled on each layer using image analysis software, etc., thereby calculating the resin (component (III)) having polar groups. I)), the content ratio of the modified conjugated diene polymer (component (II)) and the elastomer with an epoxy group (component (III)). In addition, the content ratio of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) can be determined based on the above-mentioned infrared absorption spectrum obtained by AFM observation, and based on only The peak intensity of the skeleton (specifically, the vinyl aromatic monomer unit skeleton) of the modified conjugated diene polymer (component (II)), and the modification of the modified conjugated diene polymer unit The ratio of the vinyl aromatic monomer units to the conjugated diene monomer units in the modified conjugated diene polymer is calculated by NMR, IR, GS, TOF-SIMS, etc. after separation.

The molded body of this embodiment can be made into any shape according to the use. Examples thereof include various containers, cylindrical containers, and shells. Specifically, examples include: protection and support members for box-shaped electrical and electronic component integrated modules, a plurality of separate semiconductors or modules, sensors, LED (light emitting diode) lamps, Connectors, slots, resistors, relay boxes, switches, bobbins, capacitors, variable capacitance boxes, optical pickups, oscillators, various terminal boards, recombiners, plugs, printed circuit boards, tuners, speakers , microphones, headphones, small motors, head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD suspensions, FDD chassis, motor brush holders, parabolic antennas, computer-related parts and other electrical and electronic parts. Examples include VTR (video tape recorder) parts, TV parts, irons, hair dryers, electric cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio, laser disks, and optical disks, and lighting parts. , refrigerator parts, air conditioner parts, typewriter parts, word processor parts, or water heater or bath water volume, temperature sensors and other water-use equipment parts and other household and office electrical product parts. Furthermore, examples include office computer-related parts, telephone-related parts, fax machine-related parts, photocopier-related parts, cleaning jigs, motor parts, writing machines, typewriters and other machine-related parts. Furthermore, examples include optical equipment such as microscopes, binoculars, cameras, and clocks, and parts related to precision machinery. Further examples include various valves such as alternator terminals, alternator connectors, IC (Integrated Circuit) regulators, potentiometer bases for optical cables, relay blocks, inhibitor switches, exhaust valves, etc. , various pipes related to fuel, exhaust system, and intake system, intake nozzle breather pipe, intake manifold, fuel pump, engine cooling water connector, carburetor body, carburetor gasket, exhaust gas sensor, Cooling water sensor, oil temperature sensor, brake protection sensor, throttle valve positioning sensor, crankshaft positioning sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioning, air conditioner Warm flow control valve, brush holder for radiator motor, water pump impeller, turbine blade, power motor related parts, distributor, starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, motor relay, transmission Box wiring harness, window washer nozzle, air conditioning panel switch board, coil for fuel-related solenoid valve, connector for fuse, speaker terminal, electrical parts insulating board, stepping motor rotor, lamp holder, lamp reflector, lamp cover, brake Automotive and vehicle-related parts such as pistons, solenoid reels, engine oil filters, and ignition boxes. The uses of the molded article of this embodiment are not limited to the above-mentioned uses. [Example]

Hereinafter, this embodiment will be described in detail with reference to specific examples and comparative examples. However, the present invention is not limited to the following examples and comparative examples in any way. Methods for measuring and evaluating the structure of the modified conjugated diene polymer and the physical properties of the resin composition in the Examples and Comparative Examples are shown below.

[Measurement and evaluation of the structure of the modified conjugated diene polymer and the physical properties of the resin composition] ((1) Amount of vinyl bonds in the modified conjugated diene polymer before hydrogenation) Modified conjugation The vinyl bond amount of the diene polymer is measured during each step of the polymerization process of the modified conjugated diene polymer before hydrogenation, and is sampled midway during the polymerization of the polymer block containing the conjugated diene monomer. The polymer was measured by proton nuclear magnetic resonance ( ¹ H-NMR) method. The measuring machine used ECS400 (manufactured by JEOL), the solvent used deuterated chloroform, the sample concentration was set to 50 mg/mL, the observation frequency was set to 400 MHz, the chemical shift standard was tetramethylsilane, the pulse delay was 2.904 seconds, and the number of scans was 64 , pulse width 45°, and measurement temperature 26°C. The vinyl bond amount is calculated by calculating the integral value per 1 H of each bonding pattern from the integral value of the signal attributed to the 1,4-bond and 1,2-bond, and then the 1,4-bond and 1,2-bond are calculated. -The ratio of bonds is calculated by the following formula. Amount of vinyl bonds = (1,2-bond/(1,4-bond + 1,2-bond))

((2) Hydrogenation rate based on the unsaturated bond of the conjugated diene monomer unit of the modified conjugated diene polymer) The hydrogenation rate of the modified conjugated diene polymer is based on the hydrogenation rate of the modified conjugated diene polymer. The conjugated diene polymer was measured by proton nuclear magnetic resonance ( ¹ H-NMR). The measurement conditions and measurement data processing method are the same as in (1) above. The hydrogenation rate is calculated by calculating the integrated value of the signal originating from the remaining double bonds and the signal originating from the hydrogenated conjugated diene at 4.5 to 5.5 ppm, and calculating the ratio.

((3) The amount of butene in the modified conjugated diene polymer based on 100 mol% of the total of 1,2-bonds and 1,4-bonds based on the conjugated diene monomer unit (vinyl hydrogenation rate) )) The amount of butene in the modified conjugated diene polymer based on a total of 100 mol% of the 1,2-bond and 1,4-bond of the conjugated diene compound unit is the modified cojugated diene polymer after hydrogenation. The conjugated diene polymer was measured by proton nuclear magnetic resonance ( ¹ H-NMR). The measurement conditions and measurement data processing methods are the same as those in (1) and (2) above. The signal derived from the total amount of conjugated diene monomer units in the hydrogenated modified conjugated diene-based polymer and the integrated value derived from the amount of butene were calculated, and their ratios were calculated. When calculating the above ratio, the integrated value of the signal attributed to butene (hydrogenated 1,2-bond) within 0 to 2.0 ppm of the spectrum is used. The vinyl hydrogenation rate is the amount of butene relative to 100 mol% of the total of 1,2-bonds and 1,4-bonds of the conjugated diene monomer unit.

