CN117545808A - A resin composition method for producing resin composition and molded article - Google Patents

A resin composition method for producing resin composition and molded article Download PDF

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CN117545808A
CN117545808A CN202280044175.5A CN202280044175A CN117545808A CN 117545808 A CN117545808 A CN 117545808A CN 202280044175 A CN202280044175 A CN 202280044175A CN 117545808 A CN117545808 A CN 117545808A
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component
group
conjugated diene
polymer
resin composition
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松冈裕太
助川敬
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Asahi Kasei Corp
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Asahi Kasei Corp
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Priority claimed from PCT/JP2022/028771 external-priority patent/WO2023008424A1/en
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Abstract

The present invention relates to a resin composition comprising a component (I) and at least one component (II), wherein the component (I) is a resin having a polar group (excluding the component (II)), the component (II) is a modified conjugated diene polymer having at least 2 polymer blocks selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an epoxy group, an oxetanyl group and an amino group bonded to a polymer block (A) having a vinyl aromatic monomer unit as a main component, a polymer block (B) having a conjugated diene monomer unit as a main component, and a random polymer block (C) having a vinyl aromatic monomer unit and a conjugated diene monomer unit, the composition comprises a continuous phase (A) of a component (I), and a dispersed phase (B) containing a component (II) dispersed in the continuous phase (A), wherein the dispersed phase (B) has a number average dispersed particle diameter of 1.5 [ mu ] m or less, and the component (I): mass of component (II) ratio=50/50 to 99/1.

Description

Resin composition a material (C) method for producing resin composition and molded article
Technical Field
The present invention relates to a resin composition, a method for producing the resin composition, and a molded article.
Background
It is known that conjugated diene polymers exhibit various properties by adjusting the ratio of 1, 2-bonds, the ratio of blocks constituting the conjugated diene polymer, the arrangement of the blocks, the degree of hydrogenation, and the like. In order to further impart the properties, a conjugated diene polymer (hereinafter referred to as a modified conjugated diene polymer) having an affinity group capable of generating intermolecular force with other materials or a reactive group capable of forming a chemical bond has been proposed.
For example, patent document 1 proposes an amino-modified conjugated diene polymer obtained by reacting an amino-containing compound with a terminal end of a conjugated diene polymer.
On the other hand, resins having polar groups (hereinafter, sometimes referred to as polar resins) are generally excellent in rigidity, chemical resistance, heat resistance, etc., but are hard and brittle, and thus various modifiers have been studied conventionally. The modified conjugated diene polymer is excellent in compatibility with a polar resin by a reaction based on a modifying group or intermolecular force such as hydrogen bond, and therefore is widely used as a modifier for a polar resin.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2014-210848
Disclosure of Invention
Problems to be solved by the invention
In recent years, with the popularization of high performance and IoT in automobiles, home appliances, communication equipment, and the like, there has been an increasing demand for polar resins excellent in heat resistance, chemical resistance, flame retardancy, mechanical strength, dimensional stability, electrical insulation, and dielectric characteristics in the process of advancing weight reduction and electrical packaging of each component.
On the other hand, in electronic materials, materials resistant to impact at the time of manufacture and use are being sought, and in automobile parts, safety awareness is increasing, and therefore there is a problem that it is required to improve impact resistance and toughness of hard and brittle polar resins.
For example, patent document 1 relates to improvement of toughness of polyphenylene sulfide resin (hereinafter sometimes referred to as "PPS"), and a resin composition blended with a modified conjugated diene polymer having toughness superior to PPS is proposed.
However, according to the studies of the present inventors, the resin composition disclosed in patent document 1 has a problem that toughness is still insufficient and there is room for improvement.
In view of the above problems of the prior art, an object of the present invention is to provide a resin composition having excellent impact resistance and toughness.
Means for solving the problems
The present inventors have conducted intensive studies to solve the problems of the prior art, and as a result, have found that the problems of the prior art can be solved by providing a dispersion phase (B) containing a modified conjugated diene polymer having a predetermined number average dispersion particle diameter and providing a resin having a polar group (component (I)) and a modified conjugated diene polymer having a predetermined mass ratio in a resin composition containing a resin having a polar group (component (I)) and a modified conjugated diene polymer having a predetermined polar group (component (II)), and have completed the present invention.
Namely, the present invention is as follows.
[1]
A resin composition comprising component (I) and at least one component (II),
component (I): a resin having a polar group (excluding the following component (II));
component (II): a modified conjugated diene polymer obtained by bonding at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an epoxy group, an oxetanyl group and an amino group to a block polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (A) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
Wherein,
the resin composition comprises a continuous phase (A) of the component (I) and a dispersed phase (B) containing the component (II) dispersed in the continuous phase (A), wherein the number average dispersion particle diameter of the dispersed phase (B) is 1.5 [ mu ] m or less,
the mass ratio of the component (I) to the component (II) is the component (I): component (II) =50/50 to 99/1.
[2]
The resin composition as described in the above [1], which further comprises the component (III): polymers having polar groups reactive with the above-mentioned component (I) and/or component (II) (excluding the above-mentioned components (I), (II)),
the mass ratio of the component (II) to the component (III) is the component (II): component (III) =1/99 to 99/1.
[3]
The resin composition according to the above [1], wherein the component (I) contains 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.
[4]
The resin composition according to the above [2], wherein the component (I) contains 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.
[5]
The resin composition according to any one of the above [1] to [4], wherein the component (II) comprises a hydrogenated modified conjugated diene polymer obtained by hydrogenating an aliphatic double bond derived from a conjugated diene compound.
[6]
The resin composition according to any one of the above [1] to [5], wherein the component (I) is a polyphenylene sulfide resin.
[7]
The resin composition according to any one of the above [1] to [6], wherein the component (II) comprises a modified conjugated diene polymer to which at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group is bonded.
[8]
The resin composition according to any one of [2] to [7], wherein 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 oxetane group.
[9]
The resin composition according to any one of the above [2] to [8], wherein the component (III) is an olefin elastomer having an epoxy group.
[10]
The resin composition according to any one of the above [5] to [9], wherein the hydrogenation rate of the hydrogenated modified conjugated diene polymer is 90% or less.
[11]
The resin composition according to any one of [1] to [10], wherein the content of the vinyl aromatic monomer unit in the component (II) is 40% by mass or less.
[12]
The resin composition according to any one of [2] to [11], wherein the component (III) is an elastomer having an epoxy group composed of a copolymer of a polymerizable monomer having an epoxy group and an unsaturated hydrocarbon compound.
[13]
The resin composition according to any one of the above [2] to [12], wherein the component (III) is a copolymer of a polymerizable monomer having an epoxy group and an unsaturated hydrocarbon compound and (meth) acrylate and/or vinyl acetate.
[14]
A method for producing a resin composition, wherein,
comprises a step of kneading a component (II), a component (I) and a component (III) to obtain a resin composition,
the component (II) is a modified conjugated diene polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a random polymer block (C) mainly composed of vinyl aromatic monomer units and conjugated diene monomer units, and having at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups,
the component (I) is at least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins and polybutylene terephthalate-based resins,
The component (III) is an olefin elastomer having at least one polar group selected from the group consisting of an epoxy group, an oxazoline group and an oxetane group,
the mass ratio of the polar-group-containing resin (component (I)) to the modified conjugated diene polymer (component (II)) is set to be a polar-group-containing resin: modified conjugated diene polymer=50/50 to 99/1,
the mass ratio of the modified conjugated diene polymer to the polar-group-containing olefin elastomer is set to be the modified conjugated diene polymer: olefin elastomer having polar group=1/99 to 99/1,
the production method comprises a step of providing the resin composition with a continuous phase (A) of the resin having a polar group (component (I)), and a dispersed phase (B) containing the modified conjugated diene polymer (component (II)) dispersed in the continuous phase (A), wherein the number average dispersion particle diameter of the dispersed phase (B) is 1.5 [ mu ] m or less.
