WO2023008424A1

WO2023008424A1 - Resin composition, method for producing resin composition, and molded body

Info

Publication number: WO2023008424A1
Application number: PCT/JP2022/028771
Authority: WO
Inventors: 裕太松岡; 敬助川
Original assignee: 旭化成株式会社
Priority date: 2021-07-27
Filing date: 2022-07-26
Publication date: 2023-02-02
Also published as: TWI818643B; JPWO2023008424A1; TW202309192A

Abstract

This resin composition contains: a component (I), a polar group-containing resin (excluding component (II)); and a component (II), at least one type of modified conjugated diene-based polymer in which at least one type of 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 types of polymer block selected from among a polymer block (A) comprising mainly a vinyl aromatic monomer unit, a polymer block (B) comprising mainly a conjugated diene monomer unit and a random polymer block (C) of vinyl aromatic monomer units and conjugated diene units. The resin composition has a continuous phase (A) of the component (I) and dispersed phases (B) containing component (II) that are dispersed in the continuous phase (A). The number average dispersed particle diameter of the dispersed phases (B) is 1.5 μm or less. The component (I) : component (II) mass ratio is 50/50-99/1.

Description

RESIN COMPOSITION, RESIN COMPOSITION MANUFACTURING METHOD, AND MOLDED PRODUCT

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

Conjugated diene-based polymers are known to exhibit various properties by adjusting the ratio of 1,2-bonds, the ratio of blocks constituting the conjugated diene-based polymer, the arrangement of blocks, the degree of hydrogenation, and the like. It is In addition, for the purpose of imparting further properties, a conjugated diene polymer (hereinafter referred to as modified described as a conjugated diene-based polymer) has 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. Modifiers are being considered. Modified conjugated diene-based polymers are widely used as modifiers for polar resins because they have excellent compatibility with polar resins due to intermolecular forces such as reactions with modified groups and hydrogen bonding.

JP 2014-210848 A

In recent years, as automobiles, home appliances, communication equipment, etc. have become more sophisticated and the use of IoT has spread, the weight of each component has been reduced and the use of electrical equipment has progressed. There is an increasing demand for polar resins that have excellent properties, electrical insulation, and dielectric properties.
On the other hand, there is a demand for materials that can withstand impacts during manufacturing and use in electronic materials. The challenge is the need to improve toughness.
For example, Patent Document 1 proposes a resin composition containing a modified conjugated diene-based polymer having toughness superior to that of PPS in order to improve the toughness of polyphenylene sulfide resin (hereinafter sometimes referred to as "PPS"). It is
However, according to the study of the present inventors, the resin composition disclosed in Patent Document 1 still has a problem that the toughness is not sufficient and there is room for improvement.

Therefore, in view of the above problems of the prior art, an object of the present invention is to provide a resin composition excellent in impact resistance and toughness.

The inventors of the present invention have made intensive studies to solve the above-mentioned problems of the prior art, and found that a resin having a polar group (component (I)) and a modified conjugated diene-based polymer having a predetermined polar group (component (II)), wherein the dispersed phase (B) containing the modified conjugated diene polymer has a predetermined number average dispersed particle diameter, and the resin having the polar group ( Component (I)) and the modified conjugated diene-based polymer (component (II)) are specified to have a predetermined mass ratio, thereby finding that the above-described problems of the prior art can be solved. was completed.
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,
At least two polymer blocks selected from polymer blocks (B) mainly composed of conjugated diene monomer units and random polymer blocks (C) composed of vinyl aromatic monomer units and conjugated diene monomer units to a block polymer having
at least one modified conjugated diene-based polymer to 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;
A resin composition containing
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 dispersed phase (B) has a number average dispersed particle size of 1.5 μm or less,
A resin composition wherein the mass ratio of component (I) to component (II) is component (I):component (II)=50/50 to 99/1.
[2]
Component (III): further comprising a polymer having a polar group reactive with component (I) and/or component (II) (excluding components (I) and (II)),
The mass ratio of the component (II) and the component (III) is component (II):component (III) = 1/99 to 99/1,
The resin composition according to [1] above.
[3]
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 [1] above.
[4]
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 [2] above.
[5]
The component (II) contains a hydrogenated modified conjugated diene-based polymer in which an aliphatic double bond derived from a conjugated diene compound is hydrogenated,
The resin composition according to any one of [1] to [4].
[6]
The component (I) is a polyphenylene sulfide resin,
The resin composition according to any one of [1] to [5].
[7]
The component (II) contains a modified conjugated diene-based polymer to which at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups is bonded,
The resin composition according to any one of [1] to [6].
[8]
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 [2] to [7].
[9]
wherein the component (III) is an olefin elastomer having an epoxy group;
The resin composition according to any one of [2] to [8].
[10]
The hydrogenation rate of the hydrogenated modified conjugated diene polymer is 90% or less,
The resin composition according to any one of [5] to [9].
[11]
The content of vinyl aromatic monomer units in the component (II) is 40% by mass or less.
The resin composition according to any one of [1] to [10].
[12]
The component (III) is an epoxy group-containing elastomer comprising a copolymer of an epoxy group-containing polymerizable monomer and an unsaturated hydrocarbon compound.
The resin composition according to any one of [2] to [11].
[13]
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 [2] to [12].
[14]
a polymer block (A) mainly composed of vinyl aromatic monomer units,
At least two polymer blocks selected from polymer blocks (B) mainly composed of conjugated diene monomer units and random polymer blocks (C) composed of vinyl aromatic monomer units and conjugated diene monomer units has
a modified conjugated diene-based polymer (component (II)) having at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups;
a resin (component (I)) having at least one polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins;
an olefinic elastomer (component (III)) having at least one polar group selected from the group consisting of epoxy groups, oxazoline groups, and oxetanyl groups;
of,
The mass ratio of the resin having a polar group (component (I)) and the modified conjugated diene-based polymer (component (II)) is adjusted to the resin having a polar group: modified conjugated diene-based polymer = 50/50 ~ 99/1,
The mass ratio of the modified conjugated diene-based polymer and the olefin-based elastomer having a polar group is kneaded so that the modified conjugated diene-based polymer: olefin-based elastomer having a polar group = 1/99 to 99/1. obtaining a composition;
The resin composition comprises a continuous phase (A) of the resin having a polar group (component (I)) and the modified conjugated diene polymer (component (II)) dispersed in the continuous phase (A).
A dispersed phase (B) containing
A method for producing a resin composition.
[15]
at least one resin having a polar group (component (I)) selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins;
Polymer block (A) mainly composed of vinyl aromatic monomer units, polymer block (B) mainly composed of conjugated diene monomer units, vinyl aromatic monomer units and conjugated diene monomer units a modified conjugated diene-based polymer (component (II)) having at least two polymer blocks selected from random polymer blocks (C);
an olefin-based elastomer having an epoxy group (component (III));
including,
A molded body of a resin composition,
The modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups,
A molded body, wherein the molded body satisfies the following conditions (I-1) to (II-1).
<Condition (I-1)>
A strip-shaped test piece having a width of 10 mm, a length of 170 mm, and a thickness of 2 mm obtained from the compact has a tensile elongation at break of 25% or more at room temperature and a tensile speed of 5 mm/min.
<Condition (II-1)
A strip-shaped 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 compact has a Charpy impact value of 15 kJ/m ² in a Charpy impact test at -30°C.

According to the present invention, it is possible to provide a resin composition with excellent impact resistance and toughness.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be modified and implemented as appropriate within the scope of its gist.

[Resin composition]
The resin composition of this embodiment is
Component (I): a resin having a polar group (excluding component (II) below);
Component (II): polymer block (A) mainly composed of vinyl aromatic monomer units,
At least two polymer blocks selected from polymer blocks (B) mainly composed of conjugated diene monomer units and random polymer blocks (C) composed of vinyl aromatic monomer units and conjugated diene monomer units A modified conjugated diene-based 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 with at least one
is a resin composition containing
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 dispersed phase The number average dispersed particle size of (B) is 1.5 μm or less.
The mass ratio of component (I) to component (II) is component (I):component (II)=50/50 to 99/1.
By having the above structure, a resin composition having excellent 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 sometimes referred to as polar resin (I) or component (I)).

Resins with excellent rigidity generally have 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 includes, for example, acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene-styrene copolymer resin (MBS). Polyvinyl chloride resins; Polyvinyl acetate resins and hydrolysates thereof; Polymers of acrylic acid and its esters and amides; Polyacrylate resins; Acrylonitrile and/or methacrylonitrile polymers; Nitrile resin that is a copolymer with another copolymerizable monomer containing 50% by mass or more; polyamide resin; polyester resin, thermoplastic polyurethane resin, poly-4,4'-dioxydiphenyl-2 , 2′-propane carbonate and other polycarbonate polymers; thermoplastic polysulfones such as polyethersulfone and polyallylsulfone; polyoxymethylene resins; polyphenylenes such as poly(2,6-dimethyl-1,4-phenylene) ether Ether-based resin; Polyphenylene sulfide-based resin; Polyarylate-based resin; Polyetherketone polymer or copolymer; Polyketone-based resin;
fluorine-based resin; polyethylene terephthalate-based resin; polyoxybenzoyl-based polymer, polyimide-based resin; polyethylene terephthalate-based resin; polybutylene terephthalate-based resin;

The preferred polar resin (I) varies depending on the properties required for the resin composition of the present embodiment. Epoxy resins and polyphenylene sulfide resins are preferable from the viewpoint of chemical properties, and polyphenylene sulfide resins are preferable from the viewpoint of heat resistance.

The polyethylene terephthalate-based resin may belong to the category called polyethylene terephthalate resin, and includes a diol component in which at least 90 mol% or more is ethylene glycol and a dicarboxylic acid component in which at least 90 mol% or more is terephthalic acid. A thermoplastic resin obtained by the polymerization reaction of is more preferable.

The polybutylene terephthalate-based resin may belong to the category called polybutylene terephthalate resin, and includes a dicarboxylic acid containing terephthalic acid or a derivative thereof as a main component and 1,4-butanediol or a derivative thereof as a main component. It is a polymer that can be obtained by a general polymerization method such as polycondensation reaction with a diol, and the repeating unit of butylene terephthalate is preferably 90 mol% or more, and is preferably 95 mol% or more. more preferred.

Any epoxy resin may be used as long as it belongs to the category called epoxy resin, and from the viewpoint of rigidity, it is preferable to have two or more epoxy groups in one molecule. Epoxy resins may be used singly or in combination of two or more.
Examples of epoxy resins include, but are not limited to, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and the like.

The polyphenylene sulfide resin may belong to the category called polyphenylene sulfide resin, and from the viewpoint of heat resistance, it preferably contains 70 mol % or more of p-phenylene sulfide units as its constituent units. , more preferably 90 mol % or more.
Other structural units include, for example, o-phenylene sulfide units, m-phenylene sulfide units, phenylene sulfide ether units, phenylene sulfide sulfone units, phenylene sulfide ketone units, diphenylene sulfide units, substituent-containing phenylene sulfide units, It may contain branched structure-containing phenylene sulfide units and the like.
The molecular weight of the polyphenylene sulfide-based resin is preferably 5,000 or more, more preferably 10,000 or more, from the viewpoint of the rigidity of the resin composition of the present embodiment.
The polyphenylene sulfide-based resin may be linear, crosslinked or branched.
Moreover, the polyphenylene sulfide-based resin may have a polar group such as a thiol group or a carboxyl group at the terminal or in the main chain in the polymer structure.
The method for producing the polyphenylene sulfide-based resin is not particularly limited, and includes, for example, a production method in which an alkali metal sulfide and a dihaloaromatic compound are reacted in a polymerization solvent.

(Component (II): modified conjugated diene-based polymer)
The resin composition of the present embodiment comprises a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a vinyl aromatic monomer A block polymer having at least two types of polymer blocks selected from random polymer blocks (C) composed of polymer units and conjugated diene monomer units is added with an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxyl group, and an epoxy group. , an oxetanyl group, and a modified conjugated diene-based polymer to which at least one polar group selected from the group consisting of amino groups is bonded (hereinafter referred to as modified conjugated diene-based polymer (II), component (II). There is at least one of
Since the modified conjugated diene-based polymer (II) has the polar group, it has affinity and/or reactivity with respect to the polar resin (I). It can improve toughness and impact resistance.

