JP7592874B2 - Resin composition, method for producing resin composition, and molded article - Google Patents

Description

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

It is known that conjugated diene polymers exhibit various properties by adjusting the ratio of 1,2-bonds, the ratio of blocks constituting the conjugated diene polymer, the block arrangement, the degree of hydrogenation, etc. Furthermore, for the purpose of imparting further properties, conjugated diene polymers having affinity groups capable of generating intermolecular forces with other materials or reactive groups capable of forming chemical bonds (hereinafter referred to as modified conjugated diene polymers) have been proposed.
For example, Patent Document 1 proposes an amino group-modified conjugated diene polymer obtained by reacting an amino group-containing compound with the terminal of a conjugated diene polymer.

On the other hand, resins having polar groups (hereinafter sometimes referred to as polar resins) generally have excellent rigidity, chemical resistance, heat resistance, etc., but are hard and brittle, so various modifiers have been investigated. Modified conjugated diene polymers have excellent compatibility with polar resins due to reactions caused by the modifying groups and intermolecular forces such as hydrogen bonds, and are therefore widely used as modifiers for polar resins.

JP 2014-210848 A

In recent years, with the increasing performance of automobiles, home appliances, communication devices, etc. and the spread of IoT, the weight of each component is being reduced and electrification is progressing, and there is an increasing demand for polar resins that have excellent heat resistance, chemical resistance, flame retardancy, mechanical strength, dimensional stability, electrical insulation, and dielectric properties.
On the other hand, there is a demand for electronic materials that can withstand impacts during manufacturing and use, and there is growing concern about safety in automotive parts, so there is a need to improve the impact resistance and toughness of hard and brittle polar resins.
For example, Patent Document 1 proposes a resin composition containing a modified conjugated diene polymer having toughness superior to that of polyphenylene sulfide resin (hereinafter sometimes referred to as "PPS") for improving the toughness of PPS.
However, according to the investigations of the present inventors, the resin composition disclosed in Patent Document 1 still has a problem in that the toughness is insufficient and there is room for improvement.

Therefore, in view of the problems of the conventional technology described above, the present invention aims to provide a resin composition having excellent impact resistance and toughness.

As a result of intensive research conducted by the present inventors in order to solve the problems of the conventional techniques, the present inventors have found that the problems of the conventional techniques can be solved by providing a resin composition containing a resin having a polar group (component (I)) and a modified conjugated diene-based polymer having a predetermined polar group (component (II)), in which the dispersed phase (B) containing the modified conjugated diene-based polymer has a predetermined number average dispersed particle size, and the resin having a polar group (component (I)) and the modified conjugated diene-based polymer (component (II)) are specified to have a predetermined mass ratio, thereby completing the present invention.
That is, the present invention is as follows.

[1]
Component (I): a resin having a polar group (excluding component (II) below),
Component (II):
A polymer block (A) mainly composed of vinyl aromatic monomer units,
a block polymer having at least two polymer blocks selected from a polymer block (B) mainly composed of a conjugated diene monomer unit and a random polymer block (C) composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
at least one modified conjugated diene polymer having at least one polar group bonded thereto selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxyl group, an epoxy group, an oxetanyl group, and an amino group;
Component (III): a polymer having a polar group reactive with component (I) and/or component (II) (excluding components (I) and (II));
A resin composition comprising:
The 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), and the number average dispersed particle size of the dispersed phase (B) is 1.5 μm or less;
a mass ratio of the component (I) to the component (II) is component (I):component (II)=50/50 to 99/1;
A resin composition , wherein the mass ratio of the component (II) to the component (III) is component (II):component (III)=1/99 to 99/1 .
[2]
The component (I) is
At least one resin selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, polybutylene terephthalate-based resins, and epoxy resins;
The resin composition described in [1] above.
[3]
The component (II) contains a hydrogenated modified conjugated diene polymer in which an aliphatic double bond derived from a conjugated diene compound is hydrogenated.
The resin composition according to [1] or [2] above.
[4]
The component (I) is a polyphenylene sulfide resin.
The resin composition according to any one of [1] to [3] above.
[5]
The component (II) contains a modified conjugated diene-based polymer having at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group bonded thereto.
The resin composition according to any one of [1] to [4] above.
[6]
The component (III) is a polymer having at least one polar group selected from the group consisting of an epoxy group, an oxazoline group, and an oxetanyl group.
The resin composition according to any one of [1] to [5] above.
[7]
The component (III) is an olefin-based elastomer having an epoxy group.
The resin composition according to any one of [1] to [6] above.
[8]
The hydrogenation rate of the hydrogenated modified conjugated diene polymer is 90% or less.
The resin composition according to any one of [3] to [7] above.
[9]
The content of vinyl aromatic monomer units in the component (II) is 40 mass% or less.
The resin composition according to any one of [1] to [8] above.
[10]
The component (III) is an elastomer having an epoxy group, which is composed of a copolymer of a polymerizable monomer having an epoxy group and an unsaturated hydrocarbon compound.
The resin composition according to any one of [1] to [9] above.
[11]
The component (III) is a copolymer of a polymerizable monomer having an epoxy group, an unsaturated hydrocarbon compound, and a (meth)acrylic acid ester and/or vinyl acetate.
The resin composition according to any one of [1] to [10] above.
[12]
A polymer block (A) mainly composed of vinyl aromatic monomer units,
The copolymer has at least two polymer blocks selected from a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
A modified conjugated diene-based polymer (component (II)) having at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group;
At least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins (component (I));
An olefin-based elastomer (component (III)) having at least one polar group selected from the group consisting of an epoxy group, an oxazoline group, and an oxetanyl group;
of,
a mass ratio of the resin having a polar group (component (I)) to the modified conjugated diene polymer (component (II)) is set to 50/50 to 99/1;
a step of kneading the modified conjugated diene polymer and the olefin elastomer having a polar group in a mass ratio of modified conjugated diene polymer:olefin elastomer having a polar group=1/99 to 99/1 to obtain a resin composition;
The resin composition comprises a continuous phase (A) of the resin having a polar group (component (I)) and the modified conjugated diene-based polymer (component (II)) dispersed in the continuous phase (A).
and a step of making the number average dispersed particle diameter of the dispersed phase (B) 1.5 μm or less.
A method for producing a resin composition.
[13]
At least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins (component (I));
a modified conjugated diene-based polymer (component (II)) having at least two polymer blocks selected from a polymer block (A) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) of a vinyl aromatic monomer unit and a conjugated diene monomer unit;
An olefin-based elastomer having an epoxy group (component (III)),
, including,
A molded article of a resin composition,
The modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group,
The molded article satisfies the following conditions (I-1) to (II-1).
<Condition (I-1)>
A rectangular test piece having a width of 10 mm, a length of 170 mm and a thickness of 2 mm obtained from the molded product has a tensile breaking elongation of 25% or more at room temperature and at a tensile speed of 5 mm/min.
<Condition (II-1) >
A rectangular test piece having a length of about 80 mm, a width of about 10 mm and a thickness of about 4 mm obtained from the molded body has a Charpy impact value of 15 kJ/m ² or more in a Charpy impact test at -30°C.

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

Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail.
The following embodiments are merely illustrative for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be modified appropriately within the scope of the gist thereof.

[Resin composition]
The resin composition of the present embodiment is
Component (I): a resin having a polar group (excluding component (II) below),
Component (II): a polymer block (A) mainly composed of vinyl aromatic monomer units,
at least one modified conjugated diene polymer in which at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxyl group, an epoxy group, an oxetanyl group and an amino group is bonded to a block polymer having at least two polymer blocks selected from a polymer block (B) mainly composed of a conjugated diene monomer unit and a random polymer block (C) of a vinyl aromatic monomer unit and a conjugated diene monomer unit;
The resin composition comprises:
The 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), and the number average dispersed particle size of the dispersed phase (B) is 1.5 μm or less.
The mass ratio of the component (I) to the component (II) is component (I):component (II)=50/50 to 99/1.
By having the above-mentioned constitution, a resin composition excellent in impact resistance and toughness can be obtained.

(Component (I): Resin having a polar group (excluding component (II) below))
The resin composition of the present embodiment contains a resin having a polar group (hereinafter, may be referred to as polar resin (I) or component (I)).

Generally, a resin having excellent rigidity has a polar group in the main chain from the viewpoint of entropy and enthalpy.
The polar resin (I) used in the resin composition of the present embodiment is not limited to the following, but examples thereof include acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylic acid ester-butadiene-styrene copolymer resin (MBS); polyvinyl chloride resin; polyvinyl acetate resin and its hydrolysate; polymers of acrylic acid and its esters and amides; polyacrylate resin; polymers of acrylonitrile and/or methacrylonitrile, and copolymers of these acrylonitrile monomers with other copolymerizable monomers containing 50% by mass or more. Nitrile resins which are copolymers; polyamide-based resins; polyester-based resins, thermoplastic polyurethane-based resins, polycarbonate-based polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate; thermoplastic polysulfones such as polyethersulfone and polyallylsulfone; polyoxymethylene-based resins; polyphenylene ether-based resins such as poly(2,6-dimethyl-1,4-phenylene) ether; polyphenylene sulfide-based resins; polyarylate-based resins; polyether ketone polymers or copolymers; polyketone-based resins;
Examples of the resin include fluorine-based resins, polyethylene terephthalate-based resins, polyoxybenzoyl-based polymers, polyimide-based resins, polyethylene terephthalate resins, polybutylene terephthalate-based resins, and epoxy resins.

The preferred polar resin (I) varies depending on the properties required for the resin composition of this embodiment. From the viewpoint of rigidity, polyethylene terephthalate-based resins, polybutylene terephthalate-based resins, epoxy resins, and polyphenylene sulfide-based resins are preferred; from the viewpoint of chemical resistance, epoxy resins and polyphenylene sulfide-based resins are preferred; and from the viewpoint of heat resistance, polyphenylene sulfide-based resins are preferred.

The polyethylene terephthalate resin may be any resin that falls within the category of polyethylene terephthalate resins, and is preferably a thermoplastic resin obtained by a polymerization reaction between a diol component that is at least 90 mol % or more of ethylene glycol and a dicarboxylic acid component that is at least 90 mol % or more of terephthalic acid.

Polybutylene terephthalate resins may be any resin that falls within the category of polybutylene terephthalate resins, and are polymers that can be obtained by common polymerization methods such as polycondensation of a dicarboxylic acid whose main component is terephthalic acid or a derivative thereof with a diol whose main component is 1,4-butanediol or a derivative thereof, and the repeating unit of butylene terephthalate is preferably 90 mol% or more, and more preferably 95 mol% or more.

The epoxy resin may be any resin that belongs to the category of epoxy resins, and preferably has two or more epoxy groups in one molecule from the viewpoint of rigidity. The epoxy resin may be used alone or in combination of two or more kinds.
Examples of epoxy resins include, but are not limited to, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins.

The polyphenylene sulfide-based resin may be any resin that belongs to the category known as a polyphenylene sulfide resin. From the viewpoint of heat resistance, the polyphenylene sulfide resin preferably contains 70 mol % or more, and more preferably 90 mol % or more, of p-phenylene sulfide units as its constituent units.
Furthermore, other structural units may be contained, for example, an o-phenylene sulfide unit, an m-phenylene sulfide unit, a phenylene sulfide ether unit, a phenylene sulfone unit, a phenylene sulfide ketone unit, a diphenylene sulfide unit, a phenylene sulfide unit containing a substituent, a phenylene sulfide unit containing a branched structure, or the like.
The molecular weight of the polyphenylene sulfide resin is preferably 5,000 or more, and more preferably 10,000 or more, from the viewpoint of the rigidity of the resin composition of the present embodiment.
The polyphenylene sulfide resin may be linear, crosslinked or branched.
Furthermore, the polyphenylene sulfide resin may have a polar group, such as a thiol group or a carboxyl group, at the end or in the main chain in the polymer structure.
The method for producing the polyphenylene sulfide resin is not particularly limited, and for example, a production method in which an alkali metal sulfide and a dihaloaromatic compound are reacted in a polymerization solvent can be mentioned.

(Component (II): Modified conjugated diene polymer)
The resin composition of the present embodiment contains at least one modified conjugated diene polymer (hereinafter, may be referred to as modified conjugated diene polymer (II), component (II)) in which at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxyl group, an epoxy group, an oxetanyl group, and an amino group is bonded to a block polymer having at least two polymer blocks selected from a polymer block (A) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) of a vinyl aromatic monomer unit and a conjugated diene monomer unit.
Since the modified conjugated diene polymer (II) has the polar group, it has affinity and/or reactivity with the polar resin (I), thereby improving the toughness and impact resistance of the resin composition of the present embodiment.

The above affinity means that at least one intermolecular force selected from the group consisting of ionic interaction, hydrogen bond, dipole-dipole interaction, and van der Waals force can occur between the components.
The above-mentioned reactivity means that the polar groups of each component have a covalent bond with each other. When polar groups react with each other, for example, when OH of a carboxyl group is eliminated, the original polar group changes or disappears, but when a covalent bond is formed as a result, it is included in the definition that the polar groups show "reactivity" with each other.

Since the modified conjugated diene polymer (II) has at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxyl group, an oxazoline group, an epoxy group, an oxetanyl group, and an amino group, it has excellent affinity and/or reactivity with the polar resin (I). This improves the compatibility between the polar resin (component (I)) and the modified conjugated diene polymer (component (II)). The number average dispersed particle size of the dispersed phase (B) made of component (II) in the continuous layer (A) made of component (I) is 1.5 μm or less, and the interface between the components can be strengthened, thereby contributing to improved impact resistance and toughness.