[15]
A molded article comprising a resin composition containing component (I), component (II) and component (III),
the component (I) is at least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins,
The component (II) is a modified conjugated diene polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, a random polymer block (C) mainly composed of vinyl aromatic monomer units and conjugated diene monomer units,
the component (III) is an olefin elastomer having an epoxy group,
wherein,
the modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group,
the molded article satisfies the following conditions (I-1) to (II-1).
< condition (I-1) >
A long test piece having a width of 10mm, a length of 170mm, and a thickness of 2mm, which was obtained from the molded article, had a tensile elongation at break of 25% or more at room temperature under a tensile speed of 5 mm/min.
< conditions (II-1)
A long test piece having a length of about 80mm, a width of about 10mm, and a thickness of about 4mm obtained from the molded article has a Charpy impact value of 15kJ/m in a Charpy impact test at a temperature of-30 DEG C 2 。
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a resin composition excellent in impact resistance and toughness can be provided.
Detailed Description
Hereinafter, a specific embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail.
The following embodiments are examples for illustrating the present invention, and are not intended to limit the present invention to the following. The present invention can be suitably modified and implemented within the scope of the gist thereof.
[ resin composition ]
The resin composition of the present embodiment is a resin composition comprising the component (I) and at least one component (II),
component (I): a resin having a polar group (excluding the following component (II));
component (II): a modified conjugated diene polymer obtained by bonding at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an epoxy group, an oxetanyl group and an amino group to a block polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (A) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit.
The resin composition comprises a continuous phase (A) of the component (I) and a dispersed phase (B) containing the component (II) dispersed in the continuous phase (A), wherein the number average dispersion particle diameter of the dispersed phase (B) is 1.5 [ mu ] m or less.
The mass ratio of the component (I) to the component (II) is the component (I): component (II) =50/50 to 99/1.
With the above constitution, a resin composition excellent in impact resistance and toughness can be obtained.
( Component (I): resin having polar group (excluding the following component (II)) )
The resin composition of the present embodiment contains a resin having a polar group (hereinafter, may be referred to as a polar resin (I) or a component (I)).
In general, resins having excellent rigidity have polar groups in the main chain from the viewpoint of entropy and enthalpy.
The polar resin (I) used in the resin composition of the present embodiment includes, but is not limited to, for example: acrylonitrile-butadiene-styrene copolymer resin (ABS); methacrylate-butadiene-styrene copolymer resin (MBS); polyvinyl chloride resin; polyvinyl acetate resin and its hydrolyzate; polymers of acrylic acid and esters or amides thereof; a polyacrylate resin; a polymer of acrylonitrile and/or methacrylonitrile, a nitrile resin containing 50 mass% or more of these acrylonitrile-based monomers as a copolymer with other copolymerizable monomers; a polyamide resin; polycarbonate polymers such as polyester resins, thermoplastic polyurethane resins, and poly-4, 4 '-dioxydiphenyl-2, 2' -propane carbonate; thermoplastic polysulfones such as polyether sulfone and polyallyl sulfone; a polyoxymethylene resin; polyphenylene ether resins such as poly (2, 6-dimethyl-1, 4-phenylene) ether; polyphenylene sulfide resin; polyarylate-based resins; polyether ketone polymers or copolymers; polyketone-based resins; a fluorine-based resin; polyethylene terephthalate resin; a polyoxybenzoyl polymer and a polyimide resin; polyethylene terephthalate resin; polybutylene terephthalate-based resin; an epoxy resin; etc.
The polar resin (I) is preferably selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, epoxy resin and polyphenylene sulfide resin, which are different depending on the characteristics required for the resin composition of the present embodiment, from the viewpoint of rigidity, from the viewpoint of chemical resistance, and from the viewpoint of heat resistance, from the viewpoint of heat resistance.
The polyethylene terephthalate resin may be any resin that falls into the category of a so-called polyethylene terephthalate resin, and more preferably is a thermoplastic resin obtained by polymerization of at least 90 mol% or more of a glycol component that is ethylene glycol and at least 90 mol% or more of a dicarboxylic acid component that is terephthalic acid.
The polybutylene terephthalate-series resin may be a polymer obtained by a usual polymerization method such as a polycondensation reaction of a dicarboxylic acid containing terephthalic acid or a derivative thereof as a main component and a diol containing 1, 4-butanediol or a derivative thereof as a main component, and the repeating unit of the polybutylene terephthalate is preferably 90 mol% or more, more preferably 95 mol% or more.
The epoxy resin may be one which falls within the category called epoxy resins, and from the viewpoint of rigidity, it is preferable that the epoxy resin has 2 or more epoxy groups in 1 molecule. The epoxy resin may be used alone or in combination of two or more.
Examples of the epoxy resin include, but are not limited to, a xylenol-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisphenol AF-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol novolac-type epoxy resin, a tert-butyl-catechol-type epoxy resin, a naphthalene-type epoxy resin, a naphthol-type epoxy resin, an anthracene-type epoxy resin, a glycidylamine-type epoxy resin, a glycidyl ester-type epoxy resin, a cresol novolac-type epoxy resin, a biphenyl-type epoxy resin, an alicyclic epoxy resin, a heterocyclic-type epoxy resin, a spiro-containing epoxy resin, a cyclohexane-type epoxy resin, a cyclohexanedimethanol-type epoxy resin, a naphthylene ether-type epoxy resin, a trimethylol-type epoxy resin, and a tetraphenylethane-type epoxy resin.
The polyphenylene sulfide resin may be one which falls into the category called polyphenylene sulfide resins, and from the viewpoint of heat resistance, it preferably contains 70 mol% or more of a p-phenylene sulfide unit, more preferably 90 mol% or more of a p-phenylene sulfide unit.
The other structural unit may contain, for example, an o-phenylene sulfide unit, an m-phenylene sulfide unit, a phenylene sulfide ether unit, a phenylene sulfide sulfone unit, a phenylene sulfide ketone unit, a diphenyl sulfide unit, a substituent-containing phenylene sulfide unit, a branching-structure-containing phenylene sulfide unit, or the like.
The molecular weight of the polyphenylene sulfide resin is preferably 5000 or more, more preferably 10000 or more, from the viewpoint of rigidity of the resin composition of the present embodiment.
The polyphenylene sulfide resin may be linear or may have a crosslinked or branched structure.
In addition, the polymer structure of the polyphenylene sulfide resin may have a polar group such as a mercapto group or a carboxyl group at the terminal or main chain.
The method for producing the polyphenylene sulfide resin is not particularly limited, and examples thereof include a method in which an alkali metal sulfide and a dihalo-aromatic compound are reacted in a polymerization solvent.
Component (II) modified conjugated diene polymer
The resin composition of the present embodiment contains at least one modified conjugated diene polymer (hereinafter, sometimes referred to as modified conjugated diene polymer (II), component (II)) which is a modified conjugated diene polymer formed by bonding at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an epoxy group, an oxetanyl group and an amino group to a block polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (a) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit.