The affinity means that at least one intermolecular force selected from the group consisting of ionic interaction, hydrogen bond, dipole interaction and van der Waals force can be generated between each component.
The reactivity means that the polar groups of each component have covalent bonding. When polar groups react with each other, for example, when the OH of the carboxyl group is eliminated, the original polar group changes or disappears, but when this forms a covalent bond, the polar groups are "reactive" included in the definition of indicating

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. By having the the number average dispersed particle size of the dispersed phase (B) comprising component (II) in the continuous layer (A) comprising component (I) is 1.5 μm or less, and the interface between the components is strengthened. This contributes to the improvement of 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 the present embodiment. For example, when the polar resin (I) is a polyphenylene sulfide resin, the epoxy group, oxazoline group, and amino group have excellent affinity and/or reactivity with the thiol group and carboxyl group present at the end of the polyphenylene sulfide resin. Therefore, it is preferable as the polar group of the modified conjugated diene polymer (II). Carboxyl groups, acid anhydride groups, hydroxyl groups, and dicarboxyl groups have excellent affinity and/or reactivity with epoxy groups of component (I) when component (I) is an epoxy resin. In this way, each component (I) and (II) has an affinity group and/or a reactive group that expresses affinity and/or reactivity between the components, thereby strengthening the interface between each component. becomes possible, contributing to the improvement of the toughness and impact resistance of the resin composition of the present embodiment. Furthermore, effects such as improvement in tracking resistance and prevention of deterioration in physical properties (heat cycle characteristics) when exposed alternately between high and low temperatures can be expected. 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-based resin or polybutylene terephthalate-based resin, the epoxy group and amino group of component (II) are present at the terminals of the polyethylene terephthalate-based resin or polybutylene terephthalate-based resin. Since the affinity and / or reactivity with the carboxyl group is excellent, each component has an affinity group and / or a reactive group that expresses affinity and / or reactivity between the components, so that the interface between each component can be strengthened, which contributes to improving the toughness and impact resistance of the resin composition.
Further, as the component (II), two types of modified conjugated diene-based polymers each having a different polar group from the above-described polar group species bonded thereto may be used. When two types of modified conjugated diene-based polymers (II) having different polar groups bonded thereto are used from the viewpoint of compatibility as described above, one type of modified conjugated diene-based polymer has the other modified conjugated diene-based It is preferable that a polar group reactive with the polymer and the polar resin (I) is bonded.
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 to which an epoxy group is bonded and a carboxyl group and/or Alternatively, a modified conjugated diene-based polymer having hydroxyl groups bonded thereto can be preferably used.
Further, for example, when the polar resin of component (I) is an epoxy resin, the carboxyl group, hydroxyl group, and amino group have excellent affinity and/or reactivity with the epoxy group of the epoxy resin. A modified conjugated diene polymer can be preferably used as component (II). In this way, each component has an affinity group and/or a reactive group that expresses affinity and/or reactivity between the components, so that the interface between the components can be strengthened. contributes to improving the toughness and impact resistance of the resin composition.

Generally, in a resin composition, the same components tend to aggregate and form a phase, but in the resin composition of the present embodiment, the component (II) has a polar group, so that the component The affinity and/or reactivity with (I) is enhanced, the compatibility of these components is improved, and the number average dispersed particle diameter of the dispersed phase (B) described later is 1.5 μm or less, and the resin of the present embodiment It contributes to the impact resistance and toughness of the composition.
The amount of polar groups possessed by the modified conjugated diene-based polymer (II) is preferably 0.3 mol/chain or more, more preferably 0.5 mol/chain, from the viewpoint of compatibility with the polar resin (I). or more, more preferably 0.6 mol/chain or more.
When the amount of polar groups in the modified conjugated diene-based polymer (II) is 0.3 mol/chain or more, the polymer chains having the affinity group or the reactive group are compatible with the component (I) and have an affinity for each other. The polymer chains having no functional group or reactive group and the polymer chains compatible with the component (I) aggregate as described above, so that the number average dispersed particle size of the dispersed phase (B) is reduced to 1. 0.5 μm or less, preferably 1.3 μm or less.
Such easiness of compatibility and easiness of agglomeration is determined by the structure of the resin as long as the polar groups contained in component (I) and component (II) have the necessary affinity and/or reactivity. The frequency (amount) of the polar groups in the polymer chain has a greater effect than the type of polar groups, the combination of polar groups between 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 the polar groups in the component (II).
In addition, the affinity group or reactive group of component (II) is preferably 30 mol/chain or less, since an excessive amount may cause gelation or the like in the resin composition of the present embodiment.
As used herein, the term "chain" refers to one polymer molecule, and a branched polymer structure due to chemical bonds is also counted as one molecule chain.
The amount of polar groups in the modified conjugated diene-based polymer (II) depends on the reaction conditions with the compound for forming these during the production process of the modified conjugated diene-based polymer, such as the amount of the compound added, the reaction temperature, and the reaction time. By adjusting the above, it is possible to control within the above numerical range.

The modified conjugated diene polymer (component (II)) has two or more polymer blocks selected from the group consisting of polymer blocks (A) to (C) below.
(A) Polymer block mainly composed of vinyl aromatic monomer units (hereinafter sometimes referred to as polymer block (A))
(B) a polymer block mainly composed of conjugated diene monomer units (hereinafter sometimes referred to as polymer block (B));
(C) a random polymer block of vinyl aromatic monomer units and conjugated diene monomer units (hereinafter sometimes referred to as random polymer block (C) or polymer block (C));

The (A) polymer block mainly composed of vinyl aromatic monomer units has a vinyl aromatic monomer unit content of 80% by mass or more.
Examples of vinyl aromatic compounds used to form vinyl aromatic monomer units include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene and the like.
Among these, styrene, α-methylstyrene and 4-methylstyrene are preferred, and styrene is more preferred, from the viewpoint of availability and productivity.
The (A) polymer block mainly composed of vinyl aromatic monomer units may be composed of one vinyl aromatic monomer unit, or may be composed of two or more vinyl aromatic monomer units. It may be configured by
From the viewpoint of the strength of the molded article of the resin composition of the present embodiment, the content of the vinyl aromatic monomer units contained in the polymer block (A) mainly composed of vinyl aromatic monomer units is 80 mass. % or more, preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass (other compounds are not intentionally added).

The content of the conjugated diene monomer units in the (B) polymer block mainly composed of conjugated diene monomer units is 80% by mass or more.
A diolefin having a pair of conjugated double bonds can be used as the conjugated diene compound used to form the conjugated diene monomer unit. Examples of the diolefin include, but are 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, 1,3-butadiene and isoprene are preferred from the viewpoint of availability and productivity.
(B) The polymer block mainly composed of conjugated diene monomer units may be composed of one type of conjugated diene monomer unit, or may be composed of two or more types of conjugated diene monomer units. may
From the viewpoint of impact resistance of the resin composition of the present embodiment, the content of the conjugated diene monomer unit contained in the polymer block (B) mainly composed of the conjugated diene monomer unit is 80% by mass or more. It is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass (other compounds are not intentionally added).

(C) the vinyl aromatic monomer unit contained in the random polymer block of the conjugated diene monomer unit and the vinyl aromatic monomer unit and the vinyl aromatic compound used to form the conjugated diene monomer unit , and the conjugated diene compound may be compounds that can be used for the polymer block (A) and the polymer block (B).
The distribution state of the vinyl aromatic monomer units in the random polymer block (C) is not particularly limited, and even if the vinyl aromatic monomer units in the random polymer block (C) are uniformly distributed, Or it may be distributed in a tapered shape. Further, there may be a plurality of portions in which the vinyl aromatic monomer units are uniformly distributed and/or portions in which the vinyl aromatic monomer units are distributed in a tapered manner. A plurality of different segments may exist.
The mass ratio of the vinyl aromatic monomer unit to the conjugated diene monomer unit in the random copolymer block (C) is: vinyl aromatic monomer unit/conjugated diene monomer unit=75/25 to 25/ 75 is preferred, more preferably 70/30 to 30/70, still more preferably 65/35 to 35/65.
The modified conjugated diene-based polymer (II) used in the resin composition of the present embodiment may be polymerized with other compounds copolymerizable with the conjugated diene compound and the vinyl aromatic compound.

The structure of the modified conjugated diene polymer (component (II)) is not particularly limited, but examples thereof include those having a structure represented by the following formula.
Note that the description of the polar group is omitted in the following formula.
(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, [(cb) _n -c] _m -X,
(ab) _n , b-(ab) _n , a-(ba) _n , (ab) _m -X, (ba) _m -X, [(ab) _n ] _m −X, [(b−a) _n ] _m −X, [b−(a−b) _n ] _m −X, [a−(b−a) _n ] _m −X, [(a−b ) _n -a] _m -X, [(ba) _n -b] _m -X,
(ac) _n , c-(ac) _n , a-(c-a) _n , (ac) _m -X, (c-a) _m -X, [(ac) _n ] _m -X, [(c-a) _n ] _m -X, [c-(a-c) _n ] _m -X, [a-(c-a) _n ] _m -X, [(a-c ) _n -a] _m -X, [(ca) _n -c] _m -X,
c-(b-a) _n , c-(a-b) _n ,
c-(ab-a) _n , c-(b-a-b) _n ,
ac-(b-a) _n , ac-(a-b) _n ,
ac-(b-a) _n -b, [(a-b-c) _n ] _m -X,
[a-(b-c) _n ] _m -X, [(a-b) _n -c] _m -X,
[(ab-a) _n -c] _m -X,
[(b-a-b) _n -c] _m -X, [(c-b-a) _n ] _m -X,
[c-(b-a)n] _m -X, [c-(a-b-a) _n ] _m -X, [c-(b-a-b) _n ] _m -X
a-(bc) _n , a-(c-b) _n ,
a-(c-b-c) _n , a-(b-c-b) _n ,
ca-(bc) _n , ca-(cb) _n ,
c-a-(b-c) _n -b, [(c-b-a) _n ] _m -X,
[c−(b−a) _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-(c-a) _n ,
b-(c-a-c) _n , b-(a-c-a) _n ,
cb-(ac) _n , cb-(c-a) _n ,
cb-(ac) _n -a, [(c-a-b) _n ] _m -X,
[c−(a−b) _n ] _m −X, [(c−a) _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-(a-c) _n ] _m -X, [b-(c-a-c) _n ] _m -X, [b-(a-c-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, preferably an integer of 1-5.
m is an integer of 2 or more, preferably an integer of 2-11.
X represents a residue of a coupling agent or a residue of a multifunctional initiator.
The modified conjugated diene-based polymer (component (II)) is a polymer whose basic block structure is particularly represented by the structural formulas ab, aba, and abab. Preferably.

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

The modified conjugated diene polymer (component (II)) contains vinyl aromatic monomer units.
In general, imparting impact resistance and toughness by dispersing a predetermined polymer in a highly rigid polar resin will cause the interface between the polar resin and the dispersed polymer particle component or the polymer This is because voids are formed in the particles themselves, and stress relaxation is caused by shear yielding of the matrix resin starting from the polymer particles.
Since the polymer block (A) mainly composed of vinyl aromatic monomer units is amorphous, it tends to accelerate the aforementioned shear yielding.
Therefore, the lower limit of the content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) is 1 mass from the viewpoint of promoting the above-mentioned shear yield and developing impact resistance and toughness. % or more, more preferably 3 mass % or more, still more preferably 5 mass % or more, and even more preferably 8 mass % or more.
Since the content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) is 1% by mass or more, the vinyl aromatic monomer of the modified conjugated diene polymer (II) The amorphous part of the units tends to aggregate and promote the aforementioned shear yielding. However, when voids occur at the interface between the highly rigid polar resin and dispersed polymer particle components or at the polymer particles themselves, it is important that the difference in rigidity between the matrix polar resin and the dispersed phase is large. From this point of view, the upper limit of the vinyl aromatic monomer unit of the modified conjugated diene polymer (component (II)) is the ratio of the polar resin (component (I)) and the dispersed polymer particle component (component (II)). From the viewpoint of generating voids in the interfaces or the polymer particles themselves and developing impact resistance and toughness, the content is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. By setting the vinyl aromatic monomer unit amount of component (II) to 90% by mass or less, the difference in rigidity between the dispersed phase and the matrix becomes large, and voids occur more at the interface or at the polymer particles themselves, and the resin of the present embodiment The composition tends to have improved impact resistance and toughness.
When a polyphenylene sulfide-based resin is used as the polar resin of component (I), the vinyl aromatic monomer unit of the modified conjugated diene-based polymer (component (II)) is included from the viewpoint of developing impact resistance at low temperatures. The amount 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.
The content of the vinyl aromatic monomer units in the modified conjugated diene polymer (component (II)) can be measured by the method described in Examples below.
The content of vinyl aromatic monomer units in the modified conjugated diene polymer (component (II)) can be controlled within the above numerical range by adjusting the amount of monomer added during polymer production. .