The preferred polar group of the modified conjugated diene polymer (II) varies depending on the type of polar resin (I) and the properties required for the resin composition of this embodiment. For example, when the polar resin (I) is a polyphenylene sulfide resin, an epoxy group, an oxazoline group, and an amino group have excellent affinity and/or reactivity with the thiol group and carboxyl group present at the end of the polyphenylene sulfide resin, and are therefore preferred as the polar group of the modified conjugated diene polymer (II). In addition, when component (I) is an epoxy resin, a carboxyl group, an acid anhydride group, a hydroxyl group, and a dicarboxyl group have excellent affinity and/or reactivity with the epoxy group of component (I). In this way, by each of components (I) and (II) having an affinity group and/or reactive group that exhibits affinity and/or reactivity between the components, it is possible to strengthen the interface between the components, which contributes to improving the toughness and impact resistance of the resin composition of this embodiment. In addition, it is expected to have the effect of improving tracking resistance and suppressing deterioration of physical properties when exposed to high and low temperatures alternately (heat cycle characteristics). These characteristics can be improved by controlling the compatibility state by adjusting the affinity and reactivity between each component.

For example, when the polar resin of component (I) is a polyethylene terephthalate resin or a polybutylene terephthalate resin, the epoxy groups and amino groups of component (II) have excellent affinity and/or reactivity with the carboxyl groups present at the terminals of the polyethylene terephthalate resin or the polybutylene terephthalate resin. Therefore, since each component has an affinity group and/or reactive group that expresses affinity and/or reactivity between the components, it becomes possible to strengthen the interface between the components, thereby contributing to improving the toughness and impact resistance of the resin composition.
In addition, as the component (II), two kinds of modified conjugated diene polymers each having a different polar group bonded thereto from the above-mentioned polar group species can also be used. When two kinds of modified conjugated diene polymers (II) each having a different polar group bonded thereto are used from the viewpoint of the above-mentioned compatibility, it is preferable that one kind of modified conjugated diene polymer has a polar group bonded thereto that is reactive with the other modified conjugated diene polymer and the polar resin (I).
For example, when the polar resin of component (I) is a polyphenylene sulfide-based resin, a polyethylene terephthalate-based resin, or a polybutylene terephthalate-based resin, a modified conjugated diene-based polymer having an epoxy group bonded thereto and a modified conjugated diene-based polymer having a carboxyl group and/or a hydroxyl group bonded thereto can be preferably used as component (II).
Furthermore, for example, when the polar resin of component (I) is an epoxy resin, a carboxyl group, a hydroxyl group, and an amino group have excellent affinity and/or reactivity with the epoxy group of the epoxy resin, and therefore a modified conjugated diene-based polymer having such a polar group can be preferably used as component (II). In this way, by each component having an affinity group and/or a reactive group that exhibits affinity and/or reactivity between the components, it becomes possible to strengthen the interface between the components, which contributes to improving the toughness and impact resistance of the resin composition of this embodiment.

Generally, in a resin composition, the same components tend to aggregate with each other and form a phase. However, in the resin composition of this embodiment, the component (II) has a polar group, which enhances the affinity and/or reactivity with the component (I) and improves the compatibility of these components. As a result, the number average dispersed particle size of the dispersed phase (B) described below becomes 1.5 μm or less, which contributes to the manifestation of impact resistance and toughness of the resin composition of this embodiment.
The amount of polar groups in the modified conjugated diene polymer (II) is preferably 0.3 mol/chain or more, more preferably 0.5 mol/chain or more, and even more preferably 0.6 mol/chain or more, from the viewpoint of compatibility with the polar resin (I).
When the amount of polar groups in the modified conjugated diene polymer (II) is 0.3 mol/chain or more, the polymer chains having the affinity group or reactive group are compatible with the component (I), and the polymer chains not having the affinity group or reactive group and the polymer chains compatible with the component (I) are aggregated as described above, whereby the number average dispersed particle size of the dispersed phase (B) can be made 1.5 μm or less, preferably 1.3 μm or less.
As long as the polar groups contained in each of components (I) and (II) have the necessary affinity and/or reactivity, the ease of compatibility and ease of aggregation are more affected by the frequency (amount) of the polar groups in the polymer chain than by the resin structure, the type of polar groups, or the combination of polar groups between the components. Therefore, the number average dispersed particle size of the dispersed phase (B) can be controlled to a desired value by appropriately setting the amount of polar groups in component (II).
Furthermore, if there is an excess of the affinity group or reactive group in component (II), there is a risk of gelation or the like occurring in the resin composition of this embodiment, so it is preferably 30 mol/chain or less.
In this context, the term "chain" refers to a single polymer molecule, and a polymer structure that is branched by chemical bonds is also counted as a single molecular chain.
The amount of polar groups in the modified conjugated diene polymer (II) can be controlled within the above-mentioned numerical range by adjusting the reaction conditions with the compound for forming the polar groups, such as the amount of the compound added, the reaction temperature, the reaction time, etc., during the production process of the modified conjugated diene polymer.

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

The polymer block (A) mainly composed of vinyl aromatic monomer units has a vinyl aromatic monomer unit content of 80 mass % or more.
Examples of vinyl aromatic compounds used to form the vinyl aromatic monomer units include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene.
Among these, from the viewpoints of availability and productivity, preferred are styrene, α-methylstyrene, and 4-methylstyrene, and more preferred is styrene.
The polymer block (A) mainly composed of vinyl aromatic monomer units may be composed of one type of vinyl aromatic monomer unit, or may be composed of two or more types of vinyl aromatic monomer units.
From the viewpoint of strength of a molded product of the resin composition of this embodiment, the content of the vinyl aromatic monomer unit contained in the polymer block mainly composed of (A) a vinyl aromatic monomer unit is 80 mass % or more, preferably 90 mass % or more, more preferably 95 mass % or more, and even more preferably 100 mass % (no other compounds are intentionally added).

The polymer block (B) mainly composed of conjugated diene monomer units has a conjugated diene monomer unit content of 80 mass % or more.
The conjugated diene compound used to form the conjugated diene monomer unit may be a diolefin having a pair of conjugated double bonds, including, but not limited to, 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 viewpoints of availability and productivity, 1,3-butadiene and isoprene are preferable.
The polymer block (B) 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 impact resistance of the resin composition of this embodiment, the content of the conjugated diene monomer unit contained in the polymer block mainly composed of (B) a conjugated diene monomer unit is 80 mass % or more, preferably 90 mass % or more, more preferably 95 mass % or more, and even more preferably 100 mass % (other compounds are not intentionally added).

The vinyl aromatic compound and the conjugated diene compound used for forming the vinyl aromatic monomer units and the conjugated diene monomer units contained in the random polymer block of conjugated diene monomer units and vinyl aromatic monomer units (C) may be compounds that can be used in the polymer block (A) and the polymer block (B).
The distribution state of the vinyl aromatic monomer unit in the random polymer block (C) is not particularly limited, and the vinyl aromatic monomer unit in the random polymer block (C) may be distributed uniformly or in a tapered shape. In addition, there may be a plurality of parts in which the vinyl aromatic monomer unit is distributed uniformly and/or a plurality of parts in which the vinyl aromatic monomer unit is distributed in a tapered shape, and there may be a plurality of segments with different contents of the vinyl aromatic monomer unit.
The mass ratio of the vinyl aromatic monomer unit and the conjugated diene monomer unit in the random copolymer block (C) is preferably vinyl aromatic monomer unit/conjugated diene monomer unit=75/25 to 25/75, more preferably 70/30 to 30/70, and even more preferably 65/35 to 35/65.
The modified conjugated diene polymer (II) used in the resin composition of the present embodiment may be polymerized with another compound 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, but examples thereof include those having a structure represented by the following formula.
In the following formulae, polar groups are omitted.
(b-c) _n , c-(b-c) _n , b-(c-b) _n , (b-c) _m -X, (c-b) _m -X, [(b-c) _n ] _m -X, [(c-b) _n ] _m -X, [c-(b-c) _n ] _m -X, [b-(c-b) _n ] _m -X, [(b-c) _n -b] _m -X, [(c-b) _n -c] _m -X,
(a-b) _n , b-(a-b) _n , a-(ba-a) _n , (a-b) _m -X, (ba-a) _m -X, [(a-b) _n ] _m -X, [(ba-a) _n ] _m -X, [b-(a-b) _n ] _m -X, [a-(ba) _n ] _m -X, [(a-b) _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-(a-b-a) _n , c-(b-a-b) _n ,
a-c-(ba) _n , a-c-(ab) _n ,
a-c-(ba) _n -b, [(a-b-c) _n ] _m -X,
[a-(b-c) _n ] _m -X, [(a-b) _n -c] _m -X,
[(a-b-a) _n -c] _m -X,
[(b-a-b) _n -c] _m -X, [(c-b-a) _n ] _m -X,
[c-(ba-a)n] _m -X, [c-(a-ba) _n ] _m -X, [c-(ba-b) _n ] _m -X
a-(b-c) _n , a-(c-b) _n ,
a-(c-b-c) _n , a-(b-c-b) _n ,
ca-(b-c) _n , ca-(c-b) _n ,
c-a-(b-c) _n -b, [(c-b-a) _n ] _m -X,
[c-(ba) _n ] _m -X, [(c-b) _n -a] _m -X,
[(c-b-c) _n -a] _m -X,
[(b-c-b) _n -a] _m -X, [(a-b-c) _n ] _m -X,
[a-(b-c) _n ] _m -X, [a-(c-b-c) _n ] _m -X, [a-(b-c-b) _n ] _m -X
b-(ac) _n , b-(ca) _n ,
b-(c-ac) _n , b-(ac-a) _n ,
c-b-(ac) _n , c-b-(ca) _n ,
c-b-(ac) _n -a, [(c-ab) _n ] _m -X,
[c-(a-b) _n ] _m -X, [(ca) _n -b] _m -X,
[(c-a-c) _n -b] _m -X,
[(b-c-b) _n -b] _m -X, [(b-a-c) _n ] _m -X,
[b-(ac) _n ] _m -X, [b-(ca-c) _n ] _m -X, [b-(ac-a) _n ] _m -X
In the above general formulas, a represents the polymer block (A), b represents the polymer block (B), and c represents the polymer block (C).
n is an integer of 1 or more, and preferably an integer of 1 to 5.
m is an integer of 2 or more, and preferably an integer of 2 to 11.
X represents a residue of a coupling agent or a residue of a multifunctional initiator.
The modified conjugated diene polymer (component (II)) is preferably a polymer whose basic block structure is particularly represented by the structural formula ab, aba, or aba-a-b.

The weight average molecular weight (Mw) (hereinafter also referred to as "Mw") of the modified conjugated diene polymer (component (II)) is preferably 5,000 to 600,000, more preferably 30,000 to 400,000, and even more preferably 50,000 to 300,000, from the viewpoints of mechanical strength, impact resistance, abrasion resistance, compatibility, and moldability of the resin composition of this embodiment.
The weight average molecular weight (Mw) of the modified conjugated diene polymer (component (II)) is the weight average molecular weight (Mw) obtained by measuring the peak molecular weight of a chromatogram obtained by gel permeation chromatography (GPC) based on a calibration curve (prepared using the peak molecular weight of the standard polystyrene) obtained by measuring commercially available standard polystyrene.
The molecular weight distribution of the conjugated diene polymer before modification can also be determined by GPC measurement, and is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
The single-peak molecular weight distribution of the modified conjugated diene polymer (component (II)) measured by GPC is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and even more preferably 2.5 or less.

The modified conjugated diene polymer (component (II)) contains vinyl aromatic monomer units.
In general, impact resistance and toughness are imparted to highly rigid polar resins by dispersing a specific polymer because, when the resin is subjected to impact or stretching, voids form at the interface between the polar resin and the dispersed polymer particle component or in the polymer particles themselves, causing stress relaxation due to shear yielding of the matrix resin starting from the polymer particles.
The polymer block (A) mainly composed of vinyl aromatic monomer units is amorphous and therefore tends to promote the above-mentioned shear yielding.
Therefore, the lower limit of the content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and still more preferably 8 mass% or more, from the viewpoint of promoting the above-mentioned shear yield and exhibiting impact resistance and toughness.
When the content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) is 1% by mass or more, the amorphous portion of the vinyl aromatic monomer unit of the modified conjugated diene polymer (II) tends to aggregate and promote the above-mentioned shear yield. However, when voids are generated at the interface between the highly rigid polar resin and the dispersed polymer particle component or at the polymer particle itself, it is important that the rigidity difference between the matrix polar resin and the dispersed phase is large. From this viewpoint, the upper limit of the vinyl aromatic monomer unit of the modified conjugated diene polymer (component (II)) is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of generating voids at the interface between the polar resin (component (I)) and the dispersed polymer particle component (component (II)) or at the polymer particle itself, thereby exhibiting impact resistance and toughness. By setting the amount of vinyl aromatic monomer units in component (II) to 90 mass% or less, the difference in rigidity between the dispersed phase and the matrix becomes large, and more voids are generated at the interface or in the polymer particles themselves, which tends to improve the impact resistance and toughness of the resin composition of this embodiment.
When a polyphenylene sulfide resin is used as the polar resin of component (I), from the viewpoint of exhibiting impact resistance at low temperatures, the content of vinyl aromatic monomer units in the modified conjugated diene polymer (component (II)) is preferably 40 mass% or less, more preferably 35 mass% or less, even more preferably 30 mass% or less, and even more preferably 27 mass% or less.
The content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) can be measured by the method described in the Examples below.
The content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) can be controlled within the above-mentioned range by adjusting the amount of the monomer added during the production of the polymer.

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

In the modified conjugated diene polymer (II), the amount of vinyl bonds is preferably 0 mol % or more, more preferably 5 mol % or more, based on 100 mol % in total of the conjugated diene monomer units.
The "vinyl bond content" refers to the 1,2-bond content (mol %) relative to the total amount of 1,4-bonds (cis and trans) and 1,2-bonds (however, when 3,4-bonds are incorporated into the polymer, it refers to the total amount of 1,2-bonds and 3,4-bonds) resulting from a conjugated diene compound and incorporated into the polymer before hydrogenation.
The vinyl bond content of the modified conjugated diene polymer (II) can be measured using a nuclear magnetic resonance (NMR) device or the like, and specifically, can be measured by the method described in the examples below.
The vinyl bond amount can be controlled within the above-mentioned range by using a Lewis base, for example, a compound such as an ether or an amine, as a vinyl bond amount regulator (hereinafter referred to as a vinylating agent).