The modified conjugated diene polymer (II) has affinity and/or reactivity for the polar resin (I) by having the polar group, and thus can improve the toughness and impact resistance of the resin composition of the present embodiment.
The affinity means that at least one intermolecular force selected from the group consisting of ionic interactions, hydrogen bonds, dipole interactions, and van der Waals forces can be generated between the components.
The above-mentioned reactivity means that the polar groups of the respective components have covalent bonding property with each other. When polar groups react with each other, for example, if OH of a carboxyl group is detached, the original polar groups may change or disappear, but in the case where covalent bonds are thereby formed, it is included in the definition that polar groups show "reactivity" with each other.
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 dicarboxylic group, an oxazoline group, an epoxy group, an oxetanyl group, and an amino group, and is excellent in affinity and/or reactivity with the polar resin (I), whereby the compatibility between the polar resin (component (I)) and the modified conjugated diene polymer (component (II)) is improved, and the number average dispersion particle diameter of the dispersed phase (B) of component (II) in the continuous layer (a) of component (I) can be 1.5 μm or less, and the interface between the components can be reinforced, thereby contributing to improvement in impact resistance and toughness.
The preferable polar group of the modified conjugated diene polymer (II) may also vary depending on the type of the polar resin (I) and the characteristics required for the resin composition of the present embodiment. For example, when the polar resin (I) is a polyphenylene sulfide resin, the polar group of the modified conjugated diene polymer (II) is preferably one having excellent affinity and/or reactivity with a mercapto group, a carboxyl group, or an amino group present at the terminal of the polyphenylene sulfide resin. In addition, when the component (I) is an epoxy resin, the carboxyl group, the acid anhydride group, the hydroxyl group, and the dicarboxylic group are excellent in affinity and/or reactivity with the epoxy group of the component (I). By providing each of the components (I) and (II) with an affinity group and/or a reactive group that exhibits affinity and/or reactivity between the components, the interface between the components can be reinforced, which contributes to improvement in toughness and impact resistance of the resin composition of the present embodiment. Further, it is also expected to improve the tracking resistance and to suppress the deterioration of physical properties (thermal cycle characteristics) when exposed alternately to high to low temperatures. These characteristics can be improved by controlling the compatibility state by adjusting the affinity and reactivity between the components.
For example, when the polar resin of the component (I) is a polyethylene terephthalate resin or a polybutylene terephthalate resin, the epoxy group or amino group of the component (II) has excellent affinity and/or reactivity with the carboxyl group present at the terminal of the polyethylene terephthalate resin or polybutylene terephthalate resin, and therefore, the interface between the components can be reinforced by providing each component with an affinity group and/or a reactive group that exhibits affinity and/or reactivity between the components, which contributes to improvement in toughness and impact resistance of the resin composition.
As the component (II), 2 kinds of modified conjugated diene polymers each having a different polar group from the polar group species may be used. In terms of the compatibility, when 2 modified conjugated diene polymers (II) each having a different polar group bonded thereto are used, it is preferable that 1 modified conjugated diene polymer has a polar group reactive with the other modified conjugated diene polymer and the polar resin (I) bonded thereto.
For example, when the polar resin of the component (I) is a polyphenylene sulfide resin, a polyethylene terephthalate resin, or a polybutylene terephthalate resin, the component (II) may preferably be a modified conjugated diene polymer having an epoxy group bonded thereto or a modified conjugated diene polymer having a carboxyl group and/or a hydroxyl group bonded thereto.
In addition, for example, in the case where the polar resin of the component (I) is an epoxy resin, since the affinity and/or reactivity of the carboxyl group, the hydroxyl group, the amino group and the epoxy group of the epoxy resin are excellent, the modified conjugated diene polymer having the polar group can be preferably used as the component (II). By providing each component with an affinity group and/or a reactive group that exhibits affinity and/or reactivity between components in this manner, the interface between components can be reinforced, which contributes to the improvement in toughness and impact resistance of the resin composition of the present embodiment.
In general, the resin composition has a tendency that the same components aggregate to form a phase, but in the resin composition of the present embodiment, the component (II) has a polar group, and thus affinity and/or reactivity with the component (I) are improved, and compatibility of these components is improved, so that the number average dispersion particle diameter of the dispersed phase (B) to be described later is 1.5 μm or less, which contributes to the expression of impact resistance and toughness of the resin composition of the present embodiment.
The amount of the polar group in the modified conjugated diene polymer (II) is preferably 0.3m omicron/chain or more, more preferably 0.5m omicron/chain or more, and still more preferably 0.6m omicron/chain or more, from the viewpoint of compatibility with the polar resin (I).
When the amount of the polar group in the modified conjugated diene polymer (II) is 0.3m omicron l/chain or more, the polymer chain having an affinity group or a reactive group is compatible with the component (I), and the polymer chain obtained by the compatibility of the polymer chain having no affinity group or a reactive group with the component (I) is aggregated as described above, whereby the number average dispersion particle diameter of the dispersed phase (B) can be 1.5 μm or less, preferably 1.3 μm or less.
As long as the polar groups contained in the component (I) and the component (II) respectively have a desired affinity and/or reactivity, such compatibility and aggregation easiness have a greater influence on the frequency (amount) of the polar groups in the polymer chain than the structure of the resin, the kind of the polar groups, and the combination of the polar groups between the components. Accordingly, by appropriately setting the amount of the polar group of the component (II), the number average particle diameter of the dispersed phase (B) can be controlled to a desired value.
In addition, if the affinity group or the reactive group of the component (II) is excessive, gelation or the like may occur in the resin composition of the present embodiment, and thus it is preferably 30m omicron l/chain or less.
The term "chain" as used herein refers to a molecule of a polymer, and the structure of the polymer branched by chemical bonding is also counted as a chain of a molecule.
The amount of the polar group in the modified conjugated diene polymer (II) can be controlled within the above numerical range by adjusting the reaction conditions with the compound used for forming the polymer, for example, the addition amount of the compound, the reaction temperature, the reaction time, and the like in the production process of the modified conjugated diene polymer.
The modified conjugated diene polymer (component (II)) has 2 or more kinds of polymer blocks selected from the group consisting of the polymer blocks of (a) to (C) below.
(A) Polymer blocks mainly composed of vinyl aromatic monomer units (hereinafter, sometimes referred to as polymer blocks (A))
(B) Polymer blocks mainly composed of conjugated diene monomer units (hereinafter, sometimes referred to as polymer blocks (B))
(C) Random polymer blocks of vinyl aromatic monomer units and conjugated diene monomer units (hereinafter sometimes referred to as random polymer blocks (C) and polymer blocks (C))
The content of the vinyl aromatic monomer unit in the polymer block mainly composed of the vinyl aromatic monomer unit (A) is 80% by mass or more.
Examples of the vinyl aromatic compound used for forming the vinyl aromatic monomer unit include, but are not limited to, styrene, α -methylstyrene, p-methylstyrene, divinylbenzene, 1-diphenylethylene, N-dimethyl-p-aminoethylstyrene, N-diethyl-p-aminoethylstyrene, and the like.
Among these, styrene, α -methylstyrene and 4-methylstyrene are preferable, and styrene is more preferable from the viewpoints of availability and productivity.
The polymer block (A) mainly composed of vinyl aromatic monomer units may be composed of 1 kind of vinyl aromatic monomer units or 2 or more kinds of vinyl aromatic monomer units.