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

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

The modified conjugated diene polymer (II) may contain a hydrogenated modified conjugated diene polymer in which the aliphatic double bonds derived from the conjugated diene compound are hydrogenated. Thereby, the heat resistance of the resin composition of this embodiment can be improved.
The hydrogenation rate of the aliphatic double bond derived from the conjugated diene compound is the thermally unstable 1,2-bond (however, when it is incorporated into the polymer with a 3,4-bond, the Hydrogenation of the 2-bond and 3,4-bond) improves the heat resistance, so it is preferably 10% or more, more preferably 20% or more, and still more preferably 30% or more.
Further, 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 dispersed phase (B) in the resin composition of the present embodiment has a number average dispersed particle size of 1 0.5 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 still more preferably 80% or less.
The hydrogenation rate of the modified conjugated diene-based polymer (II) can be measured using a nuclear magnetic resonance spectrometer (NMR) or the like, and specifically can be measured by the method described in Examples.
Also, the hydrogenation rate can be controlled within the above numerical range by adjusting the amount of hydrogen reacted during the hydrogenation reaction, for example.

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

The polymerization temperature is generally 0 to 180°C, preferably 20 to 160°C, more preferably 30 to 150°C.
Although the polymerization time varies depending on the desired polymer, it is usually within 48 hours, preferably 0.1 to 10 hours. From the viewpoint of obtaining a conjugated diene-based polymer having a narrow molecular weight distribution and high strength, 0.5 to 5 hours is more preferable.
The atmosphere of the polymerization system is not particularly limited as long as the pressure is in a range sufficient to maintain the nitrogen and solvent in the liquid phase.
It is preferable that impurities such as water, oxygen, carbon dioxide gas, etc. that deactivate the polymerization initiator and the living polymer do not exist 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; cyclohexane, cycloheptane, methylcyclo alicyclic hydrocarbons such as pentane; and aromatic hydrocarbons such as benzene, xylene, toluene and ethylbenzene.

An organic lithium compound is preferable as the organic alkali metal compound that is the polymerization initiator.
Organic lithium compounds include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds.
Examples of organic lithium compounds 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, lithium piperidide and the like.
When an organic lithium compound containing N such as lithium piperidide is used as a polymerization initiator, an amino group-modified conjugated diene polymer having an atomic group in which 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 the polymerization initiator depends on the molecular weight of the desired modified conjugated diene polymer, but is generally 0.01 to 1.5 phm (parts by weight per 100 parts by weight of the monomer). ), more preferably 0.02 to 0.3 phm, even more preferably 0.05 to 0.2 phm.

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

Examples of vinylizing agents include, but are not limited to, ether compounds, tertiary amine compounds, and the like.

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

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 individually by 1 type, and may use 2 or more types together.
A compound having two amines is preferable as the tertiary amine compound. Furthermore, among them, those having a structure exhibiting symmetry in the molecule are more preferable, such as N,N,N',N'-tetramethylethylenediamine and bis[2-(N,N-dimethylamino)ethyl] Ether and 1,2-dipiperidinoethane are more preferred.

The modified conjugated diene-based polymer (II) used in the resin composition of the present embodiment is polymerized using a conjugated diene compound and a vinyl aromatic compound in the presence of the above-described vinylizing agent, organolithium compound, and alkali metal alkoxide. It can be manufactured by
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).
Coexistence of an alkali metal alkoxide in the polymerization step provides the effect of controlling the amount of vinyl bonds, molecular weight distribution, polymerization rate, block ratio, and the like.

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

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

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 epoxy group, an oxetanyl group, and an amino group. there is
A hydroxyl group and a carboxyl group are more preferable from the viewpoint of affinity and/or reactivity with the polar resin (I) and a polymer having a predetermined polar group (component (III)) described later.
Further, since the polar group bonded to the modified conjugated diene polymer (II) is at least one selected from the group consisting of hydroxyl groups and carboxyl groups, a thermoplastic resin is used as the component (I), and injection molding is performed. When a resin composition in a molten state is injected into a mold and cooled to obtain an arbitrary molded body, the fluidity of the resin composition tends to be improved and the processability tends to be improved.
The method of introducing the polar group into the conjugated diene-based polymer is not particularly limited. For example, a method of introducing with a polymerization initiator having each predetermined polar group; a method of obtaining a modified conjugated diene-based polymer by polymerizing a; a method of adding a modifying agent having a polar group to the living end of the polymer;
In the modified conjugated diene-based polymer (II), the position at which each polar group is introduced is not particularly limited. and may be arranged in a tapered shape. Affinity and/or reactivity with a polar resin (component (I)) and a polymer having a predetermined polar group (component (III)) described later, and from the viewpoint of workability of the resin composition described above , is more preferably the end of the conjugated diene-based polymer.

Examples of the "modifying agent" include, but are not limited to, maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbarylic acid, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and the like. and aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid and pyromellitic acid.
In addition, 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, ε-caprolactam and the like.

As another method for introducing a polar group into a conjugated diene polymer, for example, a conjugated diene polymer is reacted (metalation reaction) with an organic alkali metal compound such as an organic lithium compound to add an organic alkali metal. A method of subjecting a polymer to an addition reaction with a modifier having a polar group can be used.

Furthermore, another method for introducing a polar group includes, for example, a method of directly grafting an atomic group having a polar group to an unmodified conjugated diene polymer.
Examples of the graft addition method include a method of reacting them in a solution containing a radical initiator, a conjugated diene polymer, and the modifier; or a radical initiator, a conjugated diene polymer, and the modifier. or a method of reacting a conjugated diene polymer without a radical initiator and a compound containing the modifier under heating and melting.

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

Examples of the radical initiator include, but are not limited to, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. The radical initiator preferably has a 1-minute half-life temperature within the kneading temperature range. More preferably, the one-minute half-life temperature is 150° C. to 250° C. Examples 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-butyl peroxylaurate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2 ,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-di-(t-butylperoxy)butane, t-butylperoxybenzonate, 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-butylperoxide, 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-butylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne -3 is preferred.
Furthermore, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are more preferred.

As another method for introducing a polar group into a conjugated diene polymer, there is a second method in which the primary modified conjugated diene polymer obtained by the above method is reacted with an atomic group having a predetermined polar group. The following modifications are mentioned.
A combination of polar groups includes 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; silanol groups, hydroxyl groups, and carboxyl groups; epoxy groups and carboxyl groups; 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 more preferred. an amino group, a dicarboxyl group, and an acid anhydride group.

As a primary modification, the method of bonding an epoxy group, an acid anhydride group, and a hydroxyl group to a conjugated diene polymer includes the above-described methods. is mentioned.

As a primary modification, the method of bonding a silanol group to a conjugated diene polymer includes the above-described methods. Examples thereof include (3-triethoxysilylpropyl)-disulfane, ethoxysiloxane oligomers, epoxy group-containing polymerizable compounds, and hydrolysates of compounds having an alkoxysilane group listed above as epoxy group-containing polymerizable compounds.

As the primary modification, the method of binding an amino group to a conjugated diene polymer includes the above-described methods. 2-imidazolidinone, N,N'-dimethylpropylene urea, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazo Lizinone, 1-methyl-3-propyl-2-imidazolidinone, 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' -diethylpropylene urea, N-methyl-N'-ethylpropylene urea and the like. 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone, 1-methyl-2-piperidone, 1,4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-isopropyl-2 -piperidone, 1-isopropyl-5,5-dimethyl-2-piperidone and the like.

Examples of the method for binding the primary modified conjugated diene-based polymer to which an amino group is bound and the secondary modifier include the methods described above. Examples of modifiers include maleic acid, oxalic acid, succinic acid, and adipine. acids, aliphatic carboxylic acids such as azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbarylic acid, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid; terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, aromatic carboxylic acids such as trimellitic acid and pyromellitic acid; In addition, 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 the like.

The shape of the modified conjugated diene-based polymer (II) obtained by the production method described above is not particularly limited, and examples thereof include pellets, sheets, strands, chips, and the like. Moreover, after melt-kneading, it can be directly molded.
By pelletizing the modified conjugated diene polymer (II), pellets of the modified conjugated diene polymer can be produced.
Pelletization methods include, for example, a method of extruding a modified conjugated diene-based polymer from a single-screw or twin-screw extruder in the form of strands and cutting in water with a rotary blade installed in front of the die; single-screw or twin-screw A method of extruding a modified conjugated diene-based polymer from an extruder into a strand, cooling it with water or air, and then cutting it with a strand cutter; For example, the sheet is cut into strips, and then cut into cubic pellets by a pelletizer.
The size and shape of the pellet are not particularly limited.

The modified conjugated diene-based polymer (II) may optionally be blended with a pellet antiblocking agent for the purpose of preventing pellet blocking.
Examples of pellet antiblocking agents include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylenebisstearylamide, talc, amorphous silica, and the like.
When the resin composition of the present embodiment is used to produce a random polypropylene composition, a tubular molded article containing the same, or a sheet-shaped molded article, from the viewpoint of their transparency, calcium stearate, polyethylene, and polypropylene are used. preferable.
A preferred amount of the pellet antiblocking agent is 500 to 6000 ppm relative to the modified conjugated diene polymer (II). A more preferable amount is 1000 to 5000 ppm with respect to the modified conjugated diene polymer (II). The pellet anti-blocking agent is preferably blended in a state attached to the pellet surface, but can 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 is a polymer having a polar group reactive with component (I) and/or component (II) (excluding component (I) and component (II)) (hereinafter referred to as polymer ( III), sometimes referred to as 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), it exhibits reactivity with the component (I) and/or the component (II). In the resin composition of the present embodiment, the number average dispersed particle size of the dispersed phase (B) tends to be 1.5 μm or less by containing the polymer (III) having a functional group having a polar group.
In addition, from the viewpoint of expressing impact resistance and toughness by increasing the difference in rigidity between the matrix polar resin (component (I)) and the dispersed phase (component (II) and component (III)) and promoting shear yield. Therefore, component (III) preferably has reactivity with component (I) and component (II).
Component (III) 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). It is a modified polymer.
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). including oligomers with a low degree of polymerization of about 2 to 10).
The lower limit of the molecular weight of component (III) is preferably 1,000 or more, more preferably 2,000 or more, from the viewpoint of maintaining practically sufficient rigidity of the resin composition of the present embodiment. From the viewpoint of fluidity of the resin composition of the present embodiment, the upper limit of the molecular weight of component (III) is preferably 5 million or less, more preferably 3 million or less, and even more preferably 1 million or less.
Further, the molecular weight of the component (III) can be appropriately set in consideration of the compatibility with the component (I) and the component (II), the fluidity of the resin composition of the present embodiment, and the like. When it is 5,000,000 or less, good fluidity of the resin composition tends to be obtained, and practically good moldability tends to be obtained.

"Reactivity" between component (III) and component (I) and/or component (II) means that the polar groups of each component have covalent bonding.
When polar groups react with each other, for example, when the OH of the carboxyl group is eliminated, the original polar group changes or disappears. included in the definition of indicating
As for the polar groups contained in component (III), one type of polar group may exhibit reactivity with both component (I) and component (II), or multiple types of polar groups may contain component (I) and component (II). It may be reactive with each of (II).
A polar group reactive with only one of component (I) and component (II) may be contained in component (III), but the affinity with both components is increased, and the dispersion phase (B) described later From the viewpoint of making the number average dispersed particle size 1.5 μm or less, preferably 1.3 μm or less, it is preferable to have a polar group that exhibits reactivity with both component (I) and component (II). For example, when component (III) has an epoxy group, component (I) is a polyphenylene sulfide resin, and component (II) is a polymer having a carboxyl group and/or a hydroxyl group, the epoxy group of component (III) shows reactivity with the carboxyl groups of both the component (I) polyphenylene sulfide resin and the component (II) polymer.
The polar group contained in component (III) has reactivity with the polar resin (component (I)) and the modified conjugated diene-based polymer (component (II)), so that the resin composition of the present embodiment has toughness and impact resistance can be improved.

(Combination of Component (I), Component (II), and Component (III))
Combinations of the polar groups of component (II) and component (III) include the following combinations.
When component (II) contains an amino group, preferable polar groups contained in component (III) include a carboxyl group, a carbonyl group, an epoxy group, a hydroxy group, an acid anhydride group, a sulfonic acid group, an aldehyde group, and the like. be done.
When component (II) contains an acid anhydride group, preferred polar groups contained in component (III) include an amino group and a hydroxy group.
When component (II) contains a carboxyl group or a dicarboxyl group, preferable polar groups contained in component (III) include an amino group and an isocyanate group.
When component (II) has an epoxy group, preferable polar groups contained in component (III) include amino group, carboxyl group, dicarboxyl group, thiol group, oxazoline group, oxetanyl group and the like.
When component (II) contains an oxetanyl group, preferred polar groups contained in component (III) include a thiol group, hydroxyl group, amino group, carboxyl group, dicarboxyl group, and the like.
When component (II) contains an oxazoline group, preferred polar groups contained in component (III) include a thiol group, hydroxyl group, amino group, carboxyl group, dicarboxyl group and the like.
Further, as a combination of polar groups contained in component (I) and component (III), respectively,
amino groups, carboxyl groups, carbonyl groups, epoxy groups, hydroxy 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 anhydride group;
a silanol group, a hydroxy group, a carboxyl group, and a dicarboxyl group;
an epoxy group, a carboxyl group, a dicarboxyl group, a thiol group, an oxazoline group, and an oxetanyl group;
a halogen group, a carboxylic acid group, a carboxylic acid ester group, an amino group, a phenol group, and a thiol group;
an alkoxy group, a hydroxy group, an alkoxide group, and an amino group;
a thiol group, an epoxy group, an oxazoline group, and an oxetanyl group;
etc.