((4) Content of vinyl aromatic monomer units in the modified conjugated diene polymer (hereinafter also referred to as "styrene content")) The content of vinyl aromatic monomer units is determined by using the modified cojugated diene polymer. The conjugated diene polymer was measured by proton nuclear magnetic resonance ( ¹ H-NMR) method. The measuring machine used ECS400 (manufactured by JEOL), the solvent used deuterated chloroform, the sample concentration was 50 mg/mL, the observation frequency was 400 MHz, the chemical shift standard used tetramethylsilane, the pulse delay was 2.904 seconds, the number of scans was 64, and the pulse The width is 45° and the measurement temperature is 26°C. The styrene content is calculated using the cumulative value of the total styrene aromatic signal within 6.2 to 7.5 ppm of the spectrum. Furthermore, the styrene content was also confirmed by calculating the vinyl aromatic monomer unit content of each polymer sampled in each step of the polymerization process of the modified conjugated diene polymer before hydrogenation.

((5) Weight average molecular weight and molecular weight distribution of modified conjugated diene polymer) The weight average molecular weight and molecular weight distribution of the modified conjugated diene polymer were measured using GPC [apparatus: HLC8220 (manufactured by Tosoh), column: TSKgelSUPER-HZM-N (4.6 mm×30 cm)]. Tetrahydrofuran was used as the solvent. The weight average molecular weight is calculated based on the molecular weight of the peak of the chromatogram and using a calibration curve (prepared using the peak molecular weight of the standard polystyrene) calculated based on the measurement of commercially available standard polystyrene. In addition, when there are multiple peaks in the chromatogram, the molecular weight is determined by calculating the weight average molecular weight based on the molecular weight of each peak and the composition ratio of each peak (calculated from the area ratio of each peak in the chromatogram). The molecular weight distribution is calculated based on the ratio of the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).

((6) Modification rate of modified conjugated diene polymer) Taking advantage of the characteristic that the modified components will be adsorbed on the GPC column filled with silica gel, for the sample solution containing the modified conjugated diene polymer and low molecular weight internal standard polystyrene, the The ratio of the modified conjugated diene polymer to the standard polystyrene in the chromatogram measured in (5) above is different from the ratio of the modified conjugated diene polymer to the standard polystyrene using a silica column GPC [apparatus: LC-10 (Shimadzu Corporation) (manufactured), column: Zorbax (manufactured by Dupont)] The ratio of the modified conjugated diene polymer to the standard polystyrene in the measured chromatogram was compared, and the ratio was measured based on the difference between them. The adsorption capacity of the silica column was determined as the modification rate. The modification rate is calculated from the following formula as the ratio (%) of amine groups having a specific structure at the end.

[Number 1]

a: Total polymer area (%) measured using polystyrene gel (PLgel) b: Area (%) of low molecular weight internal standard polystyrene (PS) measured using polystyrene gel (PLgel) c: Total polymer area (%) measured using silica column (Zorbax) d: Area (%) of low molecular weight internal standard polystyrene (PS) measured using a silica column (Zorbax)

((7) Glycidyl methacrylate bond amount) The modified conjugated diene polymer was refluxed in acetone at 60° C. for more than 1 hour to remove unreacted glycidyl methacrylate. Dissolve the above refluxed modified conjugated diene polymer in toluene, add 2 mol times more hydrochloric acid than the amount of glycidyl methacrylate added during the extrusion reaction, and reflux at 60°C for 30 minutes. As above, the epoxy group of glycidyl methacrylate and hydrochloric acid are reacted. The toluene solution after the reaction was titrated with potassium hydroxide with a coefficient of 1±0.05, thereby quantifying the unreacted hydrochloric acid, and calculating the amount of hydrochloric acid bonded to the modified conjugated diene polymer based on the amount of reacted hydrochloric acid. Amount of glycidyl methacrylate.

((8) Maleic anhydride bond amount) The modified conjugated diene polymer was dissolved in toluene and titrated with a methanol solution of sodium methoxide with a coefficient of 1±0.05 to calculate the amount of maleic anhydride bonds.

((9) Toughness of resin composition) The tensile elongation at break of the resin composition was measured based on ISO527 using a tensile testing machine [apparatus: TG-5kN (manufactured by Minebea Mitsumi)]. The test piece was used for ISO-527-2-1A dumbbells molded by an injection molding machine when polyethylene terephthalate or polyphenylene sulfide resin, which are thermoplastic resins, is used as component (I). The tensile test speed is 50 mm/min. For each composition, three or more test pieces were tested, and the average value was used as the physical property value. When an epoxy resin, which is a thermosetting resin, is used as the component (I), a test piece specified in JIS K6911 5.18.1(2) is prepared and measured at a tensile test speed of 5 mm/min.

((10) Charpy impact value) When polyethylene terephthalate or polyphenylene sulfide resin, which is a thermoplastic resin, is used as component (I), the notched Charpy impact value is measured in accordance with JIS K 7111-1 Impact strength and evaluation. The test piece is made by cutting both ends of the above-mentioned ISO dumbbell, and the parallel part is made into a short strip test piece with a length of about 80 mm, a width of about 10 mm, and a thickness of about 4 mm. The notch shape is set to A, and the striking direction is set to Along the edge. When an epoxy resin which is a thermosetting resin is used as the component (I), prepare a test piece specified in JIS K6911 5.20.2, set the notch shape to A, and set the striking direction to the edge. The measurement temperature was set to normal temperature (23°C) and -30°C. The unit is set to kJ/m ² .

((11) Processability (fluidity of resin composition)) When polyethylene terephthalate or polyphenylene sulfide resin, which is a thermoplastic resin, is used as the component (I), the following method is used to measure the spiral flow length of the resin composition and evaluate the processability. The longer the spiral flow length is, the higher the fluidity is and the better the processability is. Put the resin composition into the injection molding machine (clamping pressure 18 tf, screw system Φ16, SL screw) with the barrel temperature set to 300 to 320°C (hopper side to nozzle side), and rotate the screw at 150 rpm. The back pressure is 2 MPa, the measurement completion position is 55 mm, the filling speed is 50 mm/s, the injection pressure is 100 MPa, and the spiral flow measurement mold is used for a spiral pitch of 5 mm, a spiral thickness of 3 mm, a maximum spiral length of 850 mm, and a marking width of 10 mm. Perform injection molding. The cooling time was set to 20 s, and the spiral flow length (cm) was measured.