From the viewpoint of the strength of the molded article of the resin composition of the present embodiment, (a) the content of the vinyl aromatic monomer unit contained in the polymer block mainly composed of the vinyl aromatic monomer unit is 80 mass% or more, preferably 90 mass% or more, more preferably 95 mass% or more, still more preferably 100 mass% (other compounds are not intentionally added).
The content of the conjugated diene monomer units in the polymer block mainly composed of conjugated diene monomer units in the (B) is 80% by mass or more.
As the conjugated diene compound for forming the conjugated diene monomer unit, a diene having 1 pair of conjugated double bonds may be used. Examples of the diene 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 preferable from the viewpoints of availability and productivity.
(B) The polymer block mainly composed of conjugated diene monomer units may be composed of 1 conjugated diene monomer unit or 2 or more conjugated diene monomer units.
The content of the conjugated diene monomer units contained in the polymer block mainly composed of conjugated diene monomer units (B) is 80 mass% or more, preferably 90 mass% or more, more preferably 95 mass% or more, and still more preferably 100 mass% in terms of impact resistance of the resin composition of the present embodiment (no other compound is intentionally added).
The vinyl aromatic compound and the conjugated diene compound used for forming the vinyl aromatic monomer units and conjugated diene monomer units contained in the random polymer block of the conjugated diene monomer units (C) may be any compound 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 the vinyl aromatic monomer units in the random polymer block (C) may be uniformly distributed or may be distributed stepwise. In addition, the vinyl aromatic monomer unit may be uniformly distributed and/or the vinyl aromatic monomer unit may be distributed in a stepwise manner, and the segment having different vinyl aromatic monomer unit content may be present in a plurality.
The mass ratio of the vinyl aromatic monomer unit to the conjugated diene monomer unit in the random copolymer block (C) is preferably from 75/25 to 25/75, more preferably from 70/30 to 30/70, still more preferably from 65/35 to 35/65.
The modified conjugated diene 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, and examples thereof include a structure represented by the following formula.
In the following formula, the description of the polar group is omitted.
(b-c) n 、c-(b-c) n 、b-(c-b) n 、(b-c) m -X、(c-b) m -X、[(b-c) n ] m -X、[(c-b) n ] m -X、[c-(b-c) n ] m -X、[b-(c-b) n ] m -X、[(b-c) n -b] m -X、[(c-b) n -c] m -X、
(a-b) n 、b-(a-b) n 、a-(b-a) n 、(a-b) m -X、(b-a) m -X、[(a-b) 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、[(b-a) n -b] m -X、
(a-c) n 、c-(a-c) n 、a-(c-a) n 、(a-c) m -X、(c-a) m -X、[(a-c) 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、[(c-a) n -c] m -X、
c-(b-a) n 、c-(a-b) n 、
c-(a-b-a) n 、c-(b-a-b) n 、
a-c-(b-a) n 、a-c-(a-b) n 、
a-c-(b-a) n -b、[(a-b-c) n ] m -X、
[a-(b-c) n ] m -X、[(a-b) n -c] m -X、
[(a-b-a) n -c] m -X、
[(b-a-b) n -c] m -X、[(c-b-a) n ] m -X、
[c-(b-a)n] m -X、[c-(a-b-a) n ] m -X、[c-(b-a-b) n ] m -X
a-(b-c) n 、a-(c-b) n 、
a-(c-b-c) n 、a-(b-c-b) n 、
c-a-(b-c) n 、c-a-(c-b) 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-(a-c) n 、b-(c-a) n 、
b-(c-a-c) n 、b-(a-c-a) n 、
c-b-(a-c) n 、c-b-(c-a) n 、
c-b-(a-c) 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 general formulae, 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 to 5.
m is an integer of 2 or more, preferably an integer of 2 to 11.
X represents the residue of a coupling agent or the residue of a multifunctional initiator.
The modified conjugated diene polymer (component (II)) is particularly preferably a polymer having a basic block structure represented by the structural formulae a-b, a-b-a-b.
The weight average molecular weight (Mw) (hereinafter also referred to as "Mw") of the modified conjugated diene polymer (component (II)) is preferably 0.5 to 60 ten thousand, more preferably 3 to 40 ten thousand, and even more preferably 5 to 30 ten thousand, from the viewpoints of mechanical strength, impact resistance, abrasion resistance, compatibility, and moldability of the resin composition of the present embodiment.
The weight average molecular weight (Mw) of the modified conjugated diene polymer (component (II)) was obtained by obtaining a calibration curve (prepared using the peak molecular weight of a standard polystyrene) from the measurement of a commercially available standard polystyrene, and obtaining the peak molecular weight (Mw) of a chromatogram obtained by the measurement by Gel Permeation Chromatography (GPC) based on the calibration curve.
The molecular weight distribution of the conjugated diene polymer before modification can be similarly determined from measurement by GPC. The molecular weight distribution is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
The molecular weight distribution of the single peak of the modified conjugated diene polymer (component (II)) as measured by GPC is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.0 or less, further more preferably 2.5 or less.
The modified conjugated diene polymer (component (II)) contains a vinyl aromatic monomer unit.
In general, impact resistance and toughness are imparted by dispersing a predetermined polymer in a polar resin having high rigidity, and when impact or stretching is applied, voids are generated at the interface between the polar resin and the dispersed polymer particle component or at the polymer particles themselves, and stress relaxation due to shear yield of the matrix resin occurs from the polymer particles.
Since the polymer block (a) mainly composed of a vinyl aromatic monomer unit is amorphous, the shear yield tends to be promoted.
Accordingly, the lower limit of the content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and still more preferably 8% by mass or more, from the viewpoint of promoting the above-mentioned shear yield and exhibiting impact resistance and toughness.
By setting the content of the vinyl aromatic monomer unit in the modified conjugated diene polymer (component (II)) to 1 mass% or more, the amorphous portion of the vinyl aromatic monomer unit of the modified conjugated diene polymer (II) tends to aggregate, and the shear yield tends to be promoted. However, when voids are generated at the interface between the polar resin having high rigidity and the dispersed polymer particle component or in the polymer particles themselves, it is important that the polar resin as a matrix has a large difference in rigidity from the dispersed phase. From this point of view, the upper limit of the vinyl aromatic monomer unit of the modified conjugated diene polymer (component (II)) is preferably 90 mass% or less, more preferably 85 mass% or less, and even more preferably 80 mass% or less, from the viewpoint of voids occurring at the interface between the polar resin (component (I)) and the dispersed polymer particle component (II)) or the polymer particles themselves, and showing impact resistance and toughness. When the vinyl aromatic unit content of the component (II) is 90 mass% or less, the difference in rigidity between the dispersed phase and the matrix increases, and voids are further generated at the interface or in the polymer particles themselves, so that the resin composition of the present embodiment tends to have improved impact resistance and toughness.
When a polyphenylene sulfide resin is used as the polar resin of the component (I), the content of the vinyl aromatic monomer unit of the modified conjugated diene polymer (component (II)) is preferably 40 mass% or less, more preferably 35 mass% or less, still more preferably 30 mass% or less, still more preferably 27 mass% or less, from the viewpoint of exhibiting impact resistance at low temperature.
The content of the vinyl aromatic monomer unit of the modified conjugated diene polymer (component (II)) can be measured by the method described in examples described below.