In the resin composition of the present embodiment, it can be arbitrarily selected which of the polar groups of component (I) and component (III) is used to bond with the polar group of component (II).
When a polyphenylene sulfide-based resin, which is a polar resin having excellent rigidity, chemical resistance, and heat resistance, is used as component (I), the polar group contained in component (II) may be a carboxyl group from the viewpoint of reactivity. , hydroxyl group, epoxy group, oxazoline group and oxetanyl group are preferred, and carboxyl group and hydroxyl group are more preferred.
The polar group of component (III) is preferably an epoxy group, an oxazoline group, or an oxetanyl group because it is reactive with component (I) and component (II), and more preferably an epoxy group from the viewpoint of reactivity.

When the component (III) is a polymer having an epoxy group, the polymer having an epoxy group includes a polymer of an epoxy group-containing polymerizable compound such as an epoxy group-containing unsaturated compound, and an epoxy group-containing polymerizable compound. and copolymers of the compound with at least one other polymerizable compound.
Epoxy group-containing polymerizable compounds include, but are not limited to, epoxy group-containing unsaturated compounds such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ethers, glycidyl ethers of hydroxyalkyl (meth)acrylates, polyalkylene Glycidyl ether of glycol (meth)acrylate, glycidyl itaconate, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidyl Examples include polyepoxy compounds such as orthotoluidine, 4,4'-diglycidyl-diphenylmethylamine, 4,4'-diglycidyl-dibenzylmethylamine, and diglycidylaminomethylcyclohexane.

In addition, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy silane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane ethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiphenoxysilane sidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropyldimethylethoxysilane sidoxypropylmethyldiisopropeneoxysilane, bis(γ-glycidoxypropyl)dimethoxysilane, and bis(γ-glycidoxypropyl)diethoxysilane.

Furthermore, 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-glycidoxy propyl), tris(γ-glycidoxypropyl)methoxysilane.

Furthermore, β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tripropoxysilane , β-(3,4-epoxycyclohexyl)ethyl-tributoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triphenoxysilane.

Still further, 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-methyldipropoxy Silane, β-(3,4-epoxycyclohexyl)ethyl-methyldibutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiphenoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylmethoxysilane Silane, β-(3,4-epoxycyclohexyl), β-(3,4-epoxycyclohexyl)ethyl-dimethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylpropoxysilane, β-(3, 4-epoxycyclohexyl)ethyl-dimethylbutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylphenoxysilane.

Furthermore, β-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiisopropeneoxysilane, N-(1,3-dimethylbutylidene)-3 -(triethoxysilyl)-1-propanamine and the like.

Examples of the compound copolymerizable 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 compounds such as acrylonitrile; Vinyl monomer; vinyl acetate, (meth)acrylic acid ester, vinyl alcohol, vinyl acetate, vinyl acetate and the like.

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

Further, a polymer having an epoxy group may be obtained as the component (III) by a method of subjecting an arbitrary polymer to an addition reaction with the epoxy group-containing unsaturated compound or the like by a radical reaction or the like.
Examples of the optional polymer include polymers of unsaturated hydrocarbon compounds such as ethylene and propylene, copolymers of the unsaturated hydrocarbon compounds and polymerizable compounds having double bonds, conjugated diene compounds and vinyl aromatic compounds. Copolymers of compounds and the like can be mentioned.
Examples of the method of the addition reaction include conventionally known techniques, a production method in which these are reacted in a solution containing a radical initiator, a polymer, and an epoxy group-containing compound; a radical initiator, a polymer, and an epoxy group; A production method in which the containing compound is reacted under heating and melting; A production method in which a polymer without a radical initiator and an epoxy group-containing compound are reacted under heating and melting; Examples include a manufacturing method in which a compound and a polymer that react to form a bond, and a compound containing an epoxy group are reacted in a solution containing them or under heating and melting.
Further, a method of forming an epoxy group by oxidizing the diene portion of a polymer having a carbon bond and/or a copolymer of a polymer having a carbon bond and another polymerizable compound can also be used.

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, polyalkylene It is a glycidyl ether of glycol (meth)acrylate.

By improving the affinity between the polymer having an epoxy group (component (III)) and the modified conjugated diene polymer (component (II)), stress is applied to the dispersed phase (B) of the resin composition of the present embodiment. makes it easier to concentrate on From the viewpoint of affinity with the modified conjugated diene-based polymer (component (II)), the epoxy group-containing polymer (component (III)) is the above-mentioned epoxy group-containing polymerizable compound (epoxy group-containing polymerizable monomer ) and an unsaturated hydrocarbon-based compound, the elastomer having an epoxy group is more preferable, and the olefin-based elastomer having an epoxy group is even more preferable.
When the polymer (component (III)) is an olefin elastomer having an epoxy group, the effect of improving toughness and/or impact resistance due to shear yield caused by stress concentration at the resin interface with component (I) is improved. Furthermore, the effect of inhibiting elongation of microcracks and / or crazes generated under stress is obtained, and component (II) and component (III) bridge between microcracks and / or crazes This effect tends to further improve toughness and/or impact resistance. In particular, in applications where the component (III) is an epoxy group-containing olefin-based elastomer, toughness and/or impact resistance at low temperatures can be improved, particularly in applications where the temperature is -30°C or lower. It tends to improve. Furthermore, it can be expected to improve the tracking resistance and the effect of suppressing deterioration of physical properties (heat cycle characteristics) even when exposed alternately from high temperature to low temperature.
These effects can be improved by controlling the compatibility state by adjusting the affinity and reactivity between each component.

In addition, the polymer having an epoxy group as the component (III) contains, in addition to the unsaturated hydrocarbon and the epoxy group-containing polymerizable compound, vinyl cyanide monomers such as the aforementioned styrene and acrylonitrile, vinyl acetate, (meth) A polymerizable compound such as an acrylic acid ester, vinyl alcohol, or vinyl acetate may be copolymerized, and when the component (I) is a polyphenylene sulfide resin, from the viewpoint of affinity with the polyphenylene sulfide resin. , (meth)acrylic acid ester, vinyl acetate and vinyl acetate are more preferably copolymerized, and it is further preferred that (meth)acrylic acid ester and/or vinyl acetate are 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-based polymer (II), and polymer (III))
In the resin composition of the present embodiment, the polar resin (component (I)) and the modified conjugated diene-based polymer (component (II)) are the heat resistance, impact resistance and toughness of the resin composition of the present embodiment. and the number average dispersed particle size of the dispersed phase (B) described later is 1.5 μm or less, the mass ratio of the component (I) and the component (II) is the component (I):component ( II) = 50/50 to 99/1, preferably 55/45 to 98/2, more preferably 60/40 to 95/5.

Further, when the resin composition of the present embodiment contains the polar resin (component (I)), the modified conjugated diene-based 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 component (II) to the component (III) is: component (II): component (III) = 1/99 to It is preferably 99/1, more preferably 5/95 to 95/5, even more preferably 10/90 to 90/10, still more preferably 15/85 to 85/15.

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

(dispersion state)
The resin composition of the present embodiment comprises a continuous phase (A) of a polar resin (component (I)) and a modified conjugated diene polymer (component (II)) dispersed in the continuous phase (A). and a dispersed phase (B) comprising.
By using the polar resin (component (I)) as the continuous phase (A), excellent heat resistance and rigidity can be obtained in the resin composition of the present embodiment.
In addition, due to the presence of the dispersed phase (B), when stress is applied to the molded body made of the resin composition, the stress concentrates on the dispersed phase (B), and microcrazes are generated. Contributes to the improvement of toughness.

Dispersed phase (B) may be a phase containing component (II), and when containing component (III), which is a polymer having a polar group reactive with component (II), component (II) The modified conjugated diene-based polymer and component (III) may be in a compatible phase, component (III) may be unevenly distributed around component (II), or The component (II) may be unevenly distributed. Also, the component (III) may be in a compatible state with the component (I). When only the component (III) is dispersed in the sea composed of the polar resin (component (I)), the effect of improving the impact resistance and/or toughness of the resin composition cannot be confirmed. Therefore, as described above, the dispersed phase (B) either contains both the component (II) and the component (III), or the component (II) is dispersed alone, whereby the dispersed phase (B ) is a phenomenon corresponding to the number average dispersed grain size and the improvement of 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 polymer (component (II)). do.

A method for confirming the state of dispersion of the continuous phase (A) and dispersed phase (B) will be described.
<(1) Identification of components contained in the resin composition>
First, specifying the components contained in the resin composition of the present embodiment is useful for measuring the number average dispersed particle size of the dispersed phase (B).
Component (I) polar resins are generally known to have excellent chemical resistance. When the above-mentioned component (II) modified conjugated diene polymer and component (III) polymer are included, when the resin composition is mixed in a solvent capable of dissolving component (III) as well, the resin composition exhibits excellent chemical resistance. Therefore, undissolved component (I), unreacted component (II) and component (III) can be extracted. In particular, when a polyphenylene sulfide resin is used as component (I), there is no solvent that dissolves the polyphenylene sulfide resin at 200° C. or lower. , undissolved component (I), unreacted component (II), and unreacted component (III) can be extracted.

When component (II) and component (III) are included, examples of solvents capable of dissolving component (III) include toluene, cyclohexane, xylene, tetrahydrofuran, chloroform, nitroethane, nitropropane, ethylbenzene, etc. Chloroform, nitroethane, nitropropane, ethylbenzene, and toluene are preferred from the viewpoint of solubility.
After the extraction, undissolved component (I) is removed by filtration or the like, and the filtrate is subjected to liquid phase chromatography to separate component (II) and component (III).
In addition, when the solubility of component (II) and component (III) is different, the above-mentioned filtrate is dried in a solvent such as vacuum drying using a solvent in which component (II) dissolves and component (III) cannot be dissolved. A method of separating component (II) and component (III) by mixing the mixture of component (II) and component (III) obtained by removing again in an appropriate solvent can also be employed.
Generally, toluene, cyclohexane, and tetrahydrofuran are examples of solvents in which component (II) is highly soluble.
The structural units of component (III) which are insoluble in the aforementioned solvent are polymer units of unsaturated hydrocarbon compounds, particularly ethylene, propylene, and α-olefins having 3 to 8 carbon atoms.
Identification of component (II), component (III) is performed by nuclear magnetic resonance (NMR), infrared absorption spectroscopy (IR), gas chromatography (GS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). ), etc. Also, the types and structures of the polar groups bonded to component (II) and component (III) can be identified.
In addition, when the resin composition of the present embodiment contains components such as additives described later that can be eluted in the solvent in the extraction step, the difference in molecular weight and polarity is used by liquid phase chromatography or the like to determine each component. and can be identified by the aforementioned NMR, IR, GS, TOF-SIMS, and the like.
If the amount of component (II) and component (III) unreacted with component (I) is very small and it is difficult to separate component (II) and component (III), an atomic force microscope (AFM ) From the infrared absorption spectrum obtained by observation, the structural units of component (II) and component (III), and the polar group species bonded to component (II) and component (III) can also be specified. A test piece to be subjected to AFM measurement includes a precise cross section of a resin composition prepared with an ultramicrotome or the like.

<(2) Measurement of dispersed particle size>
[(1) AFM (soft phase particle size measurement in elastic modulus mapping)]
In general, the melting point of the component (I) polar resin is high, and at room temperature, especially at low temperatures, it has higher rigidity than component (II), and when component (III) is included, it has higher rigidity than component (III). .
In addition, after isolating the component (II) and the component (III), the constituent units of the component (II) and the component (III) are identified, and the isolated component (the mixture of the component (II) and the component (III) is It can be confirmed that component (II) and component (III) have relatively lower stiffness than component (I) by measuring the stiffness of component (II) and component (III).
In addition, from the infrared absorption spectrum and/or the force curves of viscoelasticity and elastic modulus obtained by the aforementioned AMF observation, it was confirmed that component (I) has higher rigidity than component (II) and component (III). It is possible to clarify.
When the mass ratio of the polar resin (component (I)) in the resin composition of the present embodiment is 50% by mass or more, the component (I) forms "sea" in the morphology of the resin composition. As described above, there is a difference in stiffness between component (I), component (II), and component (III). If it is softer than that, it can be identified that the portion corresponding to the "island" is component (II) and/or component (III). Therefore, the number-average dispersed particle size of the dispersed phase (B) can be calculated by obtaining the average value of the particle sizes of the soft portions in the elastic modulus mapping by the method described in the examples below.
In general, elastic modulus measurement by AFM observation is calculated from the relationship between the load and the amount of deformation of the sample by setting the upper limit of the force acting on the tip of the AFM cantilever and the sample, and pressing the sample in the vertical direction. Therefore, the distribution of components with different elastic moduli can be observed as an image to represent the degree of deformation of each dispersed phase with respect to load.