((12) Observation of the phase structure of the resin composition and measurement of the number average dispersed particle size of the dispersed phase) The phase structure in the resin composition is obtained by ultrasonic cleaning the following resin composition test molded body (ISO-527-2-1A) in ethanol for about 1 hour, cutting it using an ultramicrotome, and chipping it out. Observe after sectioning. Furthermore, cutting was performed by using a glass knife and a diamond knife at -150°C, thereby producing precise sections for AFM observation. The AFM is manufactured by Bruker, and the probe is SCANASYST-AIR. Fix the above-mentioned precision cross-section sample on the special sample fixing stage, set the measurement mode to QMN Mode in Air, the resolution to 512×256 pixels, the measurement range to 10×10 μm, the maximum indentation load to 500 pN, and scan The elastic modulus force curve obtained by setting the (Scan) speed to 1.0 Hz is used to create an elastic modulus map. The elastic modulus map is set to display a high elastic modulus as a bright image and a low elastic modulus as a dark grayscale image, and is output at 512×512 pixels. In addition, in order to remove noise, a 2-point moving average filtering process is performed to create a binary image. Binarization processing uses the Otsu method. For the particle analysis of the above binary image, the Feret diameter of each particle of the dispersed phase (B) was calculated using Analyze Partickles of ImageJ. For each resin composition, observation and Feret diameter calculation were performed in three molded bodies, and the average value of the above Feret diameters was used as the number average dispersion diameter of the dispersed phase (B).

[Manufacture of resin composition] (Component (I): resin with polar groups) Component (I): The following polar resin is used as the resin having a polar group. Polyphenylene sulfide resin: A900 (manufactured by Toray Co., Ltd.) Polyethylene terephthalate resin: TRF-8550FF (manufactured by Teijin Co., Ltd.) Epoxy resin: Bisphenol A type EXA-850CRP (manufactured by DIC Corporation)

(ingredient (II)) Component (II) is produced by the following production method of modified conjugated diene polymer. Modifiers, other components, and hydrogenation catalysts used for production are shown below. [Modifier] The following compounds are used as modifiers for producing modified conjugated diene polymers. Maleic anhydride (manufactured by Fuso Chemical Industry Co., Ltd.) 1,3-Dimethyl-2-imidazolidinone (manufactured by Tokyo Chemical Industry Co., Ltd.) Glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) Peroxide 25B (manufactured by NOF Co., Ltd.)

[Other ingredients] Epoxy resin hardener: cresol novolac resin LF-6161 (manufactured by DIC Corporation)

[Hydrogenation Catalyst] The following method was used to prepare a hydrogenation catalyst used for the hydrogenation reaction of the modified conjugated diene polymer. Add 1 L of dried and purified cyclohexane to the nitrogen-substituted reaction vessel, and add 100 mmol of bis(eta5-cyclopentadienyl)titanium dichloride while stirring thoroughly. A n-hexane solution containing 200 mmol of trimethylaluminum was reacted at room temperature for about 3 days to obtain a hydrogenation catalyst.

<Preparation of modified conjugated diene polymer (1)> Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20 mass %) containing 10 parts by mass of styrene was added. Next, 0.11 parts by mass of n-butyllithium based on 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) based on 1 mole of n-butyllithium were added, and the mixture was heated at 70°C. Polymerization was carried out for 20 minutes. Next, a cyclohexane solution containing 80 parts by mass of butadiene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 45 minutes. Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 20 minutes. Next, an equimolar amount of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added to 1 mole of n-butyllithium, and the reaction was carried out at 70° C. for 10 minutes. After the reaction, methanol was added. The terminal amine-modified conjugated diene polymer (1-A) obtained in the above manner has a styrene content of 20% by mass, a weight average molecular weight of 12.2×10 ⁴ , a molecular weight distribution of 1.10, and a vinyl bond amount of 44 %, the modification rate is 70% (the number of modifying groups in each polymer chain is 0.70). Furthermore, to the obtained terminal amine-modified conjugated diene polymer (1-A), Ti was added per 100 parts by mass of the terminal amine-modified conjugated diene polymer (1-A). It is 50 ppm of the hydrogenation catalyst prepared as above, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 2.0 hours. Next, 0.25 parts by mass of 3-(3,5-di-tert-butyl-4-hydroxyl as a stabilizer) was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (1-A). phenyl)octadecylpropionate to obtain a terminal amine-modified hydrogenated conjugated diene polymer (1-B). The obtained terminal amine-modified hydrogenated conjugated diene polymer (1-B) had a hydrogenation rate of 73% and a vinyl hydrogenation rate of 96%. The terminal amine-modified hydrogenated conjugated diene polymer (1-B) obtained in the above manner is mixed with maleic anhydride, and then supplied to a temperature setting of 150 to 200 C over the entire length of the extruder. °C in a twin-screw extruder and compounded to obtain a terminal carboxyl group-modified conjugated diene polymer (1-C). The obtained terminal carboxyl group-modified conjugated diene polymer (1-C) was subjected to GPC measurement under the above conditions, and it was confirmed that no amine groups were adsorbed to the column. That is, it means that all the amine groups have reacted with maleic anhydride, the amount of carboxyl groups is the same as that of the amine groups, and the number of modified groups per polymer chain is 0.70.

<Modified conjugated diene polymer (2)> Batch polymerization was performed using a tank-type reactor (internal volume: 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20 mass %) containing 10 parts by mass of styrene was added. Next, 0.11 parts by mass of n-butyllithium based on 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) based on 1 mole of n-butyllithium were added, and the mixture was heated at 70°C. Polymerization was carried out for 20 minutes. Next, a cyclohexane solution containing 80 parts by mass of butadiene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 45 minutes. Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 20 minutes. Next, 1.1 mol of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added with respect to 1 mol of n-butyllithium, and the reaction was carried out at 70° C. for 15 minutes. After the reaction, methanol was added. The terminal amine-modified conjugated diene polymer (2-A) obtained in the above manner has a styrene content of 20% by mass, a weight average molecular weight of 12.1×10 ⁴ , a molecular weight distribution of 1.10, and a vinyl bond amount of 45 %, the modification rate is 80% (the number of modifying groups in each polymer chain is 0.80). Furthermore, to the obtained terminal amine-modified conjugated diene polymer (2-A), Ti was added per 100 parts by mass of the terminal amine-modified conjugated diene polymer (2-A). It is 50 ppm of the hydrogenation catalyst prepared as above, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 2.0 hours. Next, 0.25 parts by mass of 3-(3,5-di-tert-butyl-4-hydroxy as a stabilizer) was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (2-A). phenyl)octadecylpropionate to obtain a terminal amine-modified hydrogenated conjugated diene polymer (2-B). The obtained terminal amine-modified hydrogenated conjugated diene polymer (2-B) had a hydrogenation rate of 74% and a vinyl hydrogenation rate of 96%. The terminal amine-modified hydrogenated conjugated diene polymer (2-B) obtained in the above manner is mixed with maleic anhydride, and then supplied to a temperature setting of 150 to 200 C over the entire length of the extruder. °C in a twin-screw extruder and compounded to obtain a terminal carboxyl group-modified conjugated diene polymer (2-C). The obtained terminal carboxyl group-modified conjugated diene polymer (2-C) was subjected to GPC measurement under the above conditions, and it was confirmed that no amine groups were adsorbed on the column. That is, it means that all the amine groups have reacted with maleic anhydride, the amount of carboxyl groups is the same as that of the amine groups, and the number of modified groups per polymer chain is 0.80.