The content of the vinyl aromatic monomer unit of the modified conjugated diene polymer (component (II)) can be controlled within the above numerical range by adjusting the amount of the monomer to be added in producing the polymer.
The lower limit of the content of the polymer block (a) in the modified conjugated diene polymer (II) is preferably 1 mass% or more, more preferably 3 mass% or more, and still more preferably 5 mass% or more in terms of productivity. The upper limit value of the content of the polymer block (a) is preferably 95 mass% or less, more preferably 90 mass% or less, and further preferably 80 mass% or less in view of exhibiting impact resistance and toughness. When a polyphenylene sulfide resin is used as the polar resin (I), the content of the polymer block (a) in the modified conjugated diene polymer (II) is preferably 40 mass% or less, more preferably 35 mass% or less, still more preferably 30 mass% or less, still more preferably 27 mass% or less, from the viewpoint of exhibiting impact resistance at low temperature.
The content of the polymer block (B) in the modified conjugated diene polymer (II) is preferably 0 mass% or more, and more preferably 10 mass% or more and 90 mass% or less in terms of impact resistance and toughness.
When a polyphenylene sulfide resin is used as the polar resin (I), the content of the polymer block (B) in the modified conjugated diene polymer (II) is preferably 60 mass% or more, more preferably 65 mass% or more, still more preferably 70 mass% or more, still more preferably 73 mass% or more, from the viewpoint of exhibiting impact resistance at low temperature.
The content of the polymer block (C) in the modified conjugated diene polymer (II) is preferably 0 mass% or more, and more preferably 10 mass% or more and 90 mass% or less in terms of compatibility with the polyphenylene sulfide resin.
In the modified conjugated diene polymer (II), the vinyl bond content is preferably 0mol% or more, more preferably 5mol% or more, based on 100mol% of the total conjugated diene monomer units.
The "vinyl bond amount" means a total amount (mol%) of 1, 2-bonds relative to 1, 4-bonds (cis and trans) and 1, 2-bonds (wherein, in the case of embedding 3, 4-bonds into a polymer, means the total amount of 1, 2-bonds and 3, 4-bonds) due to the conjugated diene compound in the polymer before hydrogenation.
The vinyl bond content of the modified conjugated diene polymer (II) can be measured by a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, can be measured by a method described in examples described later.
The vinyl bond amount can be controlled within the above numerical range by using a lewis base, a compound such as an ether, an amine, or the like as a vinyl bond amount regulator (hereinafter referred to as a vinylating agent).
The modified conjugated diene polymer (II) may include a hydrogenated modified conjugated diene polymer obtained by hydrogenating an aliphatic double bond derived from a conjugated diene compound. This can improve the heat resistance of the resin composition of the present embodiment.
For the reason of improving heat resistance by hydrogenation of thermally unstable 1, 2-linkages (wherein, in the case of embedding in a polymer in 3, 4-linkages, 1, 2-linkages and 3, 4-linkages are included), the hydrogenation rate of the aliphatic double bond derived from the conjugated diene compound is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more.
When a polyphenylene sulfide resin is used as the polar resin (I) having particularly excellent rigidity, chemical resistance and heat resistance, the hydrogenation rate is preferably 90% or less, more preferably 83% or less, and even more preferably 80% or less, from the viewpoint of further improving toughness and impact resistance by making the number average dispersion particle diameter of the dispersed phase (B) in the resin composition of the present embodiment 1.5 μm or less.
The hydrogenation rate of the modified conjugated diene polymer (II) can be measured by using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, can be measured by the method described in examples.
The hydrogenation ratio can be controlled within the above-mentioned numerical range by adjusting the amount of hydrogen to be reacted during the hydrogenation reaction, for example.
< method for producing modified conjugated diene Polymer (component (II))
The modified conjugated diene polymer (II) used in the resin composition of the present embodiment can be produced, for example, by, but not limited to, polymerizing an organic alkali metal compound as a polymerization initiator, a conjugated diene compound and a vinyl aromatic compound in an organic solvent to obtain a block polymer, and then carrying out a modification reaction.
The modified conjugated diene polymer (II) may be hydrogenated, and the hydrogenation reaction and the modification reaction are not limited to this order, but may be reversed.
The polymerization may be carried out in a batch manner, a continuous manner, or a combination thereof.
In view of keeping the size of the dispersed phase in the resin composition constant, which affects impact resistance and toughness, a batch polymerization method in which the molecular weight distribution is narrowed is preferable.
The polymerization temperature is usually 0 to 180 ℃, preferably 20 to 160 ℃, more preferably 30 to 150 ℃.
The polymerization time varies depending on the target polymer, and is usually 48 hours or less, preferably 0.1 to 10 hours. The time period is more preferably 0.5 to 5 hours, from the viewpoint of obtaining a conjugated diene polymer having a narrow molecular weight distribution and high strength.
The atmosphere of the polymerization system is not particularly limited as long as it is a pressure range sufficient to maintain nitrogen and the solvent in the liquid phase.
It is preferable that impurities such as water, oxygen, carbon dioxide, etc., which deactivate the polymerization initiator and living polymer, are not present in the polymerization system.
Examples of the organic solvent include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbon systems such as cyclohexane, cycloheptane and methylcyclopentane; aromatic hydrocarbons such as benzene, xylene, toluene, and ethylbenzene.
The organic alkali metal compound as the polymerization initiator is preferably an organolithium compound.
Examples of the organolithium compound include organomono-lithium compounds, organodi-lithium compounds, and organopoly-lithium compounds.
Examples of the organolithium compound include, but are not limited to, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, hexamethylenedilithium, butadienyl lithium, isopropenyl dilithium, and piperidine lithium.
When an organolithium compound containing N such as lithium piperidine is used as a polymerization initiator, an amino-modified conjugated diene polymer having an atomic group of x=0 in NHx can be obtained.
These polymerization initiators may be used alone in an amount of 1 or two or more kinds may be used in combination. Among these, n-butyllithium, sec-butyllithium and piperidinium are preferable from the viewpoint of polymerization activity.
The amount of the organic alkali metal compound used as the polymerization initiator is usually preferably in the range of 0.01 to 1.5phm (parts by mass per 100 parts by mass of the monomer) depending on the molecular weight of the target modified conjugated diene polymer, more preferably in the range of 0.02 to 0.3phm, still more preferably in the range of 0.05 to 0.2 phm.
The vinyl bond amount of the modified conjugated diene polymer (component (II)) can be controlled by using a lewis base, for example, a compound such as an ether or an amine, as a vinyl bond amount regulator (hereinafter referred to as a vinylating agent).
In addition, the amount of vinyl bond can be controlled by adjusting the amount of the vinylating agent.
Examples of the vinylating agent include, but are not limited to, ether compounds, tertiary amine compounds, and the like.
Examples of the ether compound include a linear ether compound and a cyclic ether compound.
Examples of the linear ether compound include, but are not limited to, dialkyl ether compounds of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dibutyl ether.
Examples of the cyclic ether compound include, but are not limited to, tetrahydrofuran, dioxane, 2, 5-dimethyltetrahydrofuran, 2, 5-tetramethyltetrahydrofuran, 2-bis (2-tetrahydrofuryl) propane, and alkyl ethers of furfuryl alcohol.
Examples of the tertiary amine compound 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-dipiperidylethane, trimethylaminoethylpiperazine, N, N ', N ' -pentamethylethylenetriamine, N, N ' -dioctyl-p-phenylenediamine, pyridine, tetramethylpropylenediamine, bis [2- (N, N-dimethylamino) ethyl ] ether, and the like.