In general, the melting temperature for mixing component (I), component (II), and optionally component (III) in a molten state is extremely high. For this reason, the low-molecular-weight compounds generated during kneading or the like may bleed, and a clear elastic modulus mapping may not be obtained. In such a case, as described in the examples below, ultrasonic cleaning is performed in a solvent such as ethanol to remove the low-molecular-weight compounds, etc., as a pre-step for preparing a precise cross-section for AFM observation. After that, it is preferable to prepare a precise section with an ultramicrotome or the like.

[(2) Identification of dispersed phase by staining]
After the isolation of component (II) and component (III) described above, when the structural units of component (II) and component (III) are identified, the structures of component (I), component (II) and component (III) Depending on the combination, each component is dyed and fixed by oxidizing it with an appropriate heavy metal, and the dispersed phase (B) is number-averaged using an electron microscope such as a transmission electron microscope (TEM) or a scanning electron microscope (SEM). A method of calculating dispersed particle diameters can also be employed.
A test piece subjected to electron microscopic observation is an ultra-thin section of the resin composition prepared by a cryomicrotome or the like, and may be prepared after the staining, or may be stained after the preparation.
For example, when component (I) has a smaller amount of aromatic skeleton than component (II) and component (III) does not have an aromatic ring skeleton, component (II) is used as a heavy metal in the staining agent to form tetraoxidation. Ruthenium available. Dyeing agents tend to oxidize the vinyl aromatic monomeric units of component (II) the most, followed by the aromatic ring backbone of component (I) polar resins, and not oxidize component (III). From the electron microscope observation of the resin composition dyed with an oxidizing agent, an image is obtained in which the component (I) is lightly dyed, the component (II) is most dyed, and the component (III) is not dyed. can be binarized using image analysis software or the like described in Examples described later to calculate the number average dispersed particle size of the dispersed phase (B) in the resin composition.
In the binarized image, when the dispersed phase (B) contains many phases other than circular phases such as ellipses, it is preferable to increase 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 field of view even in the field of view, the value obtained by doubling the particle size of the particles is defined as the fillet diameter described in the examples. , it is preferable to calculate the number average dispersed particle size of the dispersed phase (B).

From the viewpoint of concentrating more stress on the dispersed phase (B) and exhibiting sufficient impact resistance and toughness in the resin composition of the present 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 even more preferably 0.9 μm or less.
The lower limit of the number average dispersed particle size of the dispersed phase (B) is not particularly limited, but the number average dispersed particle size of 0.01 μm or more tends to facilitate maintaining the rigidity of the resin composition of the present embodiment. be.
In the resin composition of the present embodiment, as a method of maintaining sufficient rigidity for practical use, there is a method of adding a filler or the like, which will be described later. When the number average dispersed particle diameter of the dispersed phase (B) is less than 0.01 μm by increasing the amount of polar groups, the amount of side reactions in the step of adding polar groups increases, and the resistance of the resin composition increases. The dispersed phase (B) preferably has a number-average dispersed particle size of 0.01 μm or more because it tends to lower the impact resistance and toughness.

The modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of acid anhydride groups, hydroxyl groups, carboxyl groups, dicarboxyl groups, epoxy groups, oxetanyl groups, and amino groups. As a result, it exhibits high affinity and/or reactivity with the polar group of the polar resin (component (I)) and the epoxy group of the polymer having the epoxy group (component (III)).
The polar groups of component (II) and component (III) have affinity and/or reactivity with the polar resin (component (I)). Therefore, the amount of component (II) and the amount of polar groups bound to component (III) determine the affinity and/or reactivity with component (I).
As described above, from the viewpoint of increasing the reactivity of component (I), component (II) and component (III) and making the number average dispersed particle diameter of dispersed phase (B) 1.5 μm or less, modified conjugated diene polymer The amount of polar groups bonded to coalescence (II) is preferably 0.3 mol/chain or more, more preferably 0.5 mol/chain or more, and still more preferably 0.6 mol/chain or more. When the amount of polar groups in component (II) is less than 0.3 mol/chain, the amount of component (II) not reactive with component (I) and component (III) is less than the component ( II) It becomes 70 mol % or more of the total amount, and the dispersibility tends to be greatly reduced.
The mass ratio of component (II) and component (III) is, as described above, from the viewpoint of making the number average dispersed particle size of the dispersed phase (B) 1.5 μm or less, component (II):component (III) = preferably 1/99 to 99/1, more preferably 5/95 to 95/5, still more preferably 10/90 to 90/10, still more preferably 15/85 to 85/15 be.
Also, when using a polyphenylene sulfide resin as component (I), from the viewpoint of reactivity with polyphenylene sulfide resin, which is a polar resin excellent in terms of rigidity, chemical resistance, and heat resistance, it is bound to component (II). At least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group is preferable.
The polar groups bonded to component (III) are preferably reactive with the polar groups of component (I) and the polar groups of component (II), and are therefore epoxy groups, oxazoline groups, and oxetanyl groups. At least one selected from the group consisting of is preferable, and an epoxy group is more preferable.

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

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

In the resin composition of the present embodiment, a fibrous filler is preferable as the filler.
Examples of fibrous fillers include, but are not limited to, glass fibers, carbon fibers, cellulose nanofibers, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, sepiolite, and xonotlite. and fibrous inorganic fillers such as zinc oxide whiskers.
Among these, glass fiber, carbon fiber, cellulose nanofiber and wollastonite are preferable because they tend 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 reactive group for the polar resin (component (I)).
1 type of fibrous fillers may be contained, and 2 or more types may be contained.

Other additives include, but are not limited to, oils, fillers, heat stabilizers, ultraviolet absorbers, nucleating agents, antioxidants, weathering agents, light stabilizers, plasticizers, and antistatic agents. , flame retardants, slip agents, anti-blocking agents, anti-fog agents, lubricants, pigments, dyes, dispersants, copper damage inhibitors, neutralizers, anti-foaming agents, weld strength improvers, natural oils, synthetic oils, waxes, etc. of additives. Other elastomers and thermoplastics may also be used as additives in any proportion.
These may use only 1 type and may use 2 or more types together.

In addition, an auxiliary agent that improves the affinity or reactivity between the polar resin (component (I)) and the modified conjugated diene polymer (component (II)) may be added to the resin composition of the present embodiment.
As the auxiliary agent, 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 is preferred.

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, and known methods can be used.
For example, 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 )) and a Banbury mixer, a single screw extruder, a twin screw extruder, a co-kneader, a method of melt-kneading using a general kneader such as a multi-screw extruder, after dissolving or dispersing and mixing each component , a method of removing the solvent by heating, and the like are used.
From the viewpoint of controlling the number average dispersed particle size of the dispersed phase (B) to 1.5 μm or less, the method of melt-kneading is preferable.
As the method for producing the resin composition of the present embodiment, a melt-kneading method using an extruder is preferable from the viewpoint of productivity and good kneadability. In particular, by kneading each component with a multiaxial screw having two or more shafts and applying sufficient shearing energy, the interface between the polar resin and the modified conjugated diene polymer is increased, and the dispersed phase (B) is formed. .

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

In order to suppress oxidation of the modified conjugated diene-based polymer (II), melt-kneading may be performed under an inert gas such as nitrogen.
When the resin composition of the present embodiment is produced using an extruder, the positions and order of feeding the polar resin (I), the modified conjugated diene-based polymer (II), and other components are not particularly limited.
Further, when a thermosetting resin is used as component (I), component (II) obtained by dissolving a thermosetting resin in a solution form and/or a thermosetting resin in a solid form in an appropriate solvent, The resin composition of the present embodiment can be obtained by adding component (III) and, if necessary, the above-described additives, and after mixing, further adding an appropriate curing agent and mixing again.
Moreover, before adding the curing agent, the solvent in which the component (II) and the component (III) are dissolved may be removed by a method such as vacuum drying.
Examples of solvents include toluene, methyl ethyl ketone, cyclohexane, cyclohexanone, chloroform, tetrahydrofuran and the like.
When an epoxy resin, which is a polar resin excellent in terms of heat resistance, is used as the component (I), the curing agent is not particularly limited as long as it has a function of curing the polar resin (I). Examples 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. A single curing agent may be used alone, or two or more curing agents may be used in combination.
Moreover, you may add a hardening accelerator as needed. Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like.
A method of molding the resin composition of the present embodiment includes a method of injecting the resin composition into an arbitrary mold, heating the mold to an arbitrary time and temperature, and obtaining a cured product.
The mold temperature is preferably 30 to 300° C., more preferably 50 to 250° C., from the viewpoint of productivity. From the viewpoint of productivity, the heating time is preferably 1 minute to 5 hours, preferably 10 minutes to 3 hours.

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

In the manufacturing process of the resin composition of the present embodiment, the shape is not particularly limited, and may be pellet-like, sheet-like, strand-like, chip-like, or the like.

(Preferred form of method for producing resin composition)
A preferred embodiment of the method for producing the resin composition of the present embodiment includes the following method.
A polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a vinyl aromatic monomer unit and a conjugated diene monomer having at least two polymer blocks selected from random polymer blocks (C) of units,
Modified conjugated diene-based polymer (component (II)) having at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups, polyphenylene sulfide-based resin, polyethylene terephthalate-based resin, and polybutylene terephthalate-based resin A resin (component (I)) having at least one polar group selected from the group consisting of an olefin elastomer having at least one polar group selected from the group consisting of epoxy groups, oxazoline groups, and oxetanyl groups (component (III)), the mass ratio of the resin having a polar group (component (I)) and the modified conjugated diene-based polymer (component (II)) to the resin having a polar group: modified conjugated diene The mass ratio of the modified conjugated diene-based polymer to the olefin-based elastomer having a polar group was adjusted to: modified conjugated diene-based polymer: olefin-based elastomer having a polar group = a step of kneading at 1/99 to 99/1 to obtain a resin composition, wherein the resin composition comprises a continuous phase (A) of the resin having a polar group (component (I)) and the continuous It has a dispersed phase (B) containing the modified conjugated diene polymer (component (II)) dispersed in the phase (A), and the dispersed phase (B) has a number average dispersed particle diameter of 1.5 μm It has the following steps.
According to the production method described above, a resin composition having excellent impact resistance and toughness can be obtained.

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

The molded article of the present embodiment is produced by using the resin composition of the present embodiment by conventionally known methods such as extrusion molding, injection molding, two-color injection molding, sandwich molding, blow molding, compression molding, vacuum molding, and rotational molding. , powder slush molding, foam molding, laminate molding, calendar molding, blow molding, and the like.
In addition, processing such as foaming, powdering, stretching, adhesion, printing, painting, and plating may be performed as necessary.
By such molding methods, a wide variety of products such as sheets, films, injection molded products of various shapes, hollow molded products, pressure molded products, vacuum molded products, extrusion molded products, foam molded products, nonwoven fabrics and fibrous molded products, synthetic leather, etc. It can be used as a molded product. These molded products are automotive interior and exterior materials, building materials, toys, home appliance parts, medical equipment, industrial parts, various hoses, various housings, various module cases, various power control unit parts, miscellaneous goods, substrates for electronic equipment, etc. , casings, sheets, packages, etc.
From the viewpoint of stably exhibiting impact resistance and toughness, the molded article of the present embodiment is preferably used as a non-porous member. The term “porous” as used herein refers to pores penetrating through a material, and cells, which are non-penetrating pores generated by foaming, are not porous.

(Preferred Form of Molded Body)
In particular, the molded body of the present embodiment is
at least one resin having a polar group (component (I)) selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins;
Polymer block (A) mainly composed of vinyl aromatic monomer units, polymer block (B) mainly composed of conjugated diene monomer units, vinyl aromatic monomer units and conjugated diene monomer units a modified hydrogenated conjugated diene polymer (component (II)) having at least two polymer blocks selected from random polymer blocks (C);
an elastomer having an epoxy group (component (III));
A molded body of a resin composition containing
The modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups,
It is preferable that the molded body satisfies the following conditions (I-1) to (II-1) in applications where high impact resistance and toughness are required.
Applications that require high impact resistance and toughness include ducts for vehicles such as automobiles, industrial piping, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, and oscillation. Components related to electronic equipment such as terminals, various terminal boards, transformers, plugs, and printed circuit boards. These are molded articles that are used under wide temperature conditions from low to high temperatures.
<Condition (I-1)>
A strip-shaped test piece having a width of 10 mm, a length of 170 mm, and a thickness of 2 mm obtained from the compact has a tensile elongation at break of 25% or more at room temperature and a tensile speed of 5 mm/min.
<Condition (II-1)
A strip-shaped test piece having a length of about 80 mm, a width of about 10 mm, and a thickness of 4 mm obtained from the compact has a Charpy impact value of 15 kJ/m ² in a Charpy impact test at -30°C.