The modified conjugated diene polymer (II) may contain a hydrogenated modified conjugated diene polymer in which an aliphatic double bond derived from a conjugated diene compound is hydrogenated, thereby improving the heat resistance of the resin composition of the present embodiment.
The hydrogenation rate of the aliphatic double bonds derived from the conjugated diene compound is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, because heat resistance is improved by hydrogenating the thermally unstable 1,2-bonds (however, when the double bonds are incorporated into the polymer via 3,4-bonds, the 1,2-bonds and 3,4-bonds are included).
Furthermore, when a polyphenylene sulfide-based resin is used as the polar resin (I) that is particularly excellent in rigidity, chemical resistance, and heat resistance, the number average dispersed particle size of the dispersed phase (B) in the resin composition of this embodiment is set to 1.5 μm or less, and from the viewpoint of further improving toughness and impact resistance, the hydrogenation rate is preferably 90% or less, more preferably 83% or less, and even more preferably 80% or less.
The hydrogenation rate of the modified conjugated diene polymer (II) can be measured by using a nuclear magnetic resonance (NMR) device or the like, specifically, by the method described in the examples.
The hydrogenation rate can be controlled within the above-mentioned range, for example, by adjusting the amount of hydrogen reacted during the hydrogenation reaction.

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

The polymerization temperature is generally from 0 to 180°C, preferably from 20 to 160°C, and more preferably from 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, and more preferably 0.5 to 5 hours from the viewpoint of obtaining a conjugated diene-based polymer having a narrow molecular weight distribution and high strength.
The atmosphere of the polymerization system is not particularly limited as long as it is in a pressure range sufficient to maintain the nitrogen and the solvent in a liquid phase.
It is preferable that impurities that may inactivate the polymerization initiator and the living polymer, such as water, oxygen, carbon dioxide gas, etc., are not present in the polymerization system.

Examples of organic solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, xylene, toluene, and ethylbenzene.

As the organoalkali metal compound serving as the polymerization initiator, an organolithium compound is preferred.
The organolithium compound includes an organomonolithium compound, an organodilithium compound, and an organopolylithium compound.
Examples of the organolithium compound include, but are not limited to, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isopropenyldilithium, and lithium piperidide.
When an organolithium compound containing N, such as lithium piperidide, is used as a polymerization initiator, an amino group-modified conjugated diene polymer having an atomic group where X=0 in NHx is obtained.
These polymerization initiators may be used alone or in combination of two or more. Among these, n-butyllithium, sec-butyllithium, and lithium piperidide are preferred from the viewpoint of polymerization activity.

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

The vinyl bond amount of the modified conjugated diene polymer (component (II)) can be controlled by using a Lewis base, for example, a compound such as an ether or an amine, as a vinyl bond amount regulator (hereinafter referred to as a vinylizing agent).
Furthermore, the amount of vinyl bond can be controlled by adjusting the amount of the vinylating agent used.

Vinylating agents include, but are not limited to, ether compounds, tertiary amine compounds, etc.

Examples of the ether compound include linear ether compounds and cyclic ether compounds.
Examples of linear ether compounds include, but are not limited to, dialkyl ether compounds of ethylene glycol, such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; and dialkyl ether compounds of diethylene glycol, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
Examples of cyclic ether compounds include, but are not limited to, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and alkyl ethers of furfuryl alcohol.

Examples of tertiary amine compounds include, but are not limited to, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N",N"-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, pyridine, tetramethylpropanediamine, bis[2-(N,N-dimethylamino)ethyl]ether, and the like.
These may be used alone or in combination of two or more.
As the tertiary amine compound, a compound having two amines is preferable. Among them, a compound having a structure showing symmetry in a molecule is more preferable, and N,N,N',N'-tetramethylethylenediamine, bis[2-(N,N-dimethylamino)ethyl]ether, and 1,2-dipiperidinoethane are further preferable.

The modified conjugated diene polymer (II) used in the resin composition of the present embodiment can be produced by polymerization using a conjugated diene compound and a vinyl aromatic compound in the coexistence of the above-mentioned vinylating agent, organolithium compound, and alkali metal alkoxide.
Here, the alkali metal alkoxide is a compound represented by the general formula MOR (wherein M is an alkali metal and R is an alkyl group).
The coexistence of an alkali metal alkoxide in the polymerization step provides the effect of controlling the vinyl bond amount, molecular weight distribution, polymerization rate, block ratio, and the like.

As the alkali metal of the alkali metal alkoxide, sodium or potassium is preferred from the viewpoints of a high vinyl bond content, a narrow molecular weight distribution, a high polymerization rate, and a high block rate.
Examples of alkali metal alkoxides include, but are not limited to, sodium alkoxides, lithium alkoxides, and potassium alkoxides having an alkyl group having 2 to 12 carbon atoms, preferably sodium alkoxides or potassium alkoxides having an alkyl group having 3 to 6 carbon atoms, and more preferably sodium t-butoxide, sodium t-pentoxide, potassium t-butoxide, and potassium t-pentoxide.
Among these, sodium alkoxides such as sodium t-butoxide and sodium t-pentoxide are more preferable.

The modified conjugated diene polymer (II) may be hydrogenated, and the polymer block containing the conjugated diene monomer unit may be a hydrogenated product.
The hydrogenation method is not particularly limited. For example, hydrogen can be supplied to the conjugated diene polymer obtained in the polymerization step in the presence of a hydrogenation catalyst to hydrogenate the polymer, thereby obtaining a hydrogenated conjugated diene polymer in which the double bond residues of the conjugated diene monomer units are hydrogenated.
The hydrogenation rate can be controlled, for example, by the amount of catalyst used during hydrogenation. The hydrogenation rate can be controlled, for example, by adjusting the amount of catalyst used during hydrogenation, the amount of hydrogen fed, the pressure, the temperature, etc. The hydrogenation reaction step is preferably carried out at a timing after the termination of the production reaction of the conjugated diene polymer before hydrogenation.

The modified conjugated diene polymer (II) has at least one polar group bonded thereto selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxyl group, an epoxy group, an oxetanyl group, and an amino group.
From the viewpoint of affinity and/or reactivity with the polar resin (I) and the polymer having a specific polar group (component (III)) described below, a hydroxyl group and a carboxyl group are more preferred.
In addition, since 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, when a thermoplastic resin is used as component (I) and a molten resin composition is injected into a mold by injection molding and cooled to obtain a desired molded product, the fluidity of the resin composition tends to be improved and processability tends to be improved.
The method for introducing the polar group into the conjugated diene polymer is not particularly limited, and examples thereof include a method of introducing the polar group using a polymerization initiator having a predetermined polar group; a method of obtaining a modified conjugated diene polymer by polymerizing an unsaturated monomer having a polar group; and a method of adding a modifying agent having a polar group to the living end of a polymer.
In the modified conjugated diene polymer (II), the position at which each polar group is introduced is not particularly limited, and may be, for example, the terminal of the conjugated diene polymer, or may be arranged in a block or random and tapered shape in a part of the main chain. From the viewpoint of affinity and/or reactivity with the polar resin (component (I)) and the polymer having a specific polar group (component (III)) described later, and further from the viewpoint of processability of the resin composition described above, it is more preferable that the polar group be the terminal of the conjugated diene polymer.

Examples of the "modifier" include, but are not limited to, aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carballylic acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid; and aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid.
Further examples include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 5-(2,5-dioxytetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and ε-caprolactam.

Other methods for introducing polar groups into conjugated diene polymers include, for example, reacting a conjugated diene polymer with an organolithium compound or other organoalkali metal compound (metallation reaction), and then subjecting the polymer to an addition reaction with a modifier having a polar group.

Further, as another method for introducing a polar group, for example, there can be mentioned a method in which an atomic group having a polar group is directly grafted onto an unmodified conjugated diene polymer.
Examples of the graft addition method include a method of reacting a radical initiator, a conjugated diene polymer, and the modifier in a solution containing them; a method of reacting a radical initiator, a conjugated diene polymer, and the modifier under heating and melting; and a method of reacting a conjugated diene polymer and a compound containing the modifier under heating and melting without using a radical initiator.

Examples of the method for reacting each component when introducing a polar group into a polymer include a method of melt-kneading each component using a general mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. From the viewpoints of cost and production stability, a method using a single screw, twin screw or multi-screw extruder is preferable, and a method using a twin screw extruder is preferable.
During the reaction step, the components may be dry blended and charged all at once, or each component may be fed separately, or the same component may be added stepwise.
The screw rotation speed is preferably 50 to 400 rpm, more preferably 100 to 350 rpm, from the viewpoint of uniformly adding the modifier to the polymer, and is preferably 150 to 300 rpm from the viewpoint of suppressing deterioration of the polymer due to shear and performing uniform addition.
The kneading temperature is a temperature at which the conjugated diene polymer melts and at which radicals are generated from the radical initiator, and is preferably 100° C. to 350° C. From the viewpoint of controlling the amount of polar groups introduced and suppressing deterioration of the polymer due to heat, the kneading temperature is preferably 120° C. to 300° C., and more preferably 150° C. to 250° C.
In order to prevent deactivation of the radical active species by oxygen, the mixture may be melt-kneaded under an inert gas such as nitrogen.

The radical initiator is not limited to the following, but examples thereof include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, and peroxydicarbonates. The radical initiator is preferably one having a one-minute half-life temperature in the kneading temperature range. More preferably, the one-minute half-life temperature is 150° C. to 250° C., and examples thereof include 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylauric acid, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy) Examples of the peroxides include hexane, t-butyl peroxyacetate, 2,2-di-(t-butylperoxy)butane, t-butyl peroxybenzoate, n-butyl-4,4-di-(t-butylperoxy)valerate, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-methane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, and 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-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are preferred.
Further, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are more preferable.

Another method for introducing a polar group into a conjugated diene-based polymer includes secondary modification in which the primarily modified conjugated diene-based polymer obtained by the above-mentioned method is reacted with an atomic group having a predetermined polar group.
Examples of the combination of polar groups include an amino group, a dicarboxyl group, an acid anhydride group, an isocyanate group, a hydroxyl group, an oxazoline group, an oxetanyl group, and a carboxyl group; an acid anhydride group, a hydroxyl group, an oxazoline group, and an oxetanyl group; a silanol group, a hydroxyl group, and a carboxyl group; an epoxy group, and a carboxyl group. From the viewpoint of reactivity, an amino group, a dicarboxyl group, an acid anhydride group, an oxazoline group, and an oxetanyl group; a silanol group, a hydroxyl group, and a dicarboxyl group; an epoxy group, and a dicarboxyl group are preferred, and an amino group, a dicarboxyl group, and an acid anhydride group are more preferred.

As a primary modification, the above-mentioned methods can be used to bond epoxy groups, acid anhydride groups, and hydroxyl groups to a conjugated diene polymer, and the above-mentioned modifiers and epoxy group-containing polymerizable compounds can be used as modifiers.

As a primary modification, the method of bonding silanol groups to a conjugated diene polymer includes the above-mentioned method, and examples of the modifying agent include bis-(3-triethoxysilylpropyl)-tetrasulfane, bis-(3-triethoxysilylpropyl)-disulfane, ethoxysiloxane oligomer, epoxy group-containing polymerizable compounds, and hydrolysates of compounds having alkoxysilane groups listed in the epoxy group-containing polymerizable compounds described above.

As a primary modification, the method of bonding an amino group to a conjugated diene polymer can be the method described above, and examples of the modifying agent include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl 1-methyl-3-butyl-2-imidazolidinone, 1-methyl-3-(2-methoxyethyl)-2-imidazolidinone, 1-methyl-3-(2-ethoxyethyl)-2-imidazolidinone, 1,3-di-(2-ethoxyethyl)-2-imidazolidinone, 1,3-dimethylethylenethiourea, N,N'-diethylpropyleneurea, and N-methyl-N'-ethylpropyleneurea. Further examples thereof 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, and 1-isopropyl-5,5-dimethyl-2-piperidone.

The method of bonding the primary modified conjugated diene polymer having an amino group bonded thereto with the secondary modifier includes the above-mentioned method, and examples of the modifier include aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carballylic acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid; aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid; and other examples include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, and 5-(2,5-dioxytetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

The shape of the modified conjugated diene polymer (II) obtained by the above-mentioned production method is not particularly limited, and examples thereof include pellets, sheets, strands, chips, etc. After melt kneading, the polymer can be directly molded into a molded product.
Pellets of the modified conjugated diene polymer can be produced by pelletizing the modified conjugated diene polymer (II).
Examples of the pelletizing method include a method in which the modified conjugated diene polymer is extruded in the form of a strand from a single-screw or twin-screw extruder, and cut in water with a rotary blade installed in front of a die section; a method in which the modified conjugated diene polymer is extruded in the form of a strand from a single-screw or twin-screw extruder, and then cooled with water or air and cut with a strand cutter; a method in which the polymer is melt-mixed using an open roll or Banbury mixer, formed into a sheet using a roll, and the sheet is further cut into strips and then cut into cubic pellets using a pelletizer; and the like.
The size and shape of the pellets are not particularly limited.

If necessary, a pellet blocking inhibitor may be added to the pellets of the modified conjugated diene polymer (II) in order to prevent pellet blocking.
Examples of pellet blocking inhibitors include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica.
When the resin composition of this embodiment is used to produce a random polypropylene composition or a tubular or sheet-shaped molded article containing the same, calcium stearate, polyethylene, and polypropylene are preferred from the viewpoint of their transparency.
The pellet anti-blocking agent is preferably used in an amount of 500 to 6000 ppm relative to the modified conjugated diene polymer (II). A more preferred amount is 1000 to 5000 ppm relative to the modified conjugated diene polymer (II). The pellet anti-blocking agent is preferably blended in a state of adhering to the pellet surface, but may also be contained to some extent inside the pellet.