These compounds may be used alone or in combination of 2 or more.
As the tertiary amine compound, a compound having 2 amines is preferable. Further, among these compounds, compounds having a structure showing symmetry in the molecule are more preferable, and N, N' -tetramethylethylenediamine, bis [2- (N, N-dimethylamino) ethyl ] ether, and 1, 2-dipiperidylethane are more preferable.
The modified conjugated diene polymer (II) used in the resin composition of the present embodiment can be produced by polymerizing a conjugated diene compound and a vinyl aromatic compound in the presence of the above-mentioned vinylating agent, an organolithium compound, and an alkali metal alkoxide.
Here, the alkali metal alkoxide is a compound represented by the general formula MOR (in the formula, M is an alkali metal, and R is an alkyl group).
By allowing the alkali metal alkoxide to coexist in the polymerization step, the effect of controlling the vinyl bond amount, molecular weight distribution, polymerization rate, block ratio, and the like can be obtained.
The alkali metal of the alkali metal alkoxide is preferably sodium or potassium in terms of a high vinyl bond content, a narrow molecular weight distribution, a high polymerization rate, and a high block ratio.
Examples of the alkali metal alkoxide include, but are not limited to, sodium alkoxide, lithium alkoxide, and potassium alkoxide each having an alkyl group having 2 to 12 carbon atoms, preferably sodium alkoxide and potassium alkoxide each having an alkyl group having 3 to 6 carbon atoms, and more preferably sodium tert-butoxide, potassium tert-butoxide, and potassium tert-butoxide.
Among these, sodium tert-butoxide and sodium tert-amyl alcohol as sodium alkoxide are more preferable.
The modified conjugated diene polymer (II) may be hydrogenated, and the polymer block containing conjugated diene monomer units may be a hydride.
The method of hydrogenation is not particularly limited, and for example, a hydrogenated conjugated diene polymer obtained by hydrogenating a double bond residue of a conjugated diene monomer unit can be obtained by supplying hydrogen to the conjugated diene polymer obtained in the above-described polymerization step in the presence of a hydrogenation catalyst and hydrogenating the resultant product.
The hydrogenation rate (hydrogenation rate) can be controlled, for example, by the amount of the catalyst used in the hydrogenation. The hydrogenation rate can be controlled by adjusting the amount of catalyst, the amount of hydrogen fed, the pressure and the temperature during hydrogenation, for example. The hydrogenation step is preferably performed at a point in time after the reaction of producing the conjugated diene polymer before hydrogenation is stopped.
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 dicarboxylic group, an epoxy group, an oxetanyl group and an amino group bonded thereto.
From the viewpoints of affinity and/or reactivity with the polar resin (I) and a polymer having a predetermined polar group (component (III)) described later, hydroxyl groups and carboxyl groups are more preferable.
Further, when the polar group bonded to the modified conjugated diene polymer (II) is at least one selected from the group consisting of a hydroxyl group and a carboxyl group, and a thermoplastic resin is used as the component (I) and the resin composition in a molten state is injected into a mold by injection molding and cooled to obtain an arbitrary molded article, 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 polymer is not particularly limited, and examples thereof include: a method of introducing a polymerization initiator having a predetermined polar group; a method of polymerizing unsaturated monomers having respective polar groups to obtain a modified conjugated diene polymer; a method of causing an addition reaction between a modifying agent having a polar group and an active end of a polymer; etc.
The modified conjugated diene polymer (II) is not particularly limited as to the position of introduction of each polar group, and may be, for example, a terminal of a conjugated diene polymer or may be arranged in a block or random or tapered manner in a part of the main chain. The terminal of the conjugated diene polymer is more preferable from the viewpoints of affinity and/or reactivity with the polar resin (component (I)), and a polymer having a predetermined polar group (component (III)) described later, and further from the viewpoint of processability of the resin composition.
Examples of the "modifier" include, but are not limited to, aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid; aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, trimellitic acid, and pyromellitic acid.
Further, maleic anhydride, itaconic anhydride, pyromellitic dianhydride, cis-4-cyclohexane-1, 2-dicarboxylic anhydride, 1,2,4, 5-pyromellitic dianhydride, 5- (2, 5-dioxy-tetrahydroxyfuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, epsilon-caprolactam, and the like can be mentioned.
Examples of other methods for introducing a polar group into a conjugated diene polymer include the following methods: a method in which an organic alkali metal compound such as an organolithium compound is reacted with a conjugated diene polymer (metallization reaction), and a modifier having a polar group is subjected to an addition reaction with the polymer to which the organic alkali metal is added.
Further, as another method of introducing the polar group, for example, a method of directly graft-adding an atomic group having a polar group to an unmodified conjugated diene polymer is mentioned.
Examples of the method of graft addition include: a method of reacting a radical initiator and a conjugated diene polymer in a solution containing the same and a modifier; or a method in which a radical initiator and a conjugated diene polymer are reacted with each other under heating and melting; or a method in which a compound containing a conjugated diene polymer and the modifier is reacted under heating and melting conditions without containing a radical initiator; etc.
Examples of the method for reacting the components when the polar groups are introduced into the polymer include a method in which the components are melt kneaded using a common mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a worm kneader, or a multi-screw extruder. From the viewpoints of cost and production stability, a method using a single screw, twin screw or multi-screw extruder is preferable, and a method using a twin screw extruder is preferable.
In the reaction step, the components may be dry-blended and then fed at once, or the components may be fed separately, or the same components may be added in stages.
The rotation speed of the screw is preferably 50 to 400rpm, more preferably 100 to 350rpm, from the viewpoint of uniformly adding the modifier to the polymer, and preferably 150 to 300rpm, from the viewpoint of suppressing deterioration of the polymer due to shearing and performing uniform addition.
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 to 350 ℃. The temperature is preferably 120 to 300 ℃, more preferably 150 to 250 ℃, in terms of controlling the amount of polar groups introduced and suppressing degradation of the polymer by heat.
In order to suppress deactivation by oxygen of radical active species, melt kneading may be performed under an inert gas such as nitrogen.
Examples of the radical initiator include, but are not limited to, ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate. The free radical initiator preferably has a 1 minute half life temperature in the mixing temperature range. More preferably, the half-life temperature of 1 minute is 150 to 250 ℃, and examples thereof include 1, 1-di (t-hexylperoxy) cyclohexane, 1-di (t-butylperoxy) cyclohexane, 2-di (4, 4-di (t-butylperoxy) cyclohexyl) propane, t-hexylperoxy isopropyl monocarbonate, t-butylperoxymaleate, t-butylperoxy-3, 5-trimethylhexanoate, t-butylperoxy laurate, t-butylperoxy isopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2, 5-dimethyl-2, 5-di (benzoyl peroxy) hexane, t-butylperoxy acetate, 2-di (t-butylperoxy) butane, t-butylperoxy benzoate, n-butyl 4, 4-di (t-butylperoxy) valerate, di (2-t-butylperoxy isopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2, 5-dimethyl-2, 5-di-t-butylperoxy-hexane, 2, 5-di-dimethyl-3, 5-di-t-butylperoxy-3, 3-di-methyl-3-butylperoxy-3, 3-di-methyl-n-butylperoxy-3-dimethyl-3-di-butylperoxy-3-methyl-n-peroxy-3-dimethyl-n-butyl peroxide.
In particular, from the viewpoint of compatibility with the conjugated diene polymer used in the modification step, bis (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-yne are preferable.