<Modified conjugated diene polymer (3)> Batch polymerization was performed using a tank-type reactor (internal volume: 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass) was put in. Next, 0.11 parts by mass of n-butyllithium based on 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) based on 1 mole of n-butyllithium were added, and the mixture was heated at 70°C. Polymerization was carried out for 20 minutes. Next, a cyclohexane solution containing 70 parts by mass of butadiene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 45 minutes. Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 20 minutes. Next, 1.1 mol of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added with respect to 1 mol of n-butyllithium, and the reaction was carried out at 70° C. for 15 minutes. After the reaction, methanol was added. The terminal amine-modified conjugated diene polymer (3-A) obtained in the above manner has a styrene content of 30% by mass, a weight average molecular weight of 12.0×10 ⁴ , a molecular weight distribution of 1.09, and a vinyl bond amount of 43 %, the modification rate is 79% (the number of modifying groups in each polymer chain is 0.79). Furthermore, to the obtained terminal amine-modified conjugated diene polymer (3-A), Ti was added per 100 parts by mass of the terminal amine-modified conjugated diene polymer (3-A). It is 50 ppm of the hydrogenation catalyst prepared as above, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80°C for about 2.0 hours. Next, 0.25 parts by mass of 3-(3,5-di-tert-butyl-4-hydroxyl as a stabilizer) was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (3-A). phenyl)octadecylpropionate to obtain a terminal amine-modified hydrogenated conjugated diene polymer (3-B). The obtained terminal amine-modified hydrogenated conjugated diene polymer (3-B) had a hydrogenation rate of 75% and a vinyl hydrogenation rate of 96%. The terminal amine-modified hydrogenated conjugated diene polymer (3-B) obtained in the above manner is mixed with maleic anhydride, and then supplied to a temperature setting of 150 to 200°C over the entire length of the extruder. into a twin-screw extruder and compounded to obtain a terminal carboxyl-modified conjugated diene polymer (3-C). The obtained terminal carboxyl group-modified conjugated diene polymer (3-C) was subjected to GPC measurement under the above conditions, and it was confirmed that no amine groups were adsorbed on the column. That is, it means that all the amine groups have reacted with maleic anhydride, the amount of carboxyl groups is the same as the amine group, and the number of modified groups per polymer chain is 0.79.

<Modified conjugated diene polymer (4)> In addition to adding 0.2 mol of tetramethylethylenediamine (TMEDA) per mole of n-butyllithium, the above <modified conjugation was performed Diene polymer (2)>The same operation is carried out to obtain a terminal carboxyl group-modified conjugated diene polymer (4-C). The obtained terminal carboxyl group-modified conjugated diene copolymer (4-C) had a styrene content of 20% by mass, a weight average molecular weight of 12.2×10 ⁴ , a molecular weight distribution of 1.09, and a vinyl bond amount of 24%. The hydrogenation rate is 78%, the vinyl hydrogenation rate is 96%, and the modification rate is 80% (the number of modified groups per polymer chain is 0.79).

<Modified conjugated diene polymer (5)> Except for adding 0.09 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers, the same procedure as the above <modified conjugated diene polymer was carried out. (2)>The same operation is performed to obtain a terminal carboxyl-modified conjugated diene polymer (5-C). The obtained terminal carboxyl group-modified conjugated diene copolymer (5-C) had a styrene content of 20% by mass, a weight average molecular weight of 10.1×10 ⁴ , a molecular weight distribution of 1.10, and a vinyl bond amount of 43%. The hydrogenation rate is 78%, the vinyl hydrogenation rate is 96%, and the modification rate is 80% (the number of modified groups per polymer chain is 0.80).

<Modified conjugated diene polymer (6)> Batch polymerization was performed using a tank-type reactor (internal volume: 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 6.5 parts by mass of styrene was added. Next, 0.11 parts by mass of n-butyllithium based on 100 parts by mass of all monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) based on 1 mol of n-butyllithium were added, and the mixture was heated at 70°C. Polymerization was carried out for 20 minutes. Next, a cyclohexane solution (concentration 20 mass %) containing 87 parts by mass of butadiene was added, and polymerization was performed at 70° C. for 45 minutes. Next, a cyclohexane solution containing 6.5 parts by mass of styrene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 20 minutes. Next, 1.1 mol of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added with respect to 1 mol of n-butyllithium, and the reaction was carried out at 70° C. for 15 minutes. After the reaction, methanol was added. The terminal amine-modified conjugated diene polymer (6-A) obtained in the above manner has a styrene content of 13% by mass, a weight average molecular weight of 12.2×10 ⁴ , a molecular weight distribution of 1.09, and a vinyl bond amount of 35 %, the modification rate is 81% (the number of modifying groups in each polymer chain is 0.81). Furthermore, to the obtained terminal amine-modified conjugated diene polymer (6-A), 100 parts by mass of the terminal amine-modified conjugated diene polymer (6-A) was added based on Ti. The hydrogenation catalyst prepared in the above manner was calculated as 90 ppm, and the hydrogenation reaction was carried out for about 2.0 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of 3-(3,5-di-tert-butyl-4-hydroxyl as a stabilizer) was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (6-A). phenyl)octadecylpropionate to obtain a terminal amine-modified hydrogenated conjugated diene polymer (6-B). The obtained terminal amine-modified hydrogenated conjugated diene polymer (6-B) had a hydrogenation rate of 80% and a vinyl hydrogenation rate of 98%. The terminal amine-modified hydrogenated conjugated diene polymer (6-B) obtained in the above manner is mixed with maleic anhydride, and then supplied to an extruder where the temperature over the entire length is set to 150 to 200°C. into a twin-screw extruder and compounded, thereby obtaining a terminal carboxyl-modified conjugated diene polymer (6-C). The obtained terminal carboxyl group-modified conjugated diene polymer (6-C) was subjected to GPC measurement under the above conditions, and it was confirmed that no adsorption of amine groups to the column occurs. That is, it means that all the amine groups have reacted with maleic anhydride, the amount of carboxyl groups is the same as that of the amine groups, and the number of modified groups per polymer chain is 0.81.