The molded body of this embodiment can be processed into a desired shape. For example, a dumbbell-shaped test piece or a strip-shaped test piece can be produced by cutting out a test piece from a nearly flat portion of the compact. It is not essential that the test piece is perfectly flat, and it is sufficient if it is flat enough to allow tensile elongation at break and viscoelasticity measurement. For example, in the case of a cylindrical molded body, depending on the diameter of the cylinder, a measurable test piece can be obtained by cutting the test piece in the longitudinal direction. In addition, the thickness of the molded body may be thicker than 2 mm. can be measured.

The molded article of the present embodiment has excellent resistance when the modified conjugated diene polymer (component (II)) is dispersed in a resin (component (I)) having a polar group such as a polyphenylene sulfide resin. It is preferable from the viewpoint of obtaining impact resistance and toughness. The average dispersed particle diameter of (II)) is 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.2 μm or less, and still more preferably 1.1 μm or less.
The average particle size of the dispersed modified conjugated diene-based polymer (component (II)) in the molded article of the present embodiment can be measured by the method described in Examples below.

For the purpose of improving the strength, the resin composition constituting the molded article of the present embodiment may contain additives such as fillers in an amount of 1 to 50 parts by mass and 5 to 30 parts by mass with respect to 100 parts by mass of the resin composition. Parts by weight are preferred. In addition to toughness and impact resistance, in order to add functions such as flame retardancy and tracking resistance, 1 to 70 parts by mass of other additives such as flame retardants are included with respect to 100 parts by mass of the resin composition. However, 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/m ² or more.

[Method for analyzing resin composition]
A method for analyzing the components of the resin composition of the present embodiment is shown below.
The polar group of the modified conjugated diene-based polymer (component (II)) used in the resin composition of the present embodiment is a resin (component (I) )), etc., by reacting with the polar group of the component (I) when kneaded, and is thought to contribute to reducing the particle size of the dispersed phase (B). It is assumed that the polar groups of the polymer (component (II)) often remain. In addition, although the polar groups of a given polymer (component (III)) also have reactivity with component (I) and/or component (II), it is believed that unreacted polar groups remain in the resin composition. be done.
The modified conjugated diene polymer (component (II)) having at least one selected from the group consisting of hydroxyl groups and carboxyl groups and the elastomer having epoxy groups (component (III)) in the molded article of the present embodiment are qualitatively determined. In order to do so, first, the above-mentioned modified conjugated diene polymer (component (II)) and epoxy group-containing elastomer (component (III)) are dissolved, and polyphenylene sulfide-based resin and polyethylene terephthalate-based resin, which are matrix resins, are dissolved. , and a polybutylene terephthalate-based resin (each component (I)) is mixed with a solvent that cannot dissolve the resin composition, and an unreacted modified conjugated diene-based polymer (component (II)) and an epoxy group are The elastomer (component (III)) is extracted. When the matrix resin is a polyphenylene sulfide-based resin, there is no solvent that dissolves the polyphenylene sulfide-based resin at 200°C or lower. polyphenylene sulfide resin (component (I)), unreacted modified conjugated diene polymer (component (II)), and unreacted epoxy group-containing elastomer (component (III)).
Solvents include, for example, toluene, cyclohexane, xylene, tetrahydrofuran, chloroform, nitroethane, nitropropane, ethylbenzene and the like, but chloroform, nitroethane, nitropropane, ethylbenzene, and toluene are preferred from the viewpoint of solubility.
After extraction, undissolved matrix resin is removed by filtration or the like, and the filtrate is subjected to liquid phase chromatography to remove unreacted modified conjugated diene polymer (component (II)), unreacted epoxy group can be separated off (component (III)).

Further, when the modified conjugated diene polymer (component (II)) and the epoxy group-containing elastomer (component (III)) have different solubilities, the modified conjugated diene polymer (component (II)) dissolves, Using a solvent in which the epoxy group-containing elastomer (component (III)) cannot be dissolved, the solvent is removed from the filtrate by vacuum drying or the like, and the modified conjugated diene polymer obtained thereby (component (II) ), and a mixture of elastomers having epoxy groups (component (III)) are mixed again in an appropriate solvent to convert unreacted modified conjugated diene-based polymer (component (II)) and unreacted epoxy groups to A method of separating the elastomer (component (III)) can also be employed.
Solvents in which the modified conjugated diene polymer (component (II)) is generally highly soluble include toluene, cyclohexane, and tetrahydrofuran.

The modified conjugated diene polymer (component (II)) and the epoxy group-containing elastomer (component (III)) can be identified by nuclear magnetic resonance spectroscopy (NMR), infrared absorption spectroscopy (IR), and gas chromatography. It is possible by lithography (GS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like.
When the resin composition contains components such as additives described later that can be eluted into the solvent in the extraction step described above, liquid phase chromatography or the like can be used to separate the components by utilizing differences in molecular weight and polarity. It can be identified by the aforementioned NMR, IR, GS, TOF-SIMS, and the like.

As an analysis method that does not use a solvent, from the infrared absorption spectrum obtained by atomic force microscope (AFM) observation, unreacted modified conjugated diene polymer (component (II)), unreacted epoxy group It is also possible to specify the constituent units of the elastomer (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.
A test piece to be subjected to AFM measurement includes a precise cross section of a resin composition prepared with an ultramicrotome or the like.

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

Content ratio of the resin having a polar group (component (I)), the modified conjugated diene-based polymer (component (II)), and the elastomer having an epoxy group (component (III)) in the resin composition of the present embodiment uses electron microscopes such as the aforementioned AFM, TEM, and SEM to determine the modified conjugated diene-based polymer (component (II)) in the resin (component (I)) having a polar group, and the epoxy group The dispersed state of the elastomer (component (III)) is observed, and the obtained image is binarized or ternarized for each layer using image analysis software or the like to obtain a resin having a polar group (component (I )), the content ratio of the modified conjugated diene polymer (component (II)) and the epoxy group-containing elastomer (component (III)) can be calculated.
Further, the content ratio of the modified conjugated diene polymer (component (II)) and the epoxy group-containing elastomer (component (III)) was determined from the infrared absorption spectrum obtained by the AFM observation described above. The peak intensity of the skeleton (specifically, the vinyl aromatic monomer unit skeleton) possessed only by the polymer (component (II)), and the modified conjugated diene-based polymer described above are isolated and analyzed by NMR, IR, GS, and It can be calculated from the quantitative ratio of vinyl aromatic monomer units and conjugated diene monomer units in the modified conjugated diene polymer calculated by TOF-SIMS or the like.

The molded article of the present embodiment can have any shape depending on the application. Examples include various containers, cylindrical containers, and housings.
Specifically, protection and support members for box-shaped electrical and electronic component integrated modules, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, and 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 crystals, FDD carriages, FDD chassis, Electrical and electronic parts such as motor brush holders, parabolic antennas, and computer-related parts.
In addition, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio equipment, laser discs (registered trademark) and compact discs, lighting parts, refrigerator parts, air conditioner parts, Typewriter parts, word processor parts, and home and office electric product parts such as hot water heaters, bath water volume, temperature sensors, and other plumbing equipment parts.
Furthermore, machine-related parts such as office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, writers, typewriters, etc. can be mentioned.
Furthermore, optical instruments such as microscopes, binoculars, cameras, watches, etc., and parts related to precision machinery are also included.
In addition, alternator terminal, alternator connector, IC regulator, potentiometer base for light gear, relay block, inhibitor switch, various valves such as exhaust gas valves, fuel related / exhaust system / intake system various pipes, air intake nozzle snorkel, Intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pads Abrasion sensors, thermostat bases for air conditioners, heating hot air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, dust tributors, starter switches, ignition coils and their bobbins, motor insulators, motors Rotors, motor cores, starter relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors , lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device cases.
Applications of the molded article of the present embodiment are not limited to the applications described above.

Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present invention is in no way limited by the following examples and comparative examples.
The structure of the modified conjugated diene polymer and the measurement and evaluation methods of the physical properties of the resin composition in Examples and Comparative Examples are shown below.

[Structure of modified conjugated diene polymer and measurement and evaluation of physical properties of resin composition]
((1) Amount of vinyl bond before hydrogenation of modified conjugated diene polymer)
The amount of vinyl bonds in the modified conjugated diene-based polymer was measured using a polymer sampled during the polymerization of the polymer block containing the conjugated diene monomer at each step of the polymerization process of the modified conjugated diene polymer before hydrogenation. It was measured by a nuclear magnetic resonance ( ¹ H-NMR) method.
ECS400 (manufactured by JEOL) is used as the measuring instrument, deuterated chloroform is used as the solvent, the sample concentration is 50 mg/mL, the observation frequency is 400 MHz, tetramethylsilane is used as the chemical shift standard, the pulse delay is 2.904 seconds, and the scan is performed. Measurements were performed at a frequency of 64, a pulse width of 45°, and a measurement temperature of 26°C.
The amount of vinyl bonds, after calculating the integral value per 1H of each bonding mode from the integral value of the signal attributed to 1,4-bond and 1,2-bond, 1,4-bond, 1,2-bond was obtained and calculated by the following formula.
Vinyl bond amount = (1,2-bond/(1,4-bond + 1,2-bond))

((2) Hydrogenation rate of unsaturated bond based on conjugated diene monomer unit 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 measurement data processing method were the same as in (1) above.
The hydrogenation rate was calculated by calculating the integral value of the signal derived from the remaining double bond at 4.5 to 5.5 ppm and the signal derived from the hydrogenated conjugated diene, and calculating the ratio.

((3) Amount of butylene (vinyl hydrogenation rate) relative to a total of 100 mol% of 1,2-bonds and 1,4-bonds based on conjugated diene monomer units in the modified conjugated diene-based polymer)
The amount of butylene relative to a total of 100 mol% of the 1,2-bonds and 1,4-bonds based on the conjugated diene compound units of the modified conjugated diene polymer is obtained by using the modified conjugated diene polymer after hydrogenation, and the proton nucleus Measured by magnetic resonance ( ¹ H-NMR).
The measurement conditions and measurement data processing method were the same as in (1) and (2) above.
A signal derived from the total amount of conjugated diene monomer units and an integrated 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 calculation of the ratio used the integrated value of the signal attributed to butylene (hydrogenated 1,2-bond) at 0-2.0 ppm of the spectrum. The amount of butylene with respect to the total 100 mol % of 1,2-bonds and 1,4-bonds based on this conjugated diene monomer unit is the vinyl hydrogenation rate.

((4) Content of vinyl aromatic monomer unit 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) method using a modified conjugated diene polymer.
ECS400 (manufactured by JEOL) is used as the measuring instrument, deuterated chloroform is used as the solvent, the sample concentration is 50 mg/mL, the observation frequency is 400 MHz, tetramethylsilane is used as the chemical shift standard, the pulse delay is 2.904 seconds, and the number of scans is 64. times, a pulse width of 45°, and a measurement temperature of 26°C.
Styrene content was calculated using the integral of the total styrene aromatics signal at 6.2-7.5 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 of the polymerization process of the modified conjugated diene polymer before hydrogenation.

((5) Weight average molecular weight and molecular weight distribution of modified conjugated diene polymer)
The weight average molecular weight and molecular weight distribution of the modified conjugated diene polymer were measured by GPC [device: HLC8220 (manufactured by Tosoh), column: TSKgelSUPER-HZM-N (4.6 mm×30 cm)].
Tetrahydrofuran was used as a solvent.
The weight-average molecular weight was obtained from the peak molecular weight of the chromatogram using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene.
When the chromatogram has a plurality of peaks, the weight average molecular weight was obtained from the molecular weight of each peak and the composition ratio of each peak (determined 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) and number average molecular weight (Mn).

((6) Modification rate of modified conjugated diene polymer)
Applying the characteristic of adsorbing modified components to a GPC column with silica gel as a packing material, the sample solution containing a modified conjugated diene polymer and a low molecular weight internal standard polystyrene was measured in (5) above. Ratio of modified conjugated diene polymer to standard polystyrene and modified conjugate to standard polystyrene in the chromatogram measured by silica column GPC [device: LC-10 (manufactured by Shimadzu Corporation), column: Zorbax (manufactured by DuPont)] The proportions of the diene polymer were compared, the amount of adsorption to the silica column was measured from the difference between them, and this proportion was defined as the modification rate. The modification rate was calculated by the following formula as the ratio (%) of amino groups having a specific structure at the terminal.