More preferably 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane or 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne.
Further, as another method for introducing a polar group into a conjugated diene polymer, there is a secondary modification in which a primary modified conjugated diene polymer obtained by the above method is reacted with an atomic group having a predetermined polar group to be introduced.
Examples of the combination of polar groups include amino groups with dicarboxylic groups, acid anhydride groups, isocyanate groups, hydroxyl groups, oxazoline groups, oxetane groups, and carboxyl groups; anhydride groups and hydroxy, oxazoline, and oxetane groups; silanol and hydroxyl groups and carboxyl groups; epoxy and carboxyl groups. From the aspect of reactivity, amino and dicarboxylic groups, acid anhydride groups, oxazolinyl groups, and oxetanyl groups are preferable; silanol groups and hydroxyl groups and dicarboxylic groups; epoxy groups and dicarboxylic groups, more preferably amino groups and dicarboxylic groups, and acid anhydride groups.
The method of bonding the epoxy group, the acid anhydride group, and the hydroxyl group to the conjugated diene polymer by the primary modification may be the above method, and the modifier may be the above modifier, the epoxy group-containing polymerizable compound, or the like.
The method of bonding the silanol group to the conjugated diene polymer by the primary modification may be the method described above, and examples of the modifier include bis- (3-triethoxysilylpropyl) -tetrasulfane, bis- (3-triethoxysilylpropyl) -disulfane, ethoxysiloxane oligomer, epoxy group-containing polymerizable compound, and hydrolysate of an alkoxysilane group-containing compound among the epoxy group-containing polymerizable compounds described above.
The method of bonding an amino group to a conjugated diene polymer by one modification may be the above-mentioned method, and examples of the modifier include 1, 3-dimethyl-2-imidazolidinone, 1, 3-diethyl-2-imidazolidinone, N ' -dimethylpropylurea, 1, 3-diethyl-2-imidazolidinone, 1, 3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone, 1-methyl-3- (2-methoxyethyl) -2-imidazolidinone, 1-methyl-3- (2-ethoxyethyl) -2-imidazolidinone, 1, 3-bis (2-ethoxyethyl) -2-imidazolidinone, 1, 3-dimethylethylene thiourea, N ' -diethylpropenylurea, and N-methyl-N ' -ethylpropylendole. Examples of the "compound" include 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1, 5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone, 1-methyl-2-piperidone, 1, 4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-isopropyl-2-piperidone, and 1-isopropyl-5, 5-dimethyl-2-piperidone.
The method of bonding the primary modified conjugated diene polymer having an amino group bonded thereto and the secondary modifier includes the above-mentioned methods, and examples of the modifier include aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and the like; aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, trimellitic acid, and pyromellitic acid. Examples of the acid anhydride include maleic anhydride, itaconic anhydride, pyromellitic dianhydride, cis-4-cyclohexane-1, 2-dicarboxylic anhydride, 1,2,4, 5-pyromellitic dianhydride, and 5- (2, 5-dioxy-tetrahydroxyfuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
The shape of the modified conjugated diene polymer (II) obtained by the above-described production method is not particularly limited, and examples thereof include pellet, sheet, strand, chip and the like. Alternatively, the molded article may be directly produced after melt kneading.
Pellets of the modified conjugated diene polymer (II) can be produced by granulating the modified conjugated diene polymer (II).
Examples of the method of granulating include: a method in which a modified conjugated diene polymer is extruded into a strand from a single-screw or twin-screw extruder and cut in water by a rotating blade provided in front of a die head; extruding the modified conjugated diene polymer into a strand from a single-screw or double-screw extruder, performing water cooling or air cooling, and cutting by using a strand granulator; a method comprising melt-mixing with an open mill or a Banbury mixer, forming into a sheet with a roll, further cutting the sheet into a long strip shape, and cutting into a cube-shaped pellet with a pelletizer; etc.
The size and shape of the pellet are not particularly limited.
In the modified conjugated diene polymer (II), a pellet antiblocking agent may be blended with the pellets, if necessary, for the purpose of preventing the pellets from blocking.
Examples of the pellet antiblocking agent include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bis stearamide, talc, amorphous silica, and the like.
When a random polypropylene composition, a tubular molded article comprising the same, and a sheet-like molded article are produced using the resin composition of the present embodiment, calcium stearate, polyethylene, and polypropylene are preferable in terms of their transparency.
The preferable amount of the pellet antiblocking agent is 500 to 6000ppm based on the modified conjugated diene polymer (II). The amount of the modified conjugated diene polymer (II) is preferably 1000 to 5000ppm. The pellet antiblocking agent is preferably compounded in a state of adhering to the pellet surface, but may be contained inside the pellet to some extent.
(component (III) a polymer having a polar group reactive with component (I) and/or component (II) (excluding component (I) and component (II))
The resin composition of the present embodiment may contain a polymer having a polar group reactive with the component (I) and/or the component (II) (excluding the component (I) and the component (II)) (hereinafter, may be referred to as a polymer (III) or a component (III)).
Even if the polar group bonded to the modified conjugated diene polymer (II) has low affinity and/or reactivity with the component (I), the number average dispersion particle diameter of the dispersed phase (B) in the resin composition of the present embodiment tends to be 1.5 μm or less by including the polymer (III) having the polar group reactive with the component (I) and/or the component (II).
In addition, from the viewpoint of exhibiting impact resistance and toughness by increasing the difference in rigidity between the polar resin (component (I)) as a matrix and the dispersed phase (component (II) and component (III)), component (III) is preferably reactive with component (I) and component (II) to promote shear yield.
The component (III) is a modified polymer of a non-vinyl aromatic compound type which does not contain a polymer block mainly composed of a vinyl aromatic monomer unit and does not contain a polymer having the same structure as the modified conjugated diene polymer (II).
When the component (III) contains a vinyl aromatic monomer unit, the reactivity with the component (I) and the component (II) tends to be reduced by steric hindrance of the aromatic ring.
The component (III) is a polymer having a polar group reactive with the component (I) and/or the component (II), and the term "polymer" means a polymer compound having a repeating unit (including an oligomer having a repeating unit of about 2 to 10 and having a low degree of polymerization).
The lower limit of the molecular weight of the component (III) is preferably 1000 or more, more preferably 2000 or more, from the viewpoint of maintaining practically sufficient rigidity of the resin composition of the present embodiment. The upper limit of the molecular weight of the component (III) is preferably 500 ten thousand or less, more preferably 300 ten thousand or less, and still more preferably 100 ten thousand or less, from the viewpoint of fluidity of the resin composition of the present embodiment.
The molecular weight of the component (III) may be appropriately set in consideration of compatibility with the component (I) and the component (II), fluidity of the resin composition of the present embodiment, and the like. When the molecular weight is 500 ten thousand or less, good fluidity of the resin composition can be obtained and practically good moldability tends to be obtained.
"reactivity" of the component (III) with the component (I) and/or the component (II) means that the polar groups of the respective components have covalent bonding with each other.
When polar groups react with each other, for example, if OH of a carboxyl group is detached, the original polar groups are changed or disappear, but in the case where covalent bonds are formed thereby, it is included in the definition that polar groups show "reactivity" with each other.
Among the polar groups contained in the component (III), 1 polar group may exhibit reactivity with both the component (I) and the component (II), or plural polar groups may exhibit reactivity with both the component (I) and the component (II), respectively.