<Modified conjugated diene polymer (7)> Batch polymerization was performed using a tank-type reactor (internal volume: 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 25 parts by mass of styrene (concentration 20% by mass) was added. Next, 0.11 parts by mass of n-butyllithium based on 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) based on 1 mole of n-butyllithium were added, and the mixture was heated at 70°C. Polymerization was carried out for 20 minutes. Next, a cyclohexane solution (concentration 20 mass %) containing 50 parts by mass of butadiene was added, and polymerization was performed at 70° C. for 45 minutes. Next, a cyclohexane solution containing 25 parts by mass of styrene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 20 minutes. Next, 1.1 mol of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added with respect to 1 mol of n-butyllithium, and the reaction was carried out at 70° C. for 15 minutes. After the reaction, methanol was added. The terminal amine-modified conjugated diene polymer (7-A) obtained in the above manner has a styrene content of 50% by mass, a weight average molecular weight of 11.9×10 ⁴ , a molecular weight distribution of 1.11, and a vinyl bond amount of 43 %, the modification rate is 79% (the number of modifying groups in each polymer chain is 0.79). Furthermore, to the obtained terminal amine-modified conjugated diene polymer (7-A), 100 parts by mass of the terminal amine-modified conjugated diene polymer (7-A) was added based on Ti. Calculate 50 ppm of the hydrogenation catalyst prepared in the above manner, and perform a hydrogenation reaction for about 2.0 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of 3-(3,5-di-tert-butyl-4-hydroxyl as a stabilizer) was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (7-A). phenyl)octadecylpropionate to obtain a terminal amine-modified hydrogenated conjugated diene polymer (7-B). The obtained terminal amine-modified hydrogenated conjugated diene polymer (7-B) had a hydrogenation rate of 77% and a vinyl hydrogenation rate of 97%. The terminal amine-modified hydrogenated conjugated diene polymer (7-B) obtained in the above manner is mixed with maleic anhydride, and then supplied to an extruder where the temperature over the entire length is set to 150 to 200°C. in a twin-screw extruder and compounded to obtain a terminal carboxyl group-modified conjugated diene polymer (7-C). The obtained terminal carboxyl group-modified conjugated diene polymer (7-C) was subjected to GPC measurement under the above conditions, and it was confirmed that no amine groups were adsorbed to the column. That is, it means that all the amine groups have reacted with maleic anhydride, the amount of carboxyl groups is the same as the amine group, and the number of modified groups per polymer chain is 0.79.

<Modified conjugated diene polymer (8)> Batch polymerization was performed using a tank-type reactor (internal volume: 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20 mass %) containing 10 parts by mass of styrene was added. Next, 0.11 parts by mass of n-butyllithium based on 100 parts by mass of all monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) based on 1 mol of n-butyllithium were added, and the mixture was heated at 70°C. Polymerization was carried out for 20 minutes. Next, a cyclohexane solution containing 80 parts by mass of butadiene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 45 minutes. Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 20 minutes. Next, methanol is added. The conjugated diene polymer (8-A) obtained in the above manner has a styrene content of 30% by mass, a weight average molecular weight of 12.1×10 ⁴ , a molecular weight distribution of 1.10, and a vinyl bond amount of 36%. Furthermore, to the obtained conjugated diene polymer (8-A), 70 ppm based on Ti per 100 parts by mass of the conjugated diene polymer (8-A) was added in the above manner. The hydrogenation catalyst was prepared, and the hydrogenation reaction was carried out for about 3.0 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propane as a stabilizer was added based on 100 parts by mass of the conjugated diene polymer (8-A). stearyl acid ester to obtain a hydrogenated conjugated diene polymer (8-B). The obtained hydrogenated conjugated diene polymer (8-B) had a hydrogenation rate of 97% and a vinyl hydrogenation rate of 99%. The hydrogenated conjugated diene polymer (8-B) obtained in the above manner is mixed with glycidyl methacrylate, and then supplied to a twin-axis machine whose temperature is set to 150 to 220°C over the entire length of the extruder. In the extruder, Peroxide 25B is added from the middle pan of the extruder and compounded to obtain a main chain epoxy-modified conjugated diene polymer (8-C). The obtained main chain epoxy-modified conjugated diene polymer (8-C) was titrated using the above method. As a result, the glycidyl methacrylate bond amount was 1.2 mass%.

<Modified conjugated diene polymer (9)> Batch polymerization was performed using a tank-type reactor (internal volume: 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass) was put in. Next, 0.11 parts by mass of n-butyllithium based on 100 parts by mass of all monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) based on 1 mol of n-butyllithium were added, and the mixture was heated at 70°C. Polymerization was carried out for 20 minutes. Next, a cyclohexane solution containing 70 parts by mass of butadiene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 45 minutes. Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20 mass %) was added, and polymerization was performed at 70° C. for 20 minutes. Next, methanol is added. The conjugated diene polymer (9-A) obtained in the above manner has a styrene content of 30% by mass, a weight average molecular weight of 12.2×10 ⁴ , a molecular weight distribution of 1.08, and a vinyl bond amount of 37%. Furthermore, to the obtained conjugated diene polymer (9-A), 50 ppm based on Ti per 100 parts by mass of the conjugated diene polymer (9-A) was added in the above manner. The hydrogenation catalyst was prepared, and the hydrogenation reaction was carried out for about 2.0 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propane as a stabilizer was added based on 100 parts by mass of the conjugated diene polymer (9-A). stearyl acid ester to obtain a hydrogenated conjugated diene polymer (9-B). The obtained hydrogenated conjugated diene polymer (9-B) had a hydrogenation rate of 76% and a vinyl hydrogenation rate of 96%. The hydrogenated conjugated diene polymer (9-B), maleic anhydride, and organic peroxide (Perhexa 25B (manufactured by NOF Co., Ltd.)) obtained in the above manner were mixed and then supplied to The compound is compounded in a twin-screw extruder with the temperature over the entire length of the extruder set at 150 to 220°C, thereby obtaining a main chain acid anhydride group-modified conjugated diene polymer (9-C). The obtained main chain acid anhydride group-modified conjugated diene polymer (9-C) was titrated using the method shown in the above ((9) Maleic anhydride bonding amount). As a result, the maleic anhydride group was The acid anhydride bond amount is 1.5% by mass.