(Component (III): A polymer having a polar group reactive with component (I) and/or component (II) (excluding component (I) and component (II))
The resin composition of the present embodiment may contain a polymer (excluding components (I) and (II)) having a polar group reactive with component (I) and/or component (II) (hereinafter, may be referred to as polymer (III) or component (III)).
Even if the polar group bonded to the modified conjugated diene polymer (II) has low affinity and/or reactivity with the component (I), the resin composition of this embodiment tends to have a number average dispersed particle diameter of the dispersed phase (B) of 1.5 μm or less by including a polymer (III) having a functional polar group reactive with the component (I) and/or the component (II).
In addition, from the viewpoint of increasing the difference in rigidity between the matrix polar resin (component (I)) and the dispersed phase (components (II) and (III)) and promoting shear yielding to exhibit impact resistance and toughness, it is preferable that component (III) has reactivity with components (I) and (II).
Component (III) is a non-vinyl aromatic compound modified polymer that does not contain a polymer block mainly composed of vinyl aromatic monomer units and does not contain a polymer having the same structure as the modified conjugated diene polymer (II).
When component (III) contains a vinyl aromatic monomer unit, the reactivity with components (I) and (II) tends to decrease due to steric hindrance of the aromatic ring.

Component (III) is a polymer having a polar group reactive with component (I) and/or component (II), and the term "polymer" refers to a polymeric compound having a repeating unit (including an oligomer having a low degree of polymerization of about 2 to 10 repeating units).
From the viewpoint of maintaining sufficient rigidity for practical use of the resin composition of this embodiment, the lower limit of the molecular weight of component (III) is preferably at least 1000, more preferably at least 2000. From the viewpoint of the flowability of the resin composition of this embodiment, the upper limit of the molecular weight of component (III) is preferably at most 5 million, more preferably at most 3 million, and even more preferably at most 1 million.
The molecular weight of the component (III) can be appropriately set in consideration of the compatibility with the components (I) and (II) and the fluidity of the resin composition of the present embodiment, etc. By making the molecular weight 5,000,000 or less, good fluidity of the resin composition is obtained, and practically good moldability tends to be obtained.

The "reactivity" of component (III) with component (I) and/or component (II) means that the polar groups of each component have covalent bonding properties.
When polar groups react with each other, for example when the OH of a carboxyl group is eliminated, the original polar group changes or disappears, but if this results in the formation of a covalent bond, this is included in the definition of the polar groups being "reactive".
The polar group contained in component (III) may be one type of polar group that is reactive with both component (I) and component (II), or multiple types of polar groups that are reactive with each of component (I) and component (II).
Although the polar group reactive with only one of the components (I) and (II) may be contained in the component (III), it is preferable to have a polar group reactive with both the components (I) and (II) from the viewpoint of increasing the affinity with both components and making the number average dispersed particle size of the dispersed phase (B) described later 1.5 μm or less, preferably 1.3 μm or less. For example, when the component (III) has an epoxy group, the component (I) is a polyphenylene sulfide resin, and the component (II) is a polymer having a carboxyl group and/or a hydroxyl group, the epoxy group of the component (III) is reactive with the carboxyl group of both the polyphenylene sulfide resin of the component (I) and the polymer of the component (II).
The polar group contained in component (III) has reactivity with the polar resin (component (I)) and the modified conjugated diene polymer (component (II)), and thus the toughness and impact resistance of the resin composition of the present embodiment can be improved.

(Combination of Component (I), Component (II), and Component (III))
Examples of the combination of the polar groups of the component (II) and the component (III) include the following combinations.
When component (II) contains an amino group, preferred polar groups contained in component (III) include a carboxyl group, a carbonyl group, an epoxy group, a hydroxyl group, an acid anhydride group, a sulfonic acid group, and an aldehyde group.
When component (II) contains an acid anhydride group, preferred polar groups contained in component (III) include an amino group, a hydroxy group, and the like.
When component (II) contains a carboxyl group or a dicarboxyl group, preferred polar groups contained in component (III) include an amino group, an isocyanate group, and the like.
When component (II) has an epoxy group, preferred polar groups contained in component (III) include an amino group, a carboxyl group, a dicarboxyl group, a thiol group, an oxazoline group, and an oxetanyl group.
When component (II) contains an oxetanyl group, preferred polar groups contained in component (III) include a thiol group, a hydroxyl group, an amino group, a carboxyl group, and a dicarboxyl group.
When component (II) contains an oxazoline group, preferred polar groups contained in component (III) include a thiol group, a hydroxyl group, an amino group, a carboxyl group, and a dicarboxyl group.
In addition, the combination of polar groups contained in each of the components (I) and (III) is as follows:
Amino groups, carboxyl groups, carbonyl groups, epoxy groups, hydroxyl groups, acid anhydride groups, sulfonic acid groups, and aldehyde groups;
An isocyanate group, a hydroxyl group, a carboxyl group, and a dicarboxyl group;
A hydroxy group and an acid anhydride group;
silanol groups, hydroxyl groups, carboxyl groups, and dicarboxyl groups;
Epoxy groups, carboxyl groups, dicarboxyl groups, thiol groups, oxazoline groups, and oxetanyl groups;
Halogen groups, carboxylic acid groups, carboxylic ester groups, amino groups, phenol groups, and thiol groups;
Alkoxy groups, hydroxy groups, alkoxide groups, and amino groups;
Thiol groups, epoxy groups, oxazoline groups, and oxetanyl groups;
etc.

In the resin composition of this embodiment, it can be arbitrarily selected whether the polar group of component (I) or component (III) is used to bond 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 polar group contained in component (II) is preferably a carboxyl group, a hydroxyl group, an epoxy group, an oxazoline group, or an oxetanyl group, and more preferably a carboxyl group or a hydroxyl group.
Since the polar group contained in component (III) is reactive with component (I) and component (II), the polar group contained in component (III) is preferably an epoxy group, an oxazoline group, or an oxetanyl group, and from the viewpoint of reactivity, an epoxy group is more preferable.

When component (III) is a polymer having an epoxy group, examples of the polymer having an epoxy group include a polymer of an epoxy group-containing polymerizable compound such as an epoxy group-containing unsaturated compound, and a copolymer of an epoxy group-containing polymerizable compound and at least one other polymerizable compound.
Examples of the epoxy group-containing polymerizable compound include, but are not limited to, epoxy group-containing unsaturated compounds, such as polyepoxy compounds such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate, glycidyl itaconate, tetraglycidyl meta-xylylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyl diaminodiphenylmethane, diglycidyl aniline, diglycidyl orthotoluidine, 4,4'-diglycidyl-diphenylmethylamine, 4,4'-diglycidyl-dibenzylmethylamine, and diglycidyl aminomethylcyclohexane.

Also, γ-glycidoxyethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxybutyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl tripropoxysilane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyl triphenoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-glycidoxypropyl ethyl dimethoxysilane, γ-glycidoxypropyl ethyl diethoxysilane, γ-glycidoxypropyl methyl diethoxysilane, γ-glycidoxypropyl methyl Examples of the silane include glycidoxypropyl dipropoxysilane, γ-glycidoxypropyl methyldibutoxysilane, γ-glycidoxypropyl methyldiphenoxysilane, γ-glycidoxypropyl dimethylmethoxysilane, γ-glycidoxypropyl diethylethoxysilane, γ-glycidoxypropyl dimethylethoxysilane, γ-glycidoxypropyl dimethylphenoxysilane, γ-glycidoxypropyl diethylmethoxysilane, γ-glycidoxypropyl methyldiisopropeneoxysilane, bis(γ-glycidoxypropyl)dimethoxysilane, and bis(γ-glycidoxypropyl)diethoxysilane.

Further examples include bis(γ-glycidoxypropyl)dipropoxysilane, bis(γ-glycidoxypropyl)dibutoxysilane, bis(γ-glycidoxypropyl)diphenoxysilane, bis(γ-glycidoxypropyl)methylmethoxysilane, bis(γ-glycidoxypropyl)methylethoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, bis(γ-glycidoxypropyl)methylbutoxysilane, bis(γ-glycidoxypropyl), and tris(γ-glycidoxypropyl)methoxysilane.

Further examples include β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tripropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tributoxysilane, and β-(3,4-epoxycyclohexyl)ethyl-triphenoxysilane.

Furthermore, 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-epoxycyclohexyl)ethyl-methyldibutoxysilane, dimethylmethoxysilane, β-(3,4-epoxycyclohexyl), β-(3,4-epoxycyclohexyl)ethyl-dimethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylpropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylbutoxysilane, and β-(3,4-epoxycyclohexyl)ethyl-dimethylphenoxysilane.

Further examples include β-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiisopropeneoxysilane, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine, etc.

Examples of compounds that can be copolymerized with the epoxy group-containing polymerizable compound include, but are not limited to, conjugated diene compounds such as butadiene and isoprene; unsaturated hydrocarbon compounds such as ethylene and propylene; cyanide vinyl monomers such as acrylonitrile; vinyl acetate, (meth)acrylic acid esters, vinyl alcohol, vinyl acetate, vinyl acetate, and the like.

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

Alternatively, a polymer having an epoxy group may be obtained as component (III) by a method in which any polymer is subjected to an addition reaction with the epoxy group-containing unsaturated compound or the like by a radical reaction or the like.
Examples of the arbitrary polymer include polymers of unsaturated hydrocarbon compounds such as ethylene and propylene, copolymers of the unsaturated hydrocarbon compounds and polymerizable compounds having a double bond, and copolymers of conjugated diene compounds and vinyl aromatic compounds.
Examples of the addition reaction method include conventionally known techniques, such as a production method in which a radical initiator, a polymer, and an epoxy group-containing compound are reacted in a solution containing them; a production method in which a radical initiator, a polymer, and an epoxy group-containing compound are reacted under heating and melting; a production method in which a polymer and an epoxy group-containing compound are reacted without a radical initiator under heating and melting; and a production method in which a compound that reacts with both a polymer and an epoxy group-containing compound to form a bond is reacted with a polymer and an epoxy group-containing compound in a solution containing them or under heating and melting.
Also included is a method of converting a diene moiety of a polymer having a carbon bond and/or a copolymer of a polymer having a carbon bond and another polymerizable compound into an epoxy group by oxidizing the diene moiety.

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

By improving the affinity between the polymer having an epoxy group (component (III)) and the modified conjugated diene-based polymer (component (II)), stress is easily concentrated in the dispersed phase (B) of the resin composition of this embodiment. From the viewpoint of affinity with the modified conjugated diene-based polymer (component (II)), the polymer having an epoxy group (component (III)) is more preferably an elastomer having an epoxy group, which is a copolymer of the above-mentioned epoxy group-containing polymerizable compound (polymerizable monomer having an epoxy group) and an unsaturated hydrocarbon-based compound, and further preferably an olefin-based elastomer having an epoxy group.
By using the polymer (component (III)) as an olefin-based elastomer having an epoxy group, it is possible to obtain an effect of improving toughness and/or impact resistance due to shear yielding caused by stress concentration at the resin interface with component (I), and further to obtain an effect of inhibiting extension of microcracks and/or crazes generated under stress. Furthermore, the effect of components (II) and (III) bridging between microcracks and/or crazes tends to further improve toughness and/or impact resistance. In particular, in applications where the material is used at low temperatures, specifically at temperatures below -30°C, by using component (III) as an olefin-based elastomer having an epoxy group, it tends to further improve toughness and/or impact resistance at low temperatures. Furthermore, it is possible to expect improvements in tracking resistance and in the effect of suppressing deterioration in physical properties (heat cycle characteristics) even when the material is exposed to high and low temperatures alternately.
These effects can be improved by controlling the compatibility between the components and adjusting the affinity and reactivity between the components.

In addition, the polymer having an epoxy group as component (III) may be a copolymer of the unsaturated hydrocarbon compound and the epoxy group-containing polymerizable compound with the aforementioned cyanide vinyl monomer such as styrene or acrylonitrile, vinyl acetate, (meth)acrylic acid ester, vinyl alcohol, vinyl acetate, or other polymerizable compound. When component (I) is a polyphenylene sulfide resin, from the viewpoint of affinity with the polyphenylene sulfide resin, it is more preferable that a (meth)acrylic acid ester, vinyl acetate, or vinyl acetate is copolymerized, and even more preferable that a (meth)acrylic acid ester and/or vinyl acetate is copolymerized.

Examples of the unsaturated hydrocarbon compounds 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))
In the resin composition of this embodiment, the polar resin (component (I)) and the modified conjugated diene polymer (component (II)) are such that the mass ratio of component (I):component (II) is 50/50 to 99/1, preferably 55/45 to 98/2, and more preferably 60/40 to 95/5, from the viewpoints of exhibiting the heat resistance, impact resistance, and toughness of the resin composition of this embodiment and of making the number average dispersed particle size of the dispersed phase (B), which will be described later, 1.5 μm or less.

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

In addition, from the viewpoint of achieving the heat resistance, impact resistance, and toughness of the resin composition of this embodiment, and of setting the number average dispersed particle size of the dispersed phase (B) described below to 1.5 μm or less, the mass ratio of component (I) to the total amount of component (II) and component (III) of component (I):(component (II)+component (III)) is preferably 50/50 to 99/1, more preferably 60/40 to 97/3, and even more preferably 65/35 to 95/5.

(Dispersed state)
The resin composition of the present embodiment has a continuous phase (A) of a polar resin (component (I)) and a dispersed phase (B) containing a modified conjugated diene-based polymer (component (II)) dispersed in the continuous phase (A).
By having the polar resin (component (I)) form the continuous phase (A), excellent heat resistance and rigidity can be obtained in the resin composition of this embodiment.
In addition, due to the presence of the dispersed phase (B), when stress is applied to a molded article made of the resin composition, the stress is concentrated in the dispersed phase (B), and microcrazes are generated, thereby contributing to improved impact resistance and toughness.