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

((7) Glycidyl methacrylate binding amount)
The modified conjugated diene polymer was refluxed in acetone at 60° C. for 1 hour or longer to remove unreacted glycidyl methacrylate. The modified conjugated diene-based polymer after refluxing is dissolved in toluene, hydrochloric acid is added 2 mol times the amount of glycidyl methacrylate added at the time of extrusion reaction, and refluxed at 60 ° C. for 30 minutes or more to convert the epoxy groups of glycidyl methacrylate. Hydrochloric acid was reacted. The unreacted hydrochloric acid is quantified by titrating the toluene solution after this reaction with potassium hydroxide having a factor of 1 ± 0.05, and the amount of glycidyl methacrylate bound to the modified conjugated diene polymer is calculated from the amount of reacted hydrochloric acid. bottom.

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

((9) Toughness of resin composition)
The tensile elongation at break of the resin composition was measured according to ISO527 with a tensile tester [device: TG-5kN (manufactured by MinebeaMitsumi)].
When the thermoplastic resin polyethylene terephthalate or polyphenylene sulfide resin is used as the component (I), the test piece is an ISO-527-2-1A dumbbell molded by an injection molding machine, and the tensile test speed is 50 mm / min. It was measured.
Three or more test pieces were tested for each composition, and the average value was taken as the physical property value.
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 according to JIS K 7111-1. For the test piece, cut both ends of the above-mentioned ISO dumbbell to prepare a strip-shaped test piece with a parallel portion of about 80 mm in length, about 10 mm in width, and about 4 mm in thickness. bottom.
When an epoxy resin, which is a thermosetting resin, was used as the component (I), a test piece specified in JIS K6911 5.20.2 was prepared, the notch shape was A, and the hitting direction was edgewise.
The measurement temperature was normal temperature (23°C) and -30°C. The unit is kJ/m ² .

((11) Workability (fluidity of resin composition))
When polyethylene terephthalate and polyphenylene sulfide resins, which are thermoplastic resins, were used as component (I), the spiral flow length of the resin composition was measured by the following method to evaluate workability.
The longer the spiral flow length, the higher the fluidity and the better the workability.
The resin composition was put into an injection molding machine (mold clamping pressure 18tf, screw system Φ16, SL screw) with the cylinder temperature set to 300 to 320 ° C (hopper side to nozzle side), screw rotation speed 150 rpm, back pressure 2 Mpa, Injection molding was performed into a mold for spiral flow measurement with a spiral width of 5 mm, a spiral thickness of 3 mm, a maximum spiral length of 850 mm, and a stamping width of 10 mm at a weighing completion position of 55 mm at a filling speed of 50 mm/s and an injection pressure of 100 MPa. The cooling time was 20 s, and the spiral flow length (cm) was measured.

((12) Observation of phase structure of resin composition, measurement of number average dispersed particle size of dispersed phase)
The phase structure in the resin composition is obtained by ultrasonically cleaning a test molded body (ISO-527-2-1A) of the resin composition described later in ethanol for about 1 hour, cutting it with an ultramicrotome, and exposing the cross section. and observed. The cutting was performed at −150° C. using a glass knife and a diamond knife to prepare a precise cross section for AFM observation.
The AFM used was made by Bruker, and the probe used was SCANASYST-AIR.
The precision section sample was fixed to a dedicated sample fixing table, the measurement mode was QMN Mode in Air, the resolution was 512 × 256 pixels, the measurement range was 10 × 10 μm, the maximum indentation load was 500 pN, and the scan speed was 1.0 Hz. A modulus mapping was created from the modulus force curve. The elastic modulus mapping was a grayscale image in which high elastic moduli are bright and low elastic moduli are dark, and was output with 512×512 pixels. In addition, 2-point moving average filter processing was performed to remove noise, and a binarized image was created. The Otsu method was used for binarization.
Particle analysis of the binarized image was performed using ImageJ's Analyze Particles, and the fillet diameter was calculated for each particle of the dispersed phase (B).
Three molded bodies of each resin composition 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 (manufactured by Teijin Limited)
Epoxy resin: bisphenol A type EXA-850CRP (manufactured by DIC)

(Component (II))
Component (II) was produced by a method for producing a modified conjugated diene-based polymer, which will be described later.
Modifiers, other components, and hydrogenation catalysts used in the production are shown below.
[denaturant]
The following compounds were used as modifiers for producing the modified conjugated diene polymer.
Maleic anhydride (manufactured by Fuso Chemical Industry Co., Ltd.)
1,3-dimethyl-2-imidazolidinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
Glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Peroxide 25B (manufactured by NOF Corporation)

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

[Hydrogenation catalyst]
A hydrogenation catalyst used for the hydrogenation reaction of a modified conjugated diene polymer was prepared by the following method.
1 L of dried and purified cyclohexane was placed in a reaction vessel purged with nitrogen, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. and 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 reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and the mixture was heated at 70°C for 20 minutes. polymerized.
Next, a cyclohexane solution (concentration: 20% by mass) containing 80 parts by mass of butadiene was added and polymerized at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added and polymerized at 70° C. for 20 minutes.
Next, 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as “DMI”) was added in an equimolar amount to 1 mol of n-butyllithium, and reacted at 70° C. for 10 minutes. Methanol was added after completion of the reaction.
The terminal amine-modified conjugated diene polymer (1-A) obtained as described above has a styrene content of 20% by mass, a weight average molecular weight of 12.2×10 ⁴ , a molecular weight distribution of 1.10, and a vinyl bond content of 44%, and the modification rate was 70% (the number of modifying groups per polymer chain was 0.70).
Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained amine-terminated conjugated diene polymer (1-A) per 100 parts by mass of the terminal amine-modified conjugated diene polymer (1-A). 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, as a stabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate is added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (1-A) to 0. 0.25 parts by mass was added to obtain a terminal amine-modified hydrogenated conjugated diene polymer (1-B). The obtained terminal amine-modified hydrogenated conjugated diene polymer (1-B) had a hydrogenation rate of 73% and a vinyl hydrogenation rate of 96%.
After mixing the terminal amine-modified hydrogenated conjugated diene polymer (1-B) obtained as described above and maleic anhydride, the temperature is set to 150 to 200° C. over the entire length of the extruder and twin-screw extrusion is performed. A terminal carboxyl group-modified conjugated diene-based polymer (1-C) was obtained by supplying to a machine and compounding.
The terminal carboxyl group-modified conjugated diene polymer (1-C) thus obtained was subjected to GPC measurement under the conditions described above, and it was confirmed that the amino groups did not adsorb to the column.
This means that all the amino groups reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modifying groups per polymer chain was 0.70.

<Modified conjugated diene polymer (2)>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and the mixture was heated at 70°C for 20 minutes. polymerized.
Next, a cyclohexane solution (concentration: 20% by mass) containing 80 parts by mass of butadiene was added and polymerized at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added and polymerized at 70° C. for 20 minutes.
Next, 1.1 mol of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as “DMI”) was added to 1 mol of n-butyllithium, and reacted at 70° C. for 15 minutes. . Methanol was added after completion of the reaction.
The terminal amine-modified conjugated diene polymer (2-A) obtained as described above has a styrene content of 20% by mass, a weight average molecular weight of 12.1×10 ⁴ , a molecular weight distribution of 1.10, and a vinyl bond content of 45%, and the modification rate was 80% (the number of modifying groups per polymer chain was 0.80).
Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained amine-terminated conjugated diene polymer (2-A) per 100 parts by mass of the terminal amine-modified conjugated diene polymer (2-A). 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, as a stabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate is added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (2-A) to 0. 25 parts by mass was added to obtain a terminal amine-modified hydrogenated conjugated diene polymer (2-B).
The obtained terminal amine-modified hydrogenated conjugated diene polymer (2-B) had a hydrogenation rate of 74% and a vinyl hydrogenation rate of 96%.
After mixing the terminal amine-modified hydrogenated conjugated diene polymer (2-B) obtained as described above and maleic anhydride, the temperature is set to 150 to 200 ° C. over the entire length of the extruder and twin-screw extrusion is performed. A terminal carboxyl group-modified conjugated diene polymer (2-C) was obtained by supplying to a machine and compounding.
The terminal carboxyl group-modified conjugated diene polymer (2-C) thus obtained was subjected to GPC measurement under the conditions described above, and it was confirmed that the amino groups did not adsorb to the column.
This means that all the amino groups reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modifying groups per polymer chain was 0.80.

<Modified conjugated diene polymer (3)>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and the mixture was heated at 70°C for 20 minutes. polymerized.
Next, a cyclohexane solution (concentration: 20% by mass) containing 70 parts by mass of butadiene was added and polymerized at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added and polymerized at 70° C. for 20 minutes.
Next, 1.1 mol of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as “DMI”) was added to 1 mol of n-butyllithium, and reacted at 70° C. for 15 minutes. . Methanol was added after completion of the reaction.
The terminal amine-modified conjugated diene polymer (3-A) obtained as described above has a styrene content of 30% by mass, a weight average molecular weight of 12.0×10 ⁴ , a molecular weight distribution of 1.09, and a vinyl bond content of 43%, and the modification rate was 79% (the number of modifying groups per polymer chain was 0.79).
Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained amine-terminated conjugated diene polymer (3-A) per 100 parts by mass of the terminal amine-modified conjugated diene polymer (3-A). 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, as a stabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate is added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (3-A) to 0. 0.25 parts by mass was added to obtain a terminal amine-modified hydrogenated conjugated diene polymer (3-B).
The resulting hydrogenated amine-modified hydrogenated conjugated diene polymer (3-B) had a hydrogenation rate of 75% and a vinyl hydrogenation rate of 96%.
After mixing the terminal amine-modified hydrogenated conjugated diene polymer (3-B) obtained as described above and maleic anhydride, the temperature setting over the entire length of the extruder is set to 150 to 200 ° C. and twin-screw extrusion is performed. A terminal carboxyl group-modified conjugated diene polymer (3-C) was obtained by supplying to a machine and compounding.
The terminal carboxyl group-modified conjugated diene polymer (3-C) thus obtained was subjected to GPC measurement under the conditions described above, and it was confirmed that the amino groups did not adsorb to the column.
That is, it means that all amino groups reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modifying groups per polymer chain was 0.79.

<Modified conjugated diene polymer (4)>
Except for adding 0.2 mol of tetramethylethylenediamine (TMEDA) to 1 mol of n-butyllithium, the same operation as in <Modified conjugated diene-based polymer (2)> was performed to obtain a terminal carboxyl group-modified conjugated diene. A system polymer (4-C) was obtained. The obtained terminal carboxyl group-modified conjugated diene copolymer (4-C) had a styrene content of 20% by mass, a weight average molecular weight of 12.2×10 ⁴ , a molecular weight distribution of 1.09, and a vinyl bond content of 24%. The hydrogenation rate was 78%, the vinyl hydrogenation rate was 96%, and the modification rate was 80% (the number of modifying groups per polymer chain was 0.79).

<Modified conjugated diene polymer (5)>
Except for adding 0.09 parts by mass of n-butyl lithium to 100 parts by mass of all the monomers, the same operation as in <Modified conjugated diene-based polymer (2)> was performed to obtain a terminal carboxyl group-modified conjugated diene-based A polymer (5-C) was obtained. The resulting terminal carboxyl group-modified conjugated diene copolymer (5-C) had a styrene content of 20% by mass, a weight average molecular weight of 10.1×10 ⁴ , a molecular weight distribution of 1.10, and a vinyl bond content of 43%. The hydrogenation rate was 78%, the vinyl hydrogenation rate was 96%, and the modification rate was 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 reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 6.5 parts by mass of styrene was added.
Next, 0.11 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and the mixture was heated at 70° C. for 20 minutes. polymerized.
Next, a cyclohexane solution (concentration: 20% by mass) containing 87 parts by mass of butadiene was added and polymerized at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 6.5 parts by mass of styrene was added and polymerized at 70° C. for 20 minutes.
Next, 1.1 mol of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as “DMI”) was added to 1 mol of n-butyllithium, and reacted at 70° C. for 15 minutes. . Methanol was added after completion of the reaction.
The terminal amine-modified conjugated diene polymer (6-A) obtained as described above has a styrene content of 13% by mass, a weight average molecular weight of 12.2×10 ⁴ , a molecular weight distribution of 1.09, and a vinyl bond content of 35%, and the modification rate was 81% (the number of modifying groups per polymer chain was 0.81).
Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained amine-terminated conjugated diene polymer (6-A) per 100 parts by mass of the terminal amine-modified conjugated diene polymer (6-A). The 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, as a stabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate is added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (6-A) to 0. 0.25 parts by mass was added to obtain a terminal amine-modified hydrogenated conjugated diene polymer (6-B).
The obtained terminal amine-modified hydrogenated conjugated diene polymer (6-B) had a hydrogenation rate of 80% and a vinyl hydrogenation rate of 98%.
After mixing the terminal amine-modified hydrogenated conjugated diene polymer (6-B) obtained as described above and maleic anhydride, the temperature is set to 150 to 200 ° C. over the entire length of the extruder and twin-screw extrusion is performed. A terminal carboxyl group-modified conjugated diene polymer (6-C) was obtained by supplying to a machine and compounding.
The terminal carboxyl group-modified conjugated diene polymer (6-C) thus obtained was subjected to GPC measurement under the conditions described above, and it was confirmed that the amino groups did not adsorb to the column.
This means that all the amino groups reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modifying groups per polymer chain was 0.81.