The component (III) may contain a polar group reactive with only one of the component (I) and the component (II), but it is preferable to have a polar group reactive with both the component (I) and the component (II) in order to improve affinity with both the components and to make the number average dispersion particle diameter of the dispersed phase (B) described later 1.5 μm or less, preferably 1.3 μm or less. For example, when the component (III) has an epoxy group, the component (I) is a polyphenylene sulfide resin, and the component (II) is a polymer having a carboxyl group and/or a hydroxyl group, the epoxy group of the component (III) exhibits reactivity with the carboxyl groups of both the polyphenylene sulfide resin of the component (I) and the polymer of the component (II).
The polar group contained in the component (III) has reactivity with the polar resin (component (I)) and the modified conjugated diene polymer (component (II)), and thus, the resin composition of the present embodiment can have improved toughness and impact resistance.
(combination of component (I), component (II), and component (III))
The polar group combinations of the component (II) and the component (III) include the following combinations.
When the component (II) contains an amino group, preferable polar groups contained in the component (III) include carboxyl groups, carbonyl groups, epoxy groups, hydroxyl groups, acid anhydride groups, sulfonic acid groups, aldehyde groups, and the like.
When the component (II) contains an acid anhydride group, preferable polar groups contained in the component (III) include amino groups, hydroxyl groups, and the like.
When the component (II) contains a carboxyl group or a dicarboxylic group, preferable polar groups contained in the component (III) include amino groups, isocyanate groups, and the like.
When component (II) has an epoxy group, preferable polar groups contained in component (III) include amino, carboxyl, dicarboxyl, mercapto, oxazolinyl, oxetanyl and the like.
When component (II) contains an oxetanyl group, preferable polar groups contained in component (III) include mercapto groups, hydroxyl groups, amino groups, carboxyl groups, dicarboxylic groups, and the like.
When component (II) contains an oxazoline group, preferable polar groups contained in component (III) include mercapto groups, hydroxyl groups, amino groups, carboxyl groups, dicarboxylic groups, and the like.
Further, as a combination of polar groups contained in the component (I) and the component (III), there is given:
amino and carboxyl groups, carbonyl groups, epoxy groups, hydroxyl groups, anhydride groups, sulfonic acid and aldehyde groups;
isocyanate groups and hydroxyl groups, carboxyl groups and dicarboxylic groups;
hydroxy and anhydride groups;
silanol groups and hydroxy, carboxyl and dicarboxy groups;
epoxy and carboxyl, dicarboxyl, mercapto, oxazolinyl and oxetanyl;
halo and carboxylic acid groups, carboxylic ester groups, amino groups, phenol groups, and mercapto groups;
alkoxy and hydroxy, alkoxide groups, and amino groups;
mercapto and epoxy, oxazoline and oxetane groups;
etc.
In the resin composition of the present embodiment, the polar group of component (II) is bonded to the polar group of either component (I) or component (III), and may be arbitrarily selected.
When a polyphenylene sulfide resin which is a polar resin excellent in rigidity, chemical resistance and heat resistance is used as the component (I), the polar group contained in the component (II) is preferably a carboxyl group, a hydroxyl group, an epoxy group, an oxazoline group or an oxetanyl group, more preferably a carboxyl group or a hydroxyl group, from the viewpoint of reactivity.
In order to have reactivity with the component (I) and the component (II), the polar group of the component (III) is preferably an epoxy group, an oxazoline group or an oxetane group, and from the viewpoint of reactivity, an epoxy group is more preferable.
When the component (III) is a polymer having an epoxy group, examples of the polymer having an epoxy group include a polymer of a polymerizable compound having an epoxy group such as an unsaturated compound having an epoxy group, and a copolymer of a polymerizable compound having an epoxy group and at least one other polymerizable compound.
Examples of the polymerizable compound having an epoxy group include, but are not limited to, unsaturated compounds having an epoxy group, and examples thereof include: polyepoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl itaconate, tetraglycidyl m-xylylenediamine, tetraglycidyl-1, 3-diaminomethylcyclohexane, tetraglycidyl p-phenylenediamine, tetraglycidyl diaminodiphenylmethane, diglycidyl aniline, diglycidyl o-toluidine, 4 '-diglycidyl-diphenylmethylamine, 4' -diglycidyl-dibenzylmethylamine, and diglycidyl aminomethylcyclohexane.
Further, there may be mentioned: gamma-glycidoxyethyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxybutyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl tripropoxysilane, gamma-glycidoxypropyl diethylethoxysilane, gamma-glycidoxypropyl dimethylethoxysilane, gamma-glycidoxypropyl methyldimethoxysilane, gamma-glycidoxypropyl ethyldimethoxysilane, gamma-glycidoxypropyl ethyldiethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, gamma-glycidoxypropyl methyldibutoxysilane, gamma-glycidoxypropyl methyldiphenoxysilane, gamma-glycidoxypropyl dimethylmethoxysilane, gamma-glycidoxypropyl diethylethoxysilane, gamma-glycidoxypropyl diethylphenyloxysilane, gamma-glycidoxypropyl diethylethoxysilane.
Further, bis (gamma-glycidoxypropyl) dipropoxysilane, bis (gamma-glycidoxypropyl) dibutoxysilane, bis (gamma-glycidoxypropyl) diphenoxysilane, bis (gamma-glycidoxypropyl) methylmethoxysilane, bis (gamma-glycidoxypropyl) methylethoxysilane, bis (gamma-glycidoxypropyl) methylpropoxy silane, bis (gamma-glycidoxypropyl) methylbutoxysilane, bis (gamma-glycidoxypropyl) and tris (gamma-glycidoxypropyl) methoxysilane may be mentioned.
Further examples include beta- (3, 4-epoxycyclohexyl) ethyl-trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-triethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-tripropoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-tributoxysilane, and beta- (3, 4-epoxycyclohexyl) ethyl-triphenoxysilane.
Further, examples thereof include β - (3, 4-epoxycyclohexyl) propyl-trimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-methylpropyloxy silane, β - (3, 4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl-dimethylpropoxy silane, β - (3, 4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, and β - (3, 4-epoxycyclohexyl) ethyl-dimethylphenoxy silane.
Examples of the compound include beta- (3, 4-epoxycyclohexyl) ethyl-diethylmethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl-methyldiisopropenyloxysilane, and N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine.
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; vinyl cyanide monomers such as acrylonitrile; vinyl acetate, (meth) acrylate, vinyl alcohol, vinyl acetate, and the like.
Examples of the polymer having an epoxy group (component (III)) include, but are not limited to, bondfast (copolymer of ethylene-glycidyl methacrylate, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, manufactured by Sumitomo chemical Co., ltd.), ELVALOY TM PTW (ethylene-glycidyl methacrylate-butyl acrylate copolymer, manufactured by Dow chemical Co., ltd.), vylonRF (glycidyl group-containing polyester resin, manufactured by Toyo-yo Co., ltd.), ARUFONAG-4000 (epoxy group-containing acrylic resin, manufactured by Toyama Co., ltd.).
The polymer having an epoxy group as the component (III) can be obtained by a method of causing an addition reaction between an arbitrary polymer and the above-mentioned unsaturated compound having an epoxy group or the like by a radical reaction or the like.
Examples of the optional polymer include a polymer of an unsaturated hydrocarbon compound such as ethylene or propylene, a copolymer of the unsaturated hydrocarbon compound and a polymerizable compound having a double bond, and a copolymer of a