The dispersed phase (B) may be a phase containing component (II), and when it contains component (III), which is a polymer having a polar group reactive with component (II), it may be a phase in which the component (II) modified conjugated diene polymer and component (III) are compatible with each other, or component (III) may be unevenly distributed around component (II), or component (II) may be unevenly distributed around component (III). Component (III) may also be compatible with component (I). When only component (III) is dispersed in a sea of 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) either contains both component (II) and component (III), or component (II) is dispersed alone, and this results in a phenomenon in which the number average dispersed particle size of the dispersed phase (B) corresponds to the improvement in impact resistance and/or toughness. Therefore, the resin composition of the present embodiment has a continuous phase (A) of a polar resin (component (I)) and a dispersed phase (B) containing a modified conjugated diene-based polymer (component (II)).

A method for confirming the dispersion state of the continuous phase (A) and the dispersed phase (B) will be described.
<(1) Identification of components contained in the resin composition>
First, identifying the components contained in the resin composition of the present embodiment is useful for measuring the number average dispersed particle diameter of the dispersed phase (B).
In general, it is known that the polar resin (I) has excellent chemical resistance. In the case where the above-mentioned component (II) modified conjugated diene polymer and component (III) polymer are included, when the resin composition is mixed in a solvent that can also dissolve component (III), the component (I) that is undissolved due to excellent chemical resistance, and the unreacted components (II) and (III) can be extracted. In particular, when a polyphenylene sulfide resin is used as component (I), since there is no solvent that dissolves the polyphenylene sulfide resin at 200°C or less, the undissolved component (I), the unreacted component (II), and the unreacted component (III) can be extracted by mixing the resin composition with a solvent at 50 to 200°C.

In the case where component (II) and component (III) are contained, examples of solvents capable of dissolving component (III) include toluene, cyclohexane, xylene, tetrahydrofuran, chloroform, nitroethane, nitropropane, and ethylbenzene. From the viewpoint of solubility, chloroform, nitroethane, nitropropane, ethylbenzene, and toluene are preferred.
After the extraction, undissolved component (I) is removed by filtration or the like, and the filtrate is subjected to liquid phase chromatography to separate components (II) and (III).
In addition, when the solubilities of component (II) and component (III) are different, a method can also be employed in which a solvent in which component (II) dissolves but component (III) cannot dissolve is used to remove the solvent from the above-mentioned filtrate by vacuum drying or the like, and the mixture obtained by this is mixed again in an appropriate solvent to separate component (II) and component (III).
In general, examples of solvents in which component (II) is highly soluble include toluene, cyclohexane, and tetrahydrofuran.
The structural units of the component (III) which are insoluble in the above-mentioned solvents are polymer units of unsaturated hydrocarbon compounds, and in particular, ethylene, propylene, and α-olefins having 3 to 8 carbon atoms are mentioned.
The components (II) and (III) can be identified by nuclear magnetic resonance (NMR), infrared absorption spectroscopy (IR), gas chromatography (GS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), etc. In addition, the types and structures of polar groups bonded to the components (II) and (III) can also be identified.
In addition, when the resin composition of the present embodiment contains components such as additives described below that can be dissolved in the solvent in the extraction step, the components can be separated by liquid phase chromatography or the like using differences in molecular weight and polarity, and can be identified by the above-mentioned NMR, IR, GS, TOF-SIMS, and the like.
When the amount of component (II) and component (III) that have not reacted with component (I) is very small and it is difficult to separate component (II) and component (III), the structural units of component (II) and component (III) and the polar group species bonded to component (II) and component (III) can be identified from the infrared absorption spectrum obtained by observation with an atomic force microscope (AFM). The test piece to be subjected to AFM measurement can be a precision cross section of the resin composition prepared with an ultramicrotome or the like.

<(2) Measurement of Dispersed Particle Size>
[(1) AFM (measuring the particle size of the soft phase in elastic modulus mapping)]
In general, the melting point of the polar resin (I) is high, and at room temperature, particularly at low temperatures, it has higher rigidity than the component (II), and when the component (III) is contained, it has higher rigidity than the component (III).
In addition, by isolating components (II) and (III) and then identifying the constituent units of components (II) and (III) or measuring the rigidity of the isolated components (including a mixture of components (II) and (III)), it is possible to confirm that components (II) and (III) have a relatively lower rigidity than component (I).
In addition, it is possible to clarify that component (I) has higher rigidity than components (II) and (III) from the infrared absorption spectrum and/or the force curves of 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 morphology of the resin composition. As described above, component (I), component (II), and component (III) have different rigidities, so if the "island" portion observed by AFM observation is softer than the "sea" in the elastic modulus mapping, the portion corresponding to the "island" can be identified as component (II) and/or component (III). Therefore, the number average dispersed particle size of the dispersed phase (B) can be calculated by calculating the average particle size of the soft portion in the elastic modulus mapping by the method described in the examples below.
Generally, the elastic modulus is measured by AFM observation, and the upper limit of the force acting on the probe at the tip of the AFM cantilever and the sample is set, and the sample is pressed in the vertical direction to calculate the relationship between the load and the amount of deformation of the sample. Therefore, the distribution of components with different elastic moduli can be observed as an image to show the degree of deformation of each dispersed phase against the load.

In addition, generally, the melting temperature when component (I) and component (II), and optionally component (III), are mixed in a molten state is very high. For this reason, low molecular weight compounds generated during kneading, etc., may bleed out, making it difficult to obtain a clear elastic modulus mapping. In such a case, as described in the examples below, it is preferable to perform ultrasonic cleaning in a solvent such as ethanol to remove the low molecular weight compounds, etc., as a preliminary step to preparing a precision cross section for AFM observation, and then prepare a precision cross section using an ultramicrotome, etc.

(2) Identification of dispersed phase by dyeing
When the constituent units of the components (II) and (III) are identified after isolating the components (II) and (III) described above, depending on the combination of the structures of the components (I), (II) and (III), a method can also be employed in which each component is oxidized with an appropriate heavy metal to be stained and fixed, and the number average dispersed particle size of the dispersed phase (B) is calculated using an electron microscope such as a transmission electron microscope (TEM) or a scanning electron microscope (SEM).
The test piece to be subjected to the electron microscope observation is an ultrathin section of the resin composition prepared by a cryomicrotome or the like, and may be prepared after the above-mentioned staining, or may be stained after preparation.
For example, in the case where component (I) has a smaller amount of aromatic skeleton than component (II) and component (III) does not have an aromatic ring skeleton, ruthenium tetroxide can be used as the heavy metal of the dyeing agent for component (II). The dyeing agent tends to oxidize the vinyl aromatic monomer unit of component (II) the most, and then oxidize the aromatic ring skeleton of the polar resin of component (I), and component (III) is not oxidized. By observing the resin composition dyed with an oxidizing agent under an electron microscope, an image is obtained in which component (I) is lightly dyed, component (II) is most dyed, and component (III) is not dyed. This image is binarized using image analysis software or the like described in the examples below, and the number average dispersed particle size of the dispersed phase (B) in the resin composition can be calculated.
In the case where the dispersed phase (B) contains many phases other than circular such as ellipses in the binarized image, it is preferable to enlarge the measurement range in the AFM observation used for binarization to about 10 μm × 10 μm. In addition, when the particles of the dispersed phase (B) overlap the edge of the image obtained in the range of the field of view, it is preferable to define the value obtained by multiplying the particle diameter of the dispersed phase (B) by two as the fillet diameter described in the examples, and calculate the number average dispersed particle diameter of the dispersed phase (B).

In order to concentrate stress more in the dispersed phase (B) and to exhibit sufficient impact resistance and toughness in the resin composition of this embodiment, the number average dispersed particle size of the dispersed phase (B) is 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.1 μm or less, even more preferably 1.0 μm or less, and still more preferably 0.9 μm or less.
Although the lower limit of the number average dispersed particle diameter of the dispersed phase (B) is not particularly limited, 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 this embodiment.
In the resin composition of this embodiment, examples of a method for maintaining sufficient rigidity for practical use include a method of adding a filler, etc., which will be described later. In general, however, when the number average dispersed particle diameter of the dispersed phase (B) is made less than 0.01 μm by increasing the amount of polar groups bonded to components (II) and (III), the amount of side reactions in the step of adding the polar groups increases, tending to reduce the impact resistance and toughness of the resin composition. Therefore, it is preferable that the number average dispersed particle diameter of the dispersed phase (B) is 0.01 μm or more.

The modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxyl group, an epoxy group, an oxetanyl group, and an amino group, and thus exhibits high 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)). Thus, the affinity and/or reactivity with component (I) is determined by the amount of polar groups bonded to component (II) and component (III).
As described above, in order to increase the reactivity of component (I), component (II) and component (III) and to set the number average dispersed particle size of the dispersed phase (B) to 1.5 μm or less, the amount of polar groups bonded to the modified conjugated diene polymer (II) is preferably 0.3 mol/chain or more, more preferably 0.5 mol/chain or more, and even more preferably 0.6 mol/chain or more. If the amount of polar groups in component (II) is less than 0.3 mol/chain, the amount of component (II) that is not reactive with component (I) and component (III) becomes 70 mol% or more with respect to the total amount of component (II) in the resin composition, and dispersibility tends to be greatly reduced.
From the viewpoint of making the number average dispersed particle size of the dispersed phase (B) 1.5 μm or less, as described above, the mass ratio of component (II) to component (III) is preferably component (II): component (III) = 1/99 to 99/1, more preferably 5/95 to 95/5, even more preferably 10/90 to 90/10, and still more preferably 15/85 to 85/15.
Furthermore, when a polyphenylene sulfide-based resin is used as component (I), from the viewpoint of reactivity with the polyphenylene sulfide-based resin, which is a polar resin excellent in terms of rigidity, chemical resistance, and heat resistance, the polar group bonded to component (II) is preferably 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 at least one selected from the group consisting of an epoxy group, an oxazoline group, and an oxetanyl group, and more preferably an epoxy group, in order to have reactivity with the polar group of component (I) and the polar group of component (II).

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

(Additives)
From the viewpoint of increasing the strength (rigidity) of a molded article, the resin composition of the present embodiment preferably further contains various additives, for example, a filler.

In the resin composition of the present embodiment, the filler is preferably a fibrous filler.
Examples of fibrous fillers include, but are not limited to, fibrous inorganic fillers such as glass fibers, carbon fibers, cellulose nanofibers, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, sepiolite, xonotlite, and zinc oxide whiskers.
Among these, glass fiber, carbon fiber, cellulose nanofiber, and wollastonite are preferred because they are likely to increase the strength (rigidity) and heat resistance of the molded article.
The fibrous filler may be surface-treated with a compound having an affinity group or a reactive group for the polar resin (component (I)).
The fibrous filler may be contained alone or in combination of two or more kinds.

Examples of other additives include, but are not limited to, oils, fillers, heat stabilizers, ultraviolet absorbers, nucleating agents, antioxidants, weathering agents, light stabilizers, plasticizers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, dispersants, copper inhibitors, neutralizing agents, bubble inhibitors, weld strength improvers, natural oils, synthetic oils, waxes, etc. Other elastomers and thermoplastic resins may also be used as additives in any proportion.
These may be used alone or in combination of two or more.

In addition, an auxiliary that improves the affinity or reactivity of the polar resin (component (I)) and the modified conjugated diene-based polymer (component (II)) may be added to the resin composition of this embodiment.
The auxiliary is preferably an alkoxysilane compound having at least one polar group selected from the group consisting of an epoxy group, an amino group, and an isocyanate group.

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, and any known method can be used.
For example, a method of melt-kneading a polar resin (component (I)), a modified conjugated diene polymer (component (II)), and a polymer having a polar group reactive with component (I) and component (II) (component (III)) using a general mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a co-kneader, or a multi-screw extruder, or a method of dissolving or dispersing and mixing the respective components and then removing the solvent by heating, etc., can be used.
From the viewpoint of controlling the number average dispersed particle size of the above-mentioned dispersed phase (B) to 1.5 μm or less, the melt kneading method is preferred.
As a method for producing the resin composition of the present embodiment, a method of melt-kneading each component using an extruder is preferred from the viewpoints of productivity and good kneading. In particular, by kneading each component using a multi-screw having two or more screws and providing sufficient shear energy, the polar resin and the modified conjugated diene polymer increase the interface therebetween to form a dispersed phase (B).

The resin temperature during kneading may be any temperature at which the polar resin (I), the modified conjugated diene polymer (II), and the polymer (III) can be melted, and is preferably 270°C to 450°C.
From the viewpoint of suppressing deterioration of the polar resin (I), the modified conjugated diene-based polymer (II), and the polymer (III) due to heat, the temperature is more preferably 400° C. or lower.

In order to suppress oxidation of the modified conjugated diene polymer (II), the melt kneading may be carried out under an inert gas such as nitrogen.
When the resin composition of the present embodiment is produced using an extruder, the positions and order in which the polar resin (I), the modified conjugated diene polymer (II), and other components are fed are not particularly limited.
Furthermore, when a thermosetting resin is used as component (I), a resin composition of the present embodiment can be obtained by dissolving a thermosetting resin in a solution state and/or a thermosetting resin in a solid state in a suitable solvent, adding component (II) as needed, and, if necessary, component (III) and the above-mentioned additives as needed, mixing, further adding an appropriate curing agent, and mixing again.
Furthermore, before the curing agent is added, the solvent in which the components (II) and (III) are dissolved may be removed by a method such as vacuum drying.
Examples of the solvent include toluene, methyl ethyl ketone, cyclohexane, cyclohexanone, chloroform, and tetrahydrofuran.
When an epoxy resin, which is a polar resin excellent in terms of heat resistance, is used as component (I), the curing agent is not particularly limited as long as it has the function of curing the polar resin (I), and examples thereof include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents, etc. The curing agents may be used alone or in combination of two or more kinds.
If necessary, a curing accelerator may be added, such as a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, or a metal-based curing accelerator.
The method for molding the resin composition of the present embodiment includes a method in which the resin composition is injected into a mold, the mold is heated for a desired time and at a desired temperature, and a cured product is obtained.
From the viewpoint of productivity, the temperature of the mold is preferably 30 to 300° C., and more preferably 50 to 250° C. From the viewpoint of productivity, the heating time is preferably 1 minute to 5 hours, and more preferably 10 minutes to 3 hours.