<Modified conjugated diene polymer (10)> Main chain acid anhydride group-modified conjugated diene polymer M1943 (Tuftec manufactured by Asahi Kasei Co., Ltd.) was used.

(Component (III): Polymer having a polar group reactive with components (I) and (II)) The following polymer having an epoxy group was used as the component (III). Bondfast BF-7M (glycidyl methacrylate-ethylene-methyl acrylate copolymer, manufactured by Sumitomo Chemical Co., Ltd.) Epo Friend AT501 (epoxide of styrene-butadiene block copolymer, manufactured by Daicel Co., Ltd.) ELVAOY ^TM PTW (ethylene-glycidyl methacrylate-butyl acrylate copolymer, manufactured by Dow Corporation)

[Examples 1 to 15] Use the above ingredients with the composition ratio shown in Table 1 and Table 2 and use a twin-screw extruder ZSK28 (manufactured by Werner and Pfleiderer) with a barrel setting temperature of 300°C, a screw rotation speed of 200 rpm, and a discharge rate of 9 kg/hour. Melt kneading is performed to produce a resin composition. Thereafter, an injection molding machine was used to perform injection molding with the barrel temperature set at 300°C and the mold temperature set at 140°C to produce a test piece (ISO-527-2-1A).

[Comparative Examples 1 to 11] Modified conjugated diene polymers (1-B) and (1-C) are used as component (II). Other materials and conditions were the same as in Examples 1 to 15, a resin composition was produced with the composition ratio shown in Table 3, and a test piece was produced.

The number average dispersed particle size, toughness, and impact resistance of the dispersed phase (B) of each resin composition are shown in Tables 1 to 3. Furthermore, in the table, "(1)" indicates that the specimen in the Charpy impact test did not break.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 composition ratio Ingredient(I) A900 parts by mass 90 80 80 80 60 80 80 80 Ingredient(II) (1-C) 5 10 15 5 20 10 10 0 (2-C) 0 0 0 0 0 0 0 10 (3-C) 0 0 0 0 0 0 0 0 (4-C) 0 0 0 0 0 0 0 0 (5-C) 0 0 0 0 0 0 0 0 (6-C) 0 0 0 0 0 0 0 0 (7-C) 0 0 0 0 0 0 0 0 (8-C) 0 0 0 0 0 0 0 0 Ingredient(III) Bondfast BF-7M 5 10 5 15 20 0 0 10 Epo Friend AT501 0 0 0 0 0 10 0 0 ELVAOY ^™ PTW 0 0 0 0 0 0 10 0 Number average dispersed particle size of dispersed phase (B) μm 0.29 0.25 0.32 0.20 0.80 0.88 0.85 0.18 Tensile elongation at break % 35 70 66 59 110 65 68 73 Charpy impact value (23℃) kJ/m ² 37 55 ⁽¹⁾ 57 ⁽¹⁾ 48 69 ⁽¹⁾ 47 50 56 ⁽¹⁾ Charpy impact value (-30℃) kJ/m ² twenty one 41 ⁽¹⁾ twenty four 19 48 ⁽¹⁾ 26 28 45 ⁽¹⁾ Spiral flow length cm 64 26 33 twenty four 14 twenty one 25 28

[Table 2] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 composition ratio Ingredient(I) A900 parts by mass 80 80 80 80 80 90 80 Ingredient(II) (1-C) 0 0 0 0 0 0 0 (2-C) 0 0 0 0 0 0 0 (3-C) 10 0 0 0 0 0 0 (4-C) 0 10 0 0 0 0 0 (5-C) 0 0 10 0 0 0 0 (6-C) 0 0 0 10 0 0 0 (7-C) 0 0 0 0 10 0 0 (8-C) 0 0 0 0 0 10 20 Ingredient(III) Bondfast BF-7M 10 10 10 10 10 0 0 Epo Friend AT501 0 0 0 0 0 0 0 ELVAOY ^™ PTW 0 0 0 0 0 0 0 Number average dispersed particle size of dispersed phase (B) μm 0.22 0.18 0.17 0.18 0.22 1.2 1.1 Tensile elongation at break % 58 78 77 83 55 33 56 Charpy impact value (23℃) kJ/m ² 48 60 ⁽¹⁾ 58 ⁽¹⁾ 66 ⁽¹⁾ 45 35 48 ⁽¹⁾ Charpy impact value (-30℃) kJ/m ² 18 49 ⁽¹⁾ 48 ⁽¹⁾ 51 ⁽¹⁾ 17 17 38 ⁽¹⁾ Spiral flow length cm 110 26 twenty one 25 twenty four 71 52

[table 3] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Comparative example 10 Comparative example 11 composition ratio Ingredient(I) A900 parts by mass 100 80 90 90 80 80 80 80 80 80 80 Ingredient(II) (1-B) - - 10 - 20 - 10 15 - - - (1-C) - 20 - - - - - - - - - (9-B) - - - - - - - - 20 - - (9-C) - - - - - - - - - 20 - (10) - - - - - - - - - - 20 Ingredient(III) Bondfast BF-7M - - - 10 - 20 10 5 - - - Number average dispersed particle size of dispersed phase (B) μm - 2.2 2.3 - 2.4 - 1.6 1.9 3.2 2.1 2.0 Tensile elongation at break % 3.0 5.8 9.0 15 13 45 32 twenty one 4.5 4.8 4.9 Charpy impact value (23℃) kJ/m ² 6.0 8.3 12 26 13 39⑴ 31 27 6.2 6.3 6.4 Charpy impact value (-30℃) kJ/m ² 2.7 4.6 8.2 9.3 8.4 11 10 9.8 2.9 3.3 3.6 Spiral flow length cm 74 52 58 14 53 12 20 twenty two 63 25 26

[Examples 16 to 22] Use the above components (I) to (III) with the composition ratio shown in Table 4 and use a twin-screw extruder ZSK28 (manufactured by Werner and Pfleiderer), with a barrel setting temperature of 290°C, a screw rotation speed of 200 rpm, and a discharge amount. Melt kneading is performed at 9 kg/hour to produce a resin composition. Then, an injection molding machine was used to perform injection molding with a barrel set temperature of 290°C and a mold temperature set of 120°C to produce a test piece (ISO-527-2-1A).