<Modified conjugated diene polymer (7)>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 25 parts by mass of styrene was added.
Next, 0.11 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.4 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and the mixture was heated at 70°C for 20 minutes. polymerized.
Next, a cyclohexane solution (concentration of 20% by mass) containing 50 parts by mass of butadiene was added and polymerized at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 25 parts by mass of styrene was added and polymerized at 70° C. for 20 minutes.
Next, 1.1 mol of 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as “DMI”) was added to 1 mol of n-butyllithium, and reacted at 70° C. for 15 minutes. . Methanol was added after completion of the reaction.
The terminal amine-modified conjugated diene polymer (7-A) obtained as described above has a styrene content of 50% by mass, a weight average molecular weight of 11.9×10 ⁴ , a molecular weight distribution of 1.11, and a vinyl bond content of 43%, and the modification rate was 79% (the number of modifying groups per polymer chain was 0.79).
Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained amine-terminated conjugated diene polymer (7-A) per 100 parts by mass of the terminal amine-modified conjugated diene polymer (7-A). 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, as a stabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate is added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (7-A) to 0. 25 parts by mass was added to obtain a terminal amine-modified hydrogenated conjugated diene polymer (7-B).
The resulting hydrogenated amine-modified hydrogenated conjugated diene polymer (7-B) had a hydrogenation rate of 77% and a vinyl hydrogenation rate of 97%.
After mixing the terminal amine-modified hydrogenated conjugated diene polymer (7-B) obtained as described above and maleic anhydride, the temperature is set to 150 to 200° C. over the entire length of the extruder and twin-screw extrusion is performed. A terminal carboxyl group-modified conjugated diene polymer (7-C) was obtained by supplying to a machine and compounding.
The terminal carboxyl group-modified conjugated diene polymer (7-C) thus obtained was subjected to GPC measurement under the conditions described above, and it was confirmed that no adsorption of amino groups to the column occurred.
That is, it means that all amino groups reacted with maleic anhydride, the amount of carboxyl groups was the same as that of amino groups, and the number of modifying groups per polymer chain was 0.79.

<Modified conjugated diene polymer (8)>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added.
Next, 0.11 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and the mixture was heated at 70° C. for 20 minutes. polymerized.
Next, a cyclohexane solution (concentration: 20% by mass) containing 80 parts by mass of butadiene was added and polymerized at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added and polymerized at 70° C. for 20 minutes.
Methanol was then added.
The conjugated diene polymer (8-A) obtained as described above has a styrene content of 30% by mass, a weight average molecular weight of 12.1×10 ⁴ , a molecular weight distribution of 1.10, and a vinyl bond content of 36%. there were.
Furthermore, to the obtained conjugated diene polymer (8-A), the hydrogenation catalyst prepared as described above is added at 70 ppm based on Ti based on 100 parts by mass of the conjugated diene polymer (8-A), 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, as a stabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate is added in an amount of 0.25 parts by mass with respect to 100 parts by mass of the conjugated diene polymer (8-A). to obtain a hydrogenated conjugated diene polymer (8-B).
The obtained hydrogenated conjugated diene polymer (8-B) had a hydrogenation rate of 97% and a vinyl hydrogenation rate of 99%.
After mixing the hydrogenated conjugated diene polymer (8-B) obtained as described above and glycidyl methacrylate, the mixture was supplied to a twin-screw extruder at a temperature setting of 150 to 220° C. over the entire length of the extruder. , and Peroxide 25B were added from the middle stage of the extruder and compounded to obtain a main chain epoxy-modified conjugated diene polymer (8-C).
The resulting main chain epoxy group-modified conjugated diene polymer (8-C) was titrated by the method described above to find that the amount of glycidyl methacrylate bond was 1.2% by mass.

<Modified conjugated diene polymer (9)>
Batch polymerization was carried out using a tank reactor (inner volume 10 L) equipped with a stirrer and jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added.
Next, 0.11 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and the mixture was heated at 70° C. for 20 minutes. polymerized.
Next, a cyclohexane solution (concentration: 20% by mass) containing 70 parts by mass of butadiene was added and polymerized at 70° C. for 45 minutes.
Next, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added and polymerized at 70° C. for 20 minutes.
Methanol was then added.
The conjugated diene polymer (9-A) obtained as described above has a styrene content of 30% by mass, a weight average molecular weight of 12.2×10 ⁴ , a molecular weight distribution of 1.08, and a vinyl bond content of 37%. there were.
Furthermore, to the obtained conjugated diene polymer (9-A), the hydrogenation catalyst prepared as described above is added at 50 ppm on a Ti basis per 100 parts by mass of the conjugated diene polymer (9-A), 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, as a stabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate is added in an amount of 0.25 parts by mass with respect to 100 parts by mass of the conjugated diene polymer (9-A). to obtain a hydrogenated conjugated diene polymer (9-B).
The obtained hydrogenated conjugated diene polymer (9-B) had a hydrogenation rate of 76% and a vinyl hydrogenation rate of 96%.
After mixing the hydrogenated conjugated diene polymer (9-B) obtained as described above, maleic anhydride, and organic peroxide (Perhexa 25B (manufactured by NOF Corporation)), the length of the extruder The mixture was supplied to a twin-screw extruder with the temperature set to 150 to 220° C. over the entire temperature range 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) Maleic anhydride bond amount), and the maleic anhydride bond amount was 1. 0.5 mass %.

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

(Component (III): a polymer having a polar group reactive with components (I) and (II))
As component (III), the following polymers having epoxy groups were 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 ^TM PTW (ethylene-glycidyl methacrylate-butyl acrylate copolymer, manufactured by Dow)

[Examples 1 to 15]
Using the above components, the composition ratios shown in Tables 1 and 2 were melted 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. The mixture was kneaded to produce a resin composition.
Thereafter, using an injection molding machine, injection molding was performed with a cylinder temperature setting of 300° C. and a mold temperature setting of 140° C. to prepare a test piece (ISO-527-2-1A).

[Comparative Examples 1 to 11]
Modified conjugated diene polymers (1-B) and (1-C) were used as component (II).
Other materials and conditions were the same as in Examples 1 to 15, resin compositions were produced at the composition ratios shown in Table 3, and test pieces were produced.

Tables 1 to 3 show the number average dispersed particle size, toughness and impact resistance of the dispersed phase (B) of each resin composition.
In the table, "(1)" indicates that the test piece for the Charpy impact test was unbroken.

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

[Comparative Examples 12 to 15]
A modified conjugated diene polymer (9-B) was used as component (II).
Other materials and conditions were the same as in Examples 16 to 22, resin compositions were produced according to the composition ratios shown in Table 5, and test pieces were produced.

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

[Examples 23 to 27]
Using the components described above, a resin composition was produced in the composition ratio shown in Table 6.
When component (II) and component (III) are included, component (III) is dissolved in toluene at a concentration of about 20% by mass, added to the epoxy resin solution, and stirred.
It was then vacuum dried at room temperature to remove most of the toluene. Next, a curing agent was added and stirred to obtain a solution-like resin composition.
Next, after heating the solution-like resin composition to 80 ° C., the solution-like resin composition was injected into a mold having a shape specified in the toughness test and the Charpy impact test described above, and heated at 140 ° C. for 2 hours. A cured product of the resin composition was obtained by time compression molding.
Table 6 shows the number average dispersed particle diameter, toughness and impact resistance of the dispersed phase (B) of each resin composition.

[Comparative Examples 16 to 21]
A modified conjugated diene polymer (9-B) was used as component (II).
Other materials and conditions were the same as in Examples 23 to 27, resin compositions were produced according to the composition ratios shown in Table 7, and test pieces were produced.

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

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

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

The resin composition of the present invention can be used in sheets, films, injection-molded articles of various shapes, blow-molded articles, pressure-molded articles, vacuum-molded articles, extrusion-molded articles, foam-molded articles, non-woven fabrics, fibrous molded articles, synthetic leather, and the like. It can be used as a wide variety of molded products, and these molded products are automotive interior and exterior materials, building materials, toys, home appliance parts, medical equipment, industrial parts, various hoses, various housings, various module cases, and various power control unit parts. , and other miscellaneous goods, and have industrial applicability.

Claims

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 two polymer blocks selected from polymer blocks (B) mainly composed of conjugated diene monomer units and random polymer blocks (C) composed of vinyl aromatic monomer units and conjugated diene monomer units to a block polymer having
at least one modified conjugated diene-based polymer to 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;
A resin composition containing
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 dispersed phase (B) has a number average dispersed particle size of 1.5 μm or less,
A resin composition wherein the mass ratio of component (I) to component (II) is component (I):component (II)=50/50 to 99/1.
Component (III): further comprising a polymer having a polar group reactive with component (I) and/or component (II) (excluding components (I) and (II)),
The mass ratio of the component (II) and the component (III) is component (II):component (III) = 1/99 to 99/1,
The resin composition according to claim 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 (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 2.
The component (II) contains a hydrogenated modified conjugated diene-based polymer in which an aliphatic double bond derived from a conjugated diene compound is hydrogenated,
The resin composition according to claim 3 or 4.
The component (I) is a polyphenylene sulfide resin,
The resin composition according to claim 3 or 4.
The component (II) contains a modified conjugated diene-based polymer to which at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups is bonded,
The resin composition according to claim 3 or 4.
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 2 or 3.
wherein the component (III) is an olefin elastomer having an epoxy group;
The resin composition according to claim 2 or 3.
The hydrogenation rate of the hydrogenated modified conjugated diene polymer is 90% or less,
The resin composition according to claim 5.
The content of vinyl aromatic monomer units in the component (II) is 40% by mass or less.
The resin composition according to claim 3 or 4.
The component (III) is an epoxy group-containing elastomer comprising a copolymer of an epoxy group-containing polymerizable monomer and an unsaturated hydrocarbon compound.
The resin composition according to claim 2 or 3.
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 2 or 3.
a polymer block (A) mainly composed of vinyl aromatic monomer units,
At least two polymer blocks selected from polymer blocks (B) mainly composed of conjugated diene monomer units and random polymer blocks (C) composed of vinyl aromatic monomer units and conjugated diene monomer units has
a modified conjugated diene-based polymer (component (II)) having at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups;
a resin (component (I)) having at least one polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins;
an olefinic elastomer (component (III)) having at least one polar group selected from the group consisting of epoxy groups, oxazoline groups, and oxetanyl groups;
of,
The mass ratio of the resin having a polar group (component (I)) and the modified conjugated diene-based polymer (component (II)) is adjusted to the resin having a polar group: modified conjugated diene-based polymer = 50/50 ~ 99/1,
The mass ratio of the modified conjugated diene-based polymer and the olefin-based elastomer having a polar group is kneaded so that the modified conjugated diene-based polymer: olefin-based elastomer having a polar group = 1/99 to 99/1. obtaining a composition;
The resin composition comprises a continuous phase (A) of the resin having a polar group (component (I)) and the modified conjugated diene polymer (component (II)) dispersed in the continuous phase (A).
A dispersed phase (B) containing
A method for producing a resin composition.
at least one resin having a polar group (component (I)) selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins;
Polymer block (A) mainly composed of vinyl aromatic monomer units, polymer block (B) mainly composed of conjugated diene monomer units, vinyl aromatic monomer units and conjugated diene monomer units a modified conjugated diene-based polymer (component (II)) having at least two polymer blocks selected from random polymer blocks (C);
an olefin-based elastomer having an epoxy group (component (III));
including,
A molded body of a resin composition,
The modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups,
A molded body, wherein the molded body satisfies the following conditions (I-1) to (II-1).
<Condition (I-1)>
A strip-shaped test piece having a width of 10 mm, a length of 170 mm, and a thickness of 2 mm obtained from the compact has a tensile elongation at break of 25% or more at room temperature and a tensile speed of 5 mm/min.
<Condition (II-1)
A strip-shaped 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 compact has a Charpy impact value of 15 kJ/m 2 in a Charpy impact test at -30°C.