Furthermore, when a polyphenylene sulfide-based resin is used as component (I), from the viewpoint of intermolecular forces or chemical bond formation between the polyphenylene sulfide-based resin and the modified conjugated diene-based polymer (component (II)), it is preferable to use a polyphenylene sulfide-based resin that contains a thiol group or a carboxyl group.

In the manufacturing process of the resin composition of this embodiment, there are no particular limitations on its shape, but it may be in the form of pellets, sheets, strands, chips, etc.

(Preferable embodiment of the method for producing the resin composition)
A preferred embodiment of the method for producing the resin composition of the present embodiment is as follows.
The polymer block (A) mainly comprises a vinyl aromatic monomer unit, a polymer block (B) mainly comprises a conjugated diene monomer unit, and a random polymer block (C) of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
A modified conjugated diene-based polymer (component (II)) having at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group, a resin (component (I)) having at least one polar group selected from the group consisting of a polyphenylene sulfide-based resin, a polyethylene terephthalate-based resin, and a polybutylene terephthalate-based resin, and an olefin-based elastomer (component (III)) having at least one polar group selected from the group consisting of an epoxy group, an oxazoline group, and an oxetanyl group, are mixed with the resin having the polar group (component (I)) and the modified conjugated diene-based polymer (component (II)). The method includes a step of kneading a resin composition having a mass ratio of resin having a polar group:modified conjugated diene polymer of 50/50 to 99/1 and a mass ratio of the modified conjugated diene polymer and the olefin elastomer having a polar group of 1/99 to 99/1, the resin composition having a continuous phase (A) of the resin having a polar group (component (I)) and a dispersed phase (B) containing the modified conjugated diene polymer (component (II)) dispersed in the continuous phase (A), and a step of adjusting the number average dispersed particle diameter of the dispersed phase (B) to 1.5 μm or less.
According to the above-mentioned production method, a resin composition excellent in impact resistance and toughness can be obtained.

[Molded body]
The molded article of this embodiment is an article molded from the resin composition of this embodiment described above.

The molded article of the present embodiment can be produced 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, blow molding, compression molding, vacuum molding, rotational molding, powder slush molding, foam molding, laminate molding, calendar molding, blow molding, or the like.
If necessary, the material may be subjected to processing such as foaming, powdering, stretching, adhesion, printing, painting, plating, etc.
This molding method can be used to produce a wide variety of molded products, including sheets, films, injection molded products of various shapes, hollow molded products, compressed air molded products, vacuum molded products, extrusion molded products, foam molded products, nonwoven fabrics and fibrous molded products, synthetic leather, etc. These molded products can be used as automobile interior and exterior materials, building materials, toys, home appliance parts, medical instruments, industrial parts, various hoses, various housings, various module cases, various power control unit parts, other miscellaneous goods, substrates, housings, sheets, packages, etc. for electronic devices, etc.
The molded article of the present embodiment is preferably used as a non-porous member from the viewpoint of stably exhibiting impact resistance and toughness. Here, the term "porous" refers to holes penetrating the material, and bubbles, which are non-penetrating holes generated by foaming, are not considered to be porous.

(Preferred form of molded article)
The molded body of this embodiment is particularly
At least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins (component (I));
a modified hydrogenated conjugated diene-based polymer (component (II)) having at least two polymer blocks selected from a polymer block (A) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) of a vinyl aromatic monomer unit and a conjugated diene monomer unit;
An elastomer having an epoxy group (component (III)),
A molded article of a resin composition comprising:
The modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group,
In applications requiring high impact resistance and toughness, it is preferable that the molded article satisfy the following conditions (I-1) to (II-1).
Examples of applications requiring high impact resistance and toughness include vehicle ducts for automobiles and the like, industrial piping, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, and other electronic device-related parts. These are molded articles used under a wide range of temperature conditions, from low to high temperatures.
<Condition (I-1)>
A rectangular test piece having a width of 10 mm, a length of 170 mm and a thickness of 2 mm obtained from the molded product has a tensile breaking elongation of 25% or more at room temperature and at a tensile speed of 5 mm/min.
<Condition (II-1)
A rectangular test piece having a length of about 80 mm, a width of about 10 mm, and a thickness of 4 mm obtained from the molded body has a Charpy impact value of 15 kJ/ ^m2 in a Charpy impact test at -30°C.

The molded body of this embodiment can be processed into a desired shape. For example, dumbbell-shaped test pieces and rectangular test pieces can be prepared by cutting out test pieces from a part of the molded body that is close to a flat surface. It is not essential that the test piece is completely flat, and it is sufficient that it is flat enough to measure the tensile breaking elongation and viscoelasticity. For example, in the case of a cylindrical molded body, depending on the diameter of the cylinder, a measurable test piece can be made by cutting out a test piece in the longitudinal direction. In addition, the thickness of the molded body may be thicker than 2 mm. In this case, the part with a thickness of 2 mm or more can be scraped off with a file or the like to make the test piece as flat as possible and set to a thickness of 2 mm, and the breaking elongation and viscoelasticity can be measured.

In the molded article of this embodiment, a state in which the modified conjugated diene polymer (component (II)) is dispersed in a resin having a polar group (component (I)) such as a polyphenylene sulfide resin is preferred from the viewpoint of obtaining excellent impact resistance and toughness. The state in which the modified conjugated diene polymer (component (II)) is dispersed in the resin having a polar group (component (I)) is such that the average dispersed particle size of the modified conjugated diene polymer (component (II)) is 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.2 μm or less, and even more preferably 1.1 μm or less.
In the molded article of this embodiment, the average particle size of the dispersed modified conjugated diene polymer (component (II)) can be measured by the method described in the Examples below.

The resin composition constituting the molded article of this embodiment may contain 1 to 50 parts by mass, preferably 5 to 30 parts by mass, of an additive such as a filler relative to 100 parts by mass of the resin composition for the purpose of improving strength. In addition, in order to impart functions such as flame retardancy and tracking resistance in addition to toughness and impact resistance, other additives such as a flame retardant may be contained in an amount of 1 to 70 parts by mass relative to 100 parts by mass of the resin composition. When these additives are contained, 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/m2 or ^more .

[Method of Analyzing Resin Composition]
The method for analyzing the components of the resin composition of this embodiment is described below.
It is considered that the polar group of the modified conjugated diene polymer (component (II)) used in the resin composition of this embodiment contributes to reducing the particle size of the dispersed phase (B) by reacting with the polar group of the resin (component (I)) having a polar group when the modified conjugated diene polymer (component (II)) is kneaded with the resin (component (I)) having a polar group, and the like, but it is assumed that the polar group of the modified conjugated diene polymer (component (II)) often remains in the resin composition. In addition, the polar group of a specified polymer (component (III)) is also reactive with the component (I) and/or the component (II), but it is considered that unreacted polar groups remain in the resin composition.
In order to qualitatively identify the modified conjugated diene polymer having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group (component (II)) and the elastomer having an epoxy group (component (III)) in the molded article of this embodiment, the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) are first dissolved, and the resin composition is mixed using a solvent that cannot dissolve the matrix resins, that is, polyphenylene sulfide resin, polyethylene terephthalate resin, and polybutylene terephthalate resin (each of which is component (I)), to extract the unreacted modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)). When the matrix resin is a polyphenylene sulfide-based resin, there is no solvent in which the polyphenylene sulfide-based resin dissolves at 200° C. or less. Therefore, by mixing the resin composition with a solvent under a temperature condition of 50 to 200° C., it is possible to extract the undissolved polyphenylene sulfide-based resin (component (I)), the unreacted modified conjugated diene-based polymer (component (II)), and the unreacted elastomer having an epoxy group (component (III)).
Examples of the solvent include toluene, cyclohexane, xylene, tetrahydrofuran, chloroform, nitroethane, nitropropane, and ethylbenzene. From the viewpoint of solubility, chloroform, nitroethane, nitropropane, ethylbenzene, and toluene are preferred.
After the extraction, the undissolved matrix resin is removed by filtration or the like, and the filtrate is subjected to liquid phase chromatography, whereby the unreacted modified conjugated diene polymer (component (II)) and the unreacted elastomer having an epoxy group (component (III)) can be separated.

In addition, when the solubilities of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) are different, a method can also be employed in which a solvent in which the modified conjugated diene polymer (component (II)) dissolves but the elastomer having an epoxy group (component (III)) does not dissolve is used, and the filtrate is subjected to vacuum drying or the like to remove the solvent, and the mixture of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) thus obtained is mixed again in a suitable solvent to separate the unreacted modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)).
In general, examples of solvents that have a high solubility for the modified conjugated diene polymer (component (II)) include toluene, cyclohexane, and tetrahydrofuran.

The epoxy groups of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) can be identified by a nuclear magnetic resonance apparatus (NMR), infrared absorption spectroscopy (IR), gas chromatography (GS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), or the like.
When the resin composition contains components such as additives described below that can be dissolved in the solvent in the above-mentioned extraction step, the components can be separated by liquid phase chromatography or the like, taking advantage of differences in molecular weight and polarity, and can be identified by the above-mentioned NMR, IR, GS, TOF-SIMS, and the like.

As an analytical method not using a solvent, the constituent units of the unreacted modified conjugated diene polymer (component (II)), the elastomer having unreacted epoxy groups (component (III)), the polar group species bonded to the unreacted modified conjugated diene polymer, and the polar group species bonded to the elastomer having unreacted epoxy groups can also be identified from infrared absorption spectra obtained by observation with an atomic force microscope (AFM).
The test piece to be subjected to the AFM measurement may be a precision cross section of the resin composition prepared by an ultramicrotome or the like.

In addition, image stack data can be obtained using a scanning transmission X-ray microscope, spectra can be extracted from characteristic regions of the image stack data, and component-specific mapping can be created by singular value decomposition using these as reference spectra, allowing the structural units of the unreacted modified conjugated diene polymer (component (II)) and the elastomer having unreacted epoxy groups (component (III)), the polar group species bonded to the unreacted modified conjugated diene polymer, and the polar group species bonded to the elastomer having unreacted epoxy groups to be identified.

In the present embodiment, the content ratio of the resin having a polar group (component (I)), the modified conjugated diene polymer (component (II)), and the elastomer having an epoxy group (component (III)) in the resin composition can be calculated by observing the dispersion state of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) in the resin having a polar group (component (I)) using an electron microscope such as the above-mentioned AFM, TEM, or SEM, and binarizing or ternarizing each layer of the obtained image using image analysis software or the like.
The content ratio of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) can be calculated from the peak intensity of the skeleton (specifically, the vinyl aromatic monomer unit skeleton) possessed only by the modified conjugated diene polymer (component (II)) in the infrared absorption spectrum obtained by the above-mentioned AFM observation, and the quantitative ratio of the vinyl aromatic monomer unit and the conjugated diene monomer unit in the modified conjugated diene polymer calculated by NMR, IR, GS, TOF-SIMS, etc. after isolating the above-mentioned modified conjugated diene polymer.

The molded article of the present embodiment may be formed into any shape depending on the application, for example, various containers, cylindrical containers, and housings.
Specific examples of such electric and electronic components include protective and supporting members for box-shaped electric/electronic component integrated modules, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related parts.
Other examples include home and office electrical appliance parts, such as VTR parts, television parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio laser discs (registered trademark) and compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and plumbing equipment parts such as water heaters, bath water volume and temperature sensors.
Further examples include office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning tools, motor parts, lighters, typewriters and other machine related parts.
Further examples include optical instruments such as microscopes, binoculars, cameras, and clocks, and precision machine-related parts.
Furthermore, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dimmers, relay blocks, inhibitor switches, various valves such as exhaust gas valves, various pipes for fuel, exhaust systems and intake systems, air intake nozzle snorkels, intake manifolds, fuel pumps, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, heating hot air flow control valves Examples of automobile and vehicle related parts include brakes, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, ignition coils and their bobbins, motor insulators, motor rotors, motor cores, starter relays, transmission wire harnesses, windshield washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, etc.
The applications of the molded article of this embodiment are not limited to the above-mentioned applications.

Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited in any way to the following examples and comparative examples.
The structures of the modified conjugated diene polymers and the methods for measuring and evaluating the physical properties of the resin compositions in the examples and comparative examples are shown below.

[Measurement and Evaluation of the Structure of Modified Conjugated Diene Polymer and the Physical Properties of the Resin Composition]
((1) Amount of Vinyl Bonds in Modified Conjugated Diene Polymer Before Hydrogenation)
The vinyl bond content of the modified conjugated diene polymer was measured by proton nuclear magnetic resonance ( 1 H- ^NMR ) using a polymer sample taken during polymerization of a polymer block containing a conjugated diene monomer at each step of the polymerization process of the modified conjugated diene polymer before hydrogenation.
The measurement was performed using an ECS400 (manufactured by JEOL), deuterated chloroform as the solvent, a sample concentration of 50 mg/mL, an observation frequency of 400 MHz, tetramethylsilane as the chemical shift standard, a pulse delay of 2.904 seconds, a scan count of 64, a pulse width of 45°, and a measurement temperature of 26° C.
The amount of vinyl bonds was calculated by calculating the integral value per 1H of each bond type from the integral values of the signals assigned to 1,4-bonds and 1,2-bonds, and then determining the ratio of 1,4-bonds to 1,2-bonds, according to the following formula.
Amount of vinyl bonds=(1,2-bonds/(1,4-bonds+1,2-bonds))

((2) Hydrogenation rate of unsaturated bonds based on conjugated diene monomer units of modified conjugated diene polymer)
The hydrogenation rate of the modified conjugated diene polymer was measured by proton nuclear magnetic resonance ( ¹ H-NMR) using the hydrogenated modified conjugated diene polymer.
The measurement conditions and the method of processing the measurement data were the same as those in (1) above.
The hydrogenation rate was calculated by calculating the integral values of the signals derived from the remaining double bonds at 4.5 to 5.5 ppm and the signals derived from the hydrogenated conjugated dienes, and then calculating the ratio thereof.