[Comparative Examples 12 to 15] Modified conjugated diene polymer (9-B) is used as component (II). Other materials and conditions were the same as in Examples 16 to 22, a resin composition was produced with the composition ratio shown in Table 5, and a test piece was produced.

The number average dispersed particle size, toughness and impact resistance of the dispersed phase (B) of each resin composition are shown in Table 4 and Table 5.

[Table 4] Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 composition ratio Ingredient(I) TRF-8550FF parts by mass 90 80 80 80 80 80 80 Ingredient(II) (2-C) 5 10 5 10 0 0 0 (4-C) 0 0 0 0 10 0 0 (6-C) 0 0 0 0 0 10 0 (8-C) 0 0 0 0 0 0 20 Ingredients(III)) Bondfast BF-7M 5 10 15 0 10 10 0 Epo Friend AT501 0 0 0 10 0 0 0 Number average dispersed particle size of dispersed phase (B) μm 1.1 1.0 0.72 0.92 0.92 0.91 1.10 Tensile elongation at break % 6.8 11.1 15.2 10.1 13.4 14.5 9.9 Charpy impact value (23℃) kJ/m ² 18 twenty two 32 18 26 29 15 Charpy impact value (-30℃) kJ/m ² 8.7 14 19 12 17 18 10 Spiral flow length cm 322 295 244 293 288 280 300

[table 5] Comparative example 12 Comparative example 13 Comparative example 14 Comparative example 15 composition ratio Ingredient(I) TRF-8550FF parts by mass 100 90 80 80 Ingredient(II) (9-B) 0 10 20 0 Ingredient(III) Bondfast BF-7M 0 0 0 20 Number average dispersed particle size of dispersed phase (B) μm - 3.2 3.3 - Tensile elongation at break % 1.5 2.2 4.1 8.4 Charpy impact value (23℃) kJ/m ² 2.1 2.4 5.0 12 Charpy impact value (-30℃) kJ/m ² 0.9 3.3 3.4 7.4 Spiral flow length cm 362 330 311 111

[Examples 23 to 27] The above-mentioned components were used and a resin composition was produced at the composition ratio shown in Table 6. When the component (II) and the component (III) are included, the kneading is performed by dissolving the component (III) in toluene at a concentration of about 20% by mass and adding it to the epoxy resin solution for stirring. Then, vacuum drying is performed at normal temperature to remove most of the toluene. Then, a hardener is added and stirred to obtain a solution resin composition. Next, after the above-mentioned solution resin composition is heated to 80°C, the above-mentioned solution resin composition is injected into a mold having a shape specified in the above-mentioned toughness test and Charpy impact test, and compression molding is performed at 140°C for 2 hours. , thereby obtaining a cured product of the resin composition. Table 6 shows the number average dispersed particle size, toughness and impact resistance of the dispersed phase (B) of each resin composition.

[Comparative Examples 16 to 21] Modified conjugated diene polymer (9-B) is used as component (II). Other materials and conditions were the same as in Examples 23 to 27, and a resin composition was produced with the composition ratio shown in Table 7, and a test piece was produced.

The number average dispersed particle size, toughness, and impact resistance of the dispersed phase (B) of each resin composition are shown in Tables 6 and 7.

[Table 6] Example 23 Example 24 Example 25 Example 26 Example 27 composition ratio Ingredient(I) EXA-850CRP parts by mass 70 70 80 70 70 Ingredient(II) (3-B) 30 0 0 0 0 (3-C) 0 30 20 15 15 Ingredient(III) Bondfast BF-7M Epo Friend AT501 0 0 0 15 0 0 0 0 0 15 other ingredients KA-1163 20 20 25 20 20 Number average dispersed particle size of dispersed phase (B) μm 1.1 0.88 0.93 0.73 0.68 Tensile elongation at break % 6.9 9.0 6.1 10.3 11.2 Charpy impact value (23℃) kJ/m ² 8.1 10.1 7.7 11.5 13.4 Charpy impact value (-30℃) kJ/m ² 6.0 8.3 5.5 9.8 11.4

[Table 7] Comparative example 16 Comparative example 17 Comparative example 18 Comparative example 19 Comparative example 20 Comparative example 21 composition ratio Ingredient(I) EXA-850CRP parts by mass 100 70 80 70 70 70 Ingredient(II) (9-B) 0 30 20 0 0 15 Ingredient(III) Bondfast BF-7M Epo Friend AT501 0 0 0 30 0 0 0 0 0 0 30 15 other ingredients KA-1163 30 20 25 20 20 20 Number average dispersed particle size of dispersed phase (B) μm - 3.5 3.6 - - 2.4 Tensile elongation at break % 1.1 3.1 2.5 4.2 5.2 3.5 Charpy impact value (23℃) kJ/m ² 2.9 4.2 3.6 5.0 5.2 4.6 Charpy impact value (-30℃) kJ/m ² 1.2 2.1 1.8 2.9 3.3 2.7

From the results in Tables 1 to 7, it is clear that Examples 1 to 27 are excellent in impact resistance and toughness.

This application is based on an application filed with the Japan Patent Office on July 27, 2021 (Special Application No. 2021-122776), and an application filed with the Japan Patent Office on September 21, 2021 (Special Application No. 2021- 153417), the contents of which are incorporated herein by reference. [Industrial availability]

The resin composition of the present invention can be practically used as sheets, films, various shapes of injection molded products, hollow molded products, pressure molded products, vacuum molded products, extrusion molded products, foamed molded products, nonwoven fabrics, or fibrous molded products. products, synthetic leather, etc. These molded products are used as automotive interior and exterior materials, building materials, toys, home appliance parts, medical equipment, industrial parts, various hoses, various casings, and various module boxes. , various power control unit parts, other miscellaneous items, etc. Industrial availability.