((3) Amount of butylene (vinyl hydrogenation rate) relative to the total of 1,2-bonds and 1,4-bonds based on conjugated diene monomer units in the modified conjugated diene polymer (100 mol %))
The butylene content relative to the total of 100 mol % of 1,2-bonds and 1,4-bonds based on the conjugated diene compound units in the modified conjugated diene polymer was measured by proton nuclear magnetic resonance ( ¹ H-NMR) using the hydrogenated modified conjugated diene polymer.
The measurement conditions and the method of processing the measurement data were the same as those in (1) and (2) above.
The signal derived from the total amount of conjugated diene monomer units and the integral value derived from the amount of butylene in the modified conjugated diene-based polymer after hydrogenation were calculated, and the ratio thereof was calculated.
The ratio was calculated using the integral value of the signal assigned to butylene (hydrogenated 1,2-bond) in the range of 0 to 2.0 ppm in the spectrum. The amount of butylene relative to the total of 1,2-bonds and 1,4-bonds based on the conjugated diene monomer units (100 mol %) is the vinyl hydrogenation ratio.

((4) Content of Vinyl Aromatic Monomer Units in Modified Conjugated Diene Polymer (hereinafter also referred to as “Styrene Content”))
The content of vinyl aromatic monomer units was measured by proton nuclear magnetic resonance ( ¹ H-NMR) using a modified conjugated diene polymer.
The measurement was performed with an ECS400 (manufactured by JEOL), deuterated chloroform as the solvent, a sample concentration of 50 mg/mL, an observation frequency of 400 MHz, tetramethylsilane as the chemical shift standard, a pulse delay of 2.904 seconds, a scan count of 64, a pulse width of 45°, and a measurement temperature of 26° C.
Styrene content was calculated using the integration of the total styrene aromatic signals from 6.2 to 7.5 ppm of the spectrum.
The styrene content was also confirmed by calculating the content of vinyl aromatic monomer units for each polymer sampled at each step in 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 by GPC [apparatus: HLC8220 (manufactured by Tosoh Corporation), column: TSKgelSUPER-HZM-N (4.6 mm×30 cm)].
The reaction was carried out using tetrahydrofuran as a solvent.
The weight average molecular weight was determined from the molecular weight of the peak in the chromatogram using a calibration curve (prepared using the peak molecular weight of the standard polystyrene) determined from the measurement of commercially available standard polystyrene.
When there are multiple peaks in the chromatogram, the weight average molecular weight is calculated from 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 was calculated from the ratio of the obtained weight average molecular weight (Mw) to the number average molecular weight (Mn).

((6) Modification Ratio of Modified Conjugated Diene Polymer)
The characteristic of the modified component being adsorbed by a GPC column packed with silica gel was applied, and the ratio of the modified conjugated diene polymer to the standard polystyrene in the chromatogram measured in the above (5) for a sample solution containing a modified conjugated diene polymer and a low molecular weight internal standard polystyrene was compared with the ratio of the modified conjugated diene polymer to the standard polystyrene in the chromatogram measured by a silica column GPC [apparatus: LC-10 (manufactured by Shimadzu Corporation), column: Zorbax (manufactured by DuPont)], and the amount of adsorption to the silica column was measured from the difference therebetween, and this ratio was taken as the modification ratio. The modification ratio was calculated from the ratio (%) of the terminal being an amino group of a specific structure by the following formula.

a: Area (%) of the total polymer measured using a polystyrene gel (PLgel)
b: Area (%) of low molecular weight internal standard polystyrene (PS) measured on polystyrene-based gel (PLgel)
c: Area (%) of total polymer measured on a silica-based column (Zorbax)
d: Area (%) of low molecular weight internal standard polystyrene (PS) measured on a silica-based column (Zorbax)

((7) Glycidyl methacrylate bond amount)
The modified conjugated diene polymer was refluxed in acetone at 60° C. for 1 hour or more to remove unreacted glycidyl methacrylate. The modified conjugated diene polymer after reflux was dissolved in toluene, and hydrochloric acid was added in an amount 2 mol times the amount of glycidyl methacrylate added during the extrusion reaction, and refluxed at 60° C. for 30 minutes or more to react the epoxy group of glycidyl methacrylate with hydrochloric acid. The toluene solution after the reaction was titrated with potassium hydroxide having a factor of 1±0.05 to quantify the amount of unreacted hydrochloric acid, and the amount of glycidyl methacrylate bound to the modified conjugated diene polymer was calculated from the amount of reacted hydrochloric acid.

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

((9) Toughness of Resin Composition)
The tensile elongation at break of the resin composition was measured in accordance with ISO 527 using a tensile tester (apparatus: TG-5kN (manufactured by MinebeaMitsumi)).
When polyethylene terephthalate or polyphenylene sulfide resin, which is a thermoplastic resin, was used as component (I), the test pieces were ISO-527-2-1A dumbbells molded by an injection molding machine, and the tensile test speed was 50 mm/min.
For each composition, three or more test pieces were tested, and the average values were taken as the physical property values.
When an epoxy resin, which is a thermosetting resin, was used as component (I), a test piece specified in JIS K6911 5.18.1(2) was 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, was used as component (I), the notched Charpy impact strength was measured and evaluated in accordance with JIS K 7111-1. The test specimen was prepared by cutting both ends of the above-mentioned ISO dumbbell to prepare a rectangular test specimen with a length of about 80 mm, a width of about 10 mm, and a thickness of about 4 mm at the parallel portion, with a notch shape of A and an impact direction of edgewise.
When an epoxy resin, which is a thermosetting resin, was used as component (I), a test piece specified in JIS K6911 5.20.2 was prepared, the notch shape was A, and the impact direction was edgewise.
The measurement temperatures were room temperature (23° C.) and −30° C. The unit is kJ/ ^m2 .

((11) Processability (Flowability of Resin Composition))
When a thermoplastic resin such as polyethylene terephthalate or polyphenylene sulfide resin was used as component (I), the spiral flow length of the resin composition was measured by the following method to evaluate the processability.
The longer the spiral flow length, the higher the fluidity and the better the processability.
The resin composition was charged into an injection molding machine (clamping pressure 18 tf, screw system Φ16, SL screw) with a cylinder temperature set to 300-320°C (hopper side to nozzle side), and injection molding was performed at a screw rotation speed of 150 rpm, back pressure of 2 MPa, and a filling speed of 50 mm/s and an injection pressure of 100 MPa into a spiral flow measurement mold having a spiral width of 5 mm at a metering completion position of 55 mm, a spiral thickness of 3 mm, a maximum spiral length of 850 mm, and an imprint width of 10 mm. The cooling time was 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 of the resin composition was observed by subjecting a test molded product (ISO-527-2-1A) of the resin composition described below to ultrasonic cleaning in ethanol for about 1 hour, cutting it using an ultramicrotome, and exposing a cross section. The cutting was performed at -150°C using a glass knife and a diamond knife, and a precise cross section was prepared for AFM observation.
The AFM used was manufactured by Bruker, and the probe used was a SCANASYST-AIR.
The precision cross-section sample was fixed on a dedicated sample fixing stand, and an elastic modulus mapping was created from the elastic modulus force curve obtained with the measurement mode set to QMN Mode in Air, the resolution set to 512 x 256 pixels, the measurement range set to 10 x 10 μm, the maximum indentation load set to 500 pN, and the scan speed set to 1.0 Hz. The elastic modulus mapping was output as a grayscale image with high elastic modulus displayed brightly and low elastic modulus displayed darkly, with 512 x 512 pixels. In addition, a two-point moving average filter process was performed to remove noise, and a binarized image was created. The Otsu method was used for the binarization process.
The binarized image was subjected to particle analysis using Analyze Particles of ImageJ, and the fillet diameter of each particle of the dispersed phase (B) was calculated.
For each resin composition, three molded bodies were observed and the fillet diameters were calculated, and the average value of the fillet diameters was taken as the number average dispersed diameter of the dispersed phase (B).

[Production of resin composition]
(Component (I): Resin having a polar group)
Component (I): As a resin having a polar group, the following polar resin was used.
Polyphenylene sulfide resin: A900 (manufactured by Toray Industries, Inc.)
Polyethylene terephthalate resin: TRF-8550FF (Teijin Limited)
Epoxy resin: bisphenol A type EXA-850CRP (DIC Corporation)

(Component (II))
The component (II) was produced by the method for producing a modified conjugated diene polymer described below.
The modifiers, other components, and hydrogenation catalysts used in the production are shown below.
[Denaturant]
As the modifier for producing the modified conjugated diene polymer, the following compound was used.
Maleic anhydride (Fuso Chemical Co., Ltd.)
1,3-Dimethyl-2-imidazolidinone (Tokyo Chemical Industry Co., Ltd.)
Glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.)
Peroxide 25B (NOF Corporation)

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

[Hydrogenation catalyst]
A hydrogenation catalyst used in the hydrogenation reaction of the modified conjugated diene polymer was prepared by the following method.
1 L of dried and purified cyclohexane was placed in a nitrogen-substituted reaction vessel, and 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added thereto. Then, with sufficient stirring, an n-hexane solution containing 200 mmol of trimethylaluminum was added thereto, and the mixture 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 stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 80 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.
Next, 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added in an amount of equimolar to 1 mole of n-butyllithium, and the mixture was reacted for 10 minutes at 70° C. After completion of the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (1-A) obtained as described above had a styrene content of 20 mass%, a weight average molecular weight of 12.2 × 10 ⁴ , a molecular weight distribution of 1.10, a vinyl bond amount of 44%, and a modification rate of 70% (the number of modified groups per polymer chain was 0.70).
Further, the hydrogenation catalyst prepared as described above was added to the obtained terminal amine-modified conjugated diene polymer (1-A) in an amount of 50 ppm based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (1-A), and a hydrogenation reaction was 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 octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the terminal amine-modified hydrogenated conjugated diene polymer (1-A) to obtain a terminal amine-modified hydrogenated conjugated diene polymer (1-B). The hydrogenation rate of the obtained terminal amine-modified hydrogenated conjugated diene polymer (1-B) was 73% and the vinyl hydrogenation rate was 96%.
The thus obtained terminal amine-modified hydrogenated conjugated diene polymer (1-B) and maleic anhydride were mixed, and the mixture was fed to a twin-screw extruder with the temperature set to 150 to 200° C. throughout the entire length of the 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-mentioned conditions, and it was confirmed that no adsorption of amino groups occurred on the column.
This means that all of the amino groups had reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modified groups per polymer chain was 0.70.

<Modified conjugated diene polymer (2)>
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 80 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.
Next, 1.1 moles of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added per mole of n-butyllithium, and the mixture was reacted for 15 minutes at 70° C. After completion of the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (2-A) obtained as described above had a styrene content of 20 mass%, a weight average molecular weight of 12.1 × 10 ⁴ , a molecular weight distribution of 1.10, a vinyl bond amount of 45%, and a modification rate of 80% (the number of modifying groups per polymer chain was 0.80).
Further, the hydrogenation catalyst prepared as described above was added to the obtained terminal amine-modified conjugated diene polymer (2-A) in an amount of 50 ppm based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (2-A), and a hydrogenation reaction was 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 octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the terminal amine-modified conjugated diene polymer (2-A) to obtain a terminal amine-modified hydrogenated conjugated diene polymer (2-B).
The hydrogenation rate of the resulting terminal amine-modified hydrogenated conjugated diene polymer (2-B) was 74%, and the vinyl hydrogenation rate was 96%.
The thus obtained terminal amine-modified hydrogenated conjugated diene polymer (2-B) and maleic anhydride were mixed, and then the mixture was fed to a twin-screw extruder with the temperature set to 150 to 200° C. throughout the entire length of the 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-mentioned conditions, and it was confirmed that no adsorption of amino groups occurred on the column.
This means that all of the amino groups had reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modified groups per polymer chain was 0.80.

<Modified conjugated diene polymer (3)>
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.
Next, 1.1 moles of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added per mole of n-butyllithium, and the mixture was reacted for 15 minutes at 70° C. After completion of the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (3-A) obtained as described above had a styrene content of 30 mass%, a weight average molecular weight of 12.0 × 10 ⁴ , a molecular weight distribution of 1.09, a vinyl bond amount of 43%, and a modification rate of 79% (the number of modifying groups per polymer chain was 0.79).
Further, the hydrogenation catalyst prepared as described above was added to the obtained terminal amine-modified conjugated diene polymer (3-A) in an amount of 50 ppm based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (3-A), and a hydrogenation reaction was 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 octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the terminal amine-modified conjugated diene polymer (3-A) to obtain a terminal amine-modified hydrogenated conjugated diene polymer (3-B).
The hydrogenation rate of the resulting terminal amine-modified hydrogenated conjugated diene polymer (3-B) was 75%, and the vinyl hydrogenation rate was 96%.
The thus obtained terminal amine-modified hydrogenated conjugated diene polymer (3-B) and maleic anhydride were mixed, and then the mixture was fed to a twin-screw extruder with the temperature set to 150 to 200° C. throughout the entire length of the extruder, and compounded to obtain a terminal carboxyl group-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-mentioned conditions, and it was confirmed that no adsorption of amino groups to the column occurred.
This means that all of the amino groups had reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modified groups per polymer chain was 0.79.

<Modified conjugated diene polymer (4)>
A terminal carboxyl group-modified conjugated diene polymer (4-C) was obtained by the same procedure as in the above-mentioned <Modified conjugated diene polymer (2)>, except that 0.2 mol of tetramethylethylenediamine (TMEDA) was added per mol of n-butyllithium. The 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, a vinyl bond amount of 24%, a hydrogenation rate of 78%, a vinyl hydrogenation rate of 96%, and a modification rate of 80% (the number of modifying groups per polymer chain was 0.79).

<Modified conjugated diene polymer (5)>
The same operation as in the above <Modified conjugated diene polymer (2)> was carried out, except that 0.09 parts by mass of n-butyllithium was added relative to 100 parts by mass of the total monomers, to obtain a terminal carboxyl group-modified conjugated diene polymer (5-C). The terminal carboxyl group-modified conjugated diene copolymer (5-C) obtained 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, a vinyl bond amount of 43%, a hydrogenation rate of 78%, a vinyl hydrogenation rate of 96%, and a modification rate of 80% (the number of modifying groups per polymer chain was 0.80).

<Modified conjugated diene polymer (6)>
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 6.5 parts by mass of styrene (concentration: 20% by mass) was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 87 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 6.5 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.
Next, 1.1 moles of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added per mole of n-butyllithium, and the mixture was reacted for 15 minutes at 70° C. After completion of the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (6-A) obtained as described above had a styrene content of 13 mass%, a weight average molecular weight of 12.2 × 10 ⁴ , a molecular weight distribution of 1.09, a vinyl bond content of 35%, and a modification rate of 81% (the number of modifying groups per polymer chain was 0.81).
Further, the hydrogenation catalyst prepared as described above was added to the obtained terminal amine-modified conjugated diene polymer (6-A) in an amount of 90 ppm based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (6-A), and a hydrogenation reaction was 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 octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the terminal amine-modified conjugated diene polymer (6-A) to obtain a terminal amine-modified hydrogenated conjugated diene polymer (6-B).
The hydrogenation rate of the resulting terminal amine-modified hydrogenated conjugated diene polymer (6-B) was 80%, and the vinyl hydrogenation rate was 98%.
The thus obtained terminal amine-modified hydrogenated conjugated diene polymer (6-B) and maleic anhydride were mixed, and then the mixture was fed to a twin-screw extruder with the temperature set to 150 to 200° C. throughout the entire length of the extruder, and compounded to obtain a terminal carboxyl group-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-mentioned conditions, and it was confirmed that no adsorption of amino groups occurred on the column.
This means that all of the amino groups had reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modified groups per polymer chain was 0.81.

<Modified conjugated diene polymer (7)>
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 25 parts by mass of styrene (concentration: 20% by mass) was charged.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 50 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 25 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.
Next, 1.1 moles of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added per mole of n-butyllithium, and the mixture was reacted for 15 minutes at 70° C. After completion of the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (7-A) obtained as described above had a styrene content of 50 mass%, a weight average molecular weight of 11.9 × 10 ⁴ , a molecular weight distribution of 1.11, a vinyl bond amount of 43%, and a modification rate of 79% (the number of modifying groups per polymer chain was 0.79).
Further, the hydrogenation catalyst prepared as described above was added to the obtained terminal amine-modified conjugated diene polymer (7-A) in an amount of 50 ppm based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (7-A), and a hydrogenation reaction was 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 octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the terminal amine-modified conjugated diene polymer (7-A) to obtain a terminal amine-modified hydrogenated conjugated diene polymer (7-B).
The hydrogenation rate of the resulting terminal amine-modified hydrogenated conjugated diene polymer (7-B) was 77%, and the vinyl hydrogenation rate was 97%.
The thus obtained terminal amine-modified hydrogenated conjugated diene polymer (7-B) and maleic anhydride were mixed, and then the mixture was fed to a twin-screw extruder with the temperature set to 150 to 200° C. throughout the entire length of the 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-mentioned conditions, and it was confirmed that no adsorption of amino groups occurred on the column.
This means that all of the amino groups had reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modified groups per polymer chain was 0.79.

<Modified conjugated diene polymer (8)>
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 80 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.
Methanol was then added.
The conjugated diene polymer (8-A) obtained as described above had 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%.
Further, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene polymer (8-A) in an amount of 70 ppm based on Ti per 100 parts by mass of the conjugated diene polymer (8-A), and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80° C. for about 3.0 hours.
Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the conjugated diene polymer (8-A) to obtain a hydrogenated conjugated diene polymer (8-B).
The hydrogenation rate of the resulting hydrogenated conjugated diene polymer (8-B) was 97%, and the vinyl hydrogenation rate was 99%.
The hydrogenated conjugated diene polymer (8-B) and glycidyl methacrylate obtained as described above were mixed, and then the mixture was fed to a twin-screw extruder with the temperature set to 150 to 220° C. throughout the entire length of the extruder. Peroxide 25B was added from the middle of the extruder, and the mixture was compounded to obtain a main-chain epoxy-modified conjugated diene polymer (8-C).
The obtained main chain epoxy group-modified conjugated diene polymer (8-C) was titrated by the above-mentioned method, and the glycidyl methacrylate bond amount was found to be 1.2% by mass.

<Modified conjugated diene polymer (9)>
Batch polymerization was carried out using a tank-type reactor (internal volume: 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of the total monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was carried out at 70° C. for 20 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 70° C. for 45 minutes.
Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration: 20% by mass) was added, and polymerization was carried out at 70° C. for 20 minutes.
Methanol was then added.
The conjugated diene polymer (9-A) obtained as described above had 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%.
Further, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene polymer (9-A) in an amount of 50 ppm based on Ti per 100 parts by mass of the conjugated diene polymer (9-A), and a hydrogenation reaction was 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 octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the conjugated diene polymer (9-A) to obtain a hydrogenated conjugated diene polymer (9-B).
The hydrogenation rate of the resulting hydrogenated conjugated diene polymer (9-B) was 76%, and the vinyl hydrogenation rate was 96%.
The hydrogenated conjugated diene polymer (9-B) obtained as described above, maleic anhydride, and organic peroxide (Perhexa 25B (manufactured by NOF Corporation)) were mixed, and the mixture was fed to a twin-screw extruder with the temperature set to 150 to 220° C. throughout the entire length of the extruder, and compounded to obtain 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 by the method shown in ((9) Amount of maleic anhydride bond) above, and the amount of maleic anhydride bond was found to be 1.5% by mass.

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

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

[Examples 1 to 13, Reference Examples 14 to 15]
The above components were melt-kneaded in the composition ratios shown in Tables 1 and 2 using a twin-screw extruder ZSK28 (manufactured by Werner and Pfleiderer) at a cylinder setting temperature of 300° C., a screw rotation speed of 200 rpm, and a discharge rate of 9 kg/hour to produce resin compositions.
Thereafter, using an injection molding machine, injection molding was carried out at a cylinder temperature of 300° C. and a mold temperature of 140° C. to prepare test pieces (ISO-527-2-1A).

Comparative Examples 1 to 11
As the component (II), modified conjugated diene polymers (1-B) and (1-C) were used.
Other materials and conditions were the same as in Examples 1 to 13 and Reference Examples 14 to 15, and resin compositions were produced in the composition ratios shown in Table 3, and test specimens were prepared.

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.
In the table, "(1)" indicates that the test piece in the Charpy impact test was not broken.

[Examples 16 to 21, Reference Example 22]
The above-mentioned components (I) to (III) were melt-kneaded in the composition ratios shown in Table 4 using a twin-screw extruder ZSK28 (manufactured by Werner and Pfleiderer) at a cylinder setting temperature of 290° C., a screw rotation speed of 200 rpm, and a discharge rate of 9 kg/hour to produce resin compositions.
Thereafter, using an injection molding machine, injection molding was carried out at a cylinder temperature of 290° C. and a mold temperature of 120° C. to prepare test pieces (ISO-527-2-1A).

Comparative Examples 12 to 15
As the component (II), a modified conjugated diene polymer (9-B) was used.
Other materials and conditions were the same as in Examples 16 to 21 and Reference Example 22, and resin compositions were produced in the composition ratios shown in Table 5, and test specimens were prepared.

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

[Reference Examples 23 to 25, Examples 26 to 27]
Using the above components, resin compositions were produced in the composition ratios shown in Table 6.
In the case where the epoxy resin solution contained the component (II) and the component (III), the component (III) was dissolved in toluene at a concentration of about 20 mass % and added to the epoxy resin solution, followed by stirring.
Next, the mixture was vacuum-dried at room temperature to remove most of the toluene. Next, a curing agent was added and the mixture was stirred to obtain a resin composition in a solution state.
Next, the solution-like resin composition was heated to 80°C, and then injected into a mold having a shape specified for the above-mentioned toughness test and Charpy impact test, and a cured resin composition was obtained by compression molding at 140°C for 2 hours.
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]
As the component (II), a modified conjugated diene polymer (9-B) was used.
The other materials and conditions were the same as those of Reference Examples 23 to 25 and Examples 26 to 27, and resin compositions were produced with the composition ratios shown in Table 7, and test pieces were prepared.

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.

The results in Tables 1 to 7 reveal that Examples 1 to 13, Reference Examples 14 to 15, Examples 16 to 21, Reference Examples 22 to 25, and Examples 26 to 27 are excellent in impact resistance and toughness.

This application is based on a Japanese patent application (Patent Application No. 2021-122776) filed with the Japan Patent Office on July 27, 2021, and a Japanese patent application (Patent Application No. 2021-153417) filed with the Japan Patent Office on September 21, 2021, the contents of which are incorporated herein by reference.

The resin composition of the present invention can be used to produce a wide variety of molded products, including sheets, films, injection molded products of various shapes, hollow molded products, compressed air molded products, vacuum molded products, extrusion molded products, foam molded products, nonwoven fabrics and fibrous molded products, and synthetic leather. These molded products have industrial applicability for use in automotive interior and exterior materials, building materials, toys, home appliance parts, medical instruments, industrial parts, various hoses, various housings, various module cases, various power control unit parts, and other miscellaneous goods.

Claims (13)

Component (I): a resin having a polar group (excluding component (II) below),
Component (II):
A polymer block (A) mainly composed of vinyl aromatic monomer units,
a block polymer having at least two polymer blocks selected from a polymer block (B) mainly composed of a conjugated diene monomer unit and a random polymer block (C) composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
at least one modified conjugated diene polymer having at least one polar group bonded thereto selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxyl group, an epoxy group, an oxetanyl group, and an amino group;
Component (III): a polymer having a polar group reactive with component (I) and/or component (II) (excluding components (I) and (II));
A resin composition comprising:
The 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), and the number average dispersed particle size of the dispersed phase (B) is 1.5 μm or less;
a mass ratio of the component (I) to the component (II) is component (I):component (II)=50/50 to 99/1;
A resin composition , wherein the mass ratio of the component (II) to the component (III) is component (II):component (III)=1/99 to 99/1 . The component (I) is
At least one resin selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, polybutylene terephthalate-based resins, and epoxy resins;
The resin composition according to claim 1. The component (II) contains a hydrogenated modified conjugated diene polymer in which an aliphatic double bond derived from a conjugated diene compound is hydrogenated.
The resin composition according to claim 2 . The component (I) is a polyphenylene sulfide resin.
The resin composition according to claim 2 . The component (II) contains a modified conjugated diene-based polymer having at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group bonded thereto.
The resin composition according to claim 2 . The component (III) is a polymer having at least one polar group selected from the group consisting of an epoxy group, an oxazoline group, and an oxetanyl group.
The resin composition according to claim 1 or 2 . The component (III) is an olefin-based elastomer having an epoxy group.
The resin composition according to claim 1 or 2 . The hydrogenation rate of the hydrogenated modified conjugated diene polymer is 90% or less.
The resin composition according to claim 3 . The content of vinyl aromatic monomer units in the component (II) is 40 mass% or less.
The resin composition according to claim 2 . The component (III) is an elastomer having an epoxy group, which is composed of a copolymer of a polymerizable monomer having an epoxy group and an unsaturated hydrocarbon compound.
The resin composition according to claim 1 or 2 . The component (III) is a copolymer of a polymerizable monomer having an epoxy group, an unsaturated hydrocarbon compound, and a (meth)acrylic acid ester and/or vinyl acetate.
The resin composition according to claim 1 or 2 . A polymer block (A) mainly composed of vinyl aromatic monomer units,
The copolymer has at least two polymer blocks selected from a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
A modified conjugated diene-based polymer (component (II)) having at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group;
At least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins (component (I));
An olefin-based elastomer (component (III)) having at least one polar group selected from the group consisting of an epoxy group, an oxazoline group, and an oxetanyl group;
of,
a mass ratio of the resin having a polar group (component (I)) to the modified conjugated diene polymer (component (II)) is set to 50/50 to 99/1;
a step of kneading the modified conjugated diene polymer and the olefin elastomer having a polar group in a mass ratio of modified conjugated diene polymer:olefin elastomer having a polar group=1/99 to 99/1 to obtain a resin composition;
The resin composition comprises a continuous phase (A) of the resin having a polar group (component (I)) and the modified conjugated diene-based polymer (component (II)) dispersed in the continuous phase (A).
and a step of making the number average dispersed particle diameter of the dispersed phase (B) 1.5 μm or less.
A method for producing a resin composition. At least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins (component (I));
a modified conjugated diene-based polymer (component (II)) having at least two polymer blocks selected from a polymer block (A) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) of a vinyl aromatic monomer unit and a conjugated diene monomer unit;
An olefin-based elastomer having an epoxy group (component (III)),
, including,
A molded article of a resin composition,
The modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group,
The molded article satisfies the following conditions (I-1) to (II-1).
<Condition (I-1)>
A rectangular test piece having a width of 10 mm, a length of 170 mm and a thickness of 2 mm obtained from the molded product has a tensile breaking elongation of 25% or more at room temperature and at a tensile speed of 5 mm/min.
<Condition (II-1) >
A rectangular test piece having a length of about 80 mm, a width of about 10 mm and a thickness of about 4 mm obtained from the molded body has a Charpy impact value of 15 kJ/m ² or more in a Charpy impact test at -30°C.