Claims (12)

A resin composition comprising: component (I): selected from the group consisting of polyphenylene sulfide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and epoxy resin. At least one resin with a polar group in the group (except the following component (II)); component (II): at least one modified conjugated diene polymer, the modified conjugated diene polymer The material has a polar group bonded to a block polymer, and the block polymer has: a polymer block (A) selected from a vinyl aromatic monomer unit as the main body, a conjugated diene monomer At least two types of polymer blocks among the polymer block (B) as the main unit and the random polymer block (C) of the vinyl aromatic monomer unit and the conjugated diene monomer unit, the above-mentioned polarity The group is at least one selected from the group consisting of acid anhydride group, hydroxyl group, carboxyl group, dicarboxyl group, epoxy group, oxetanyl group and amine group, and the above-mentioned conjugated diene monomer unit is selected from the group consisting of 1,3 -Butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2- At least one or more species from the group consisting of methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene; and component (III): having a group selected from the group consisting of epoxy,

A polymer with at least one polar group in the group consisting of an oxetanyl group and an oxetanyl group (excluding the above-mentioned components (I) and (II)); the above-mentioned resin composition has a continuous phase of the above-mentioned component (I) (A), and a dispersed phase (B) containing the above-mentioned component (II) dispersed in the above-mentioned continuous phase (A), the number average dispersed particle diameter of the above-mentioned dispersed phase (B) is 1.5 μm or less, the above-mentioned component (I) The mass ratio of the above-mentioned component (II) is component (I): component (II) = 50/50~99/1, and the mass ratio of the above-mentioned component (II) to the above-mentioned component (III) is component (II): component ( III)=1/99~99/1. The resin composition of claim 1, wherein the component (I) is selected from the group consisting of polyphenylene sulfide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and epoxy resin. At least one resin in the group consisting of resins. The resin composition of claim 1 or 2, wherein the component (II) includes a hydrogenated modified conjugated diene polymer obtained by hydrogenating aliphatic double bonds derived from a conjugated diene compound. The resin composition of claim 1 or 2, wherein the above component (I) is a polyphenylene sulfide resin. The resin composition according to claim 1 or 2, wherein the component (II) includes a modified conjugated diene polymer to which at least one polar group selected from the group consisting of hydroxyl and carboxyl groups is bonded. The resin composition of claim 1, wherein the component (III) is an olefin elastomer having an epoxy group. The resin composition of claim 3, wherein the hydrogenation rate of the hydrogenated modified conjugated diene polymer is 90% or less. The resin composition of claim 1 or 2, wherein the vinyl aromatic monomer in the above component (II) The content of unit units is 40% by mass or less. The resin composition according to claim 1, wherein the component (III) is an elastomer having an epoxy group which is a copolymer of a polymerizable monomer having an epoxy group and an unsaturated hydrocarbon compound. The resin composition of claim 1, wherein the component (III) is a copolymer of a polymerizable monomer having an epoxy group, an unsaturated hydrocarbon compound, (meth)acrylate and/or vinyl acetate. A method for producing a resin composition, which has the following steps: for a modified conjugated diene polymer (component (II)), which has a polymer block selected from the group consisting of a vinyl aromatic monomer unit as a main body ( A), the polymer block (B) mainly composed of conjugated diene monomer units, and the random polymer block (C) of vinyl aromatic monomer units and conjugated diene monomer units. At least two types of polymer blocks have at least one polar group selected from the group consisting of hydroxyl and carboxyl groups. The above-mentioned conjugated diene monomer unit is selected from the group consisting of 1,3-butadiene and 2-methyl. 1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene At least one or more of the group consisting of dienes, 1,3-hexadiene, and farnesene; a resin (component (I)) having a polar group, which is selected from the group consisting of polyphenylene sulfide resins, polyphenylene sulfide resins, and polyphenylene sulfide resins. At least one kind from the group consisting of ethylene terephthalate resin and polybutylene terephthalate resin; and an olefin elastomer (component (III)) having an epoxy group selected from the group consisting of ,

At least one polar group in the group consisting of an oxetanyl group and an oxetanyl group; The above-mentioned resin having a polar group (component (I)) and the above-mentioned modified conjugated diene polymer (component (II) )) is set to resin with polar groups: modified conjugated diene polymer = 50/50~99/1, and the above modified conjugated diene polymer and the above olefin series with polar groups are The mass ratio of the elastomer is set to modified conjugated diene polymer: olefin elastomer with polar group = 1/99~99/1, and kneading is performed to obtain a resin composition; and making the above resin The composition has a continuous phase (A) of the resin having a polar group (component (I)), and a modified conjugated diene polymer (component (II)) dispersed in the continuous phase (A). the dispersed phase (B), and the step of making the number average dispersed particle size of the dispersed phase (B) 1.5 μm or less. A molded article, which is a molded article of a resin composition containing: a resin (component (I)) having a polar group, which is selected from the group consisting of polyphenylene sulfide resin, polyethylene terephthalate At least one kind from the group consisting of ester resin and polybutylene terephthalate resin; a modified conjugated diene polymer (component (II)) having a vinyl aromatic Polymer block (A) containing monomer units as the main body, polymer block (B) containing conjugated diene monomer units as the main body, vinyl aromatic monomer units and conjugated diene monomer units. At least two kinds of polymer blocks in the regular polymer block (C), the above-mentioned conjugated diene monomer unit is selected from 1,3-butadiene, 2-methyl-1,3-butadiene ( Isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene , and at least one or more of the group consisting of farnesene; and an olefin elastomer having an epoxy group (component (III)); and the above-mentioned modified conjugated diene polymer (component (II)) Having at least one polar group selected from the group consisting of hydroxyl group and carboxyl group, the above-mentioned molded article satisfies the following conditions (I-1) to (II-1): <Condition (I-1)> Obtained from the molded article The tensile elongation at break of a short strip test piece with a width of 10mm, a length of 170mm and a thickness of 2mm at room temperature and a tensile speed of 5mm/min is more than 25%, <Condition (II-1) Obtained from the molded body The Charpy impact value of a short strip test piece with a length of about 80mm, a width of about 10mm and a thickness of about 4mm in the Charpy impact test at -30°C is 15kJ/m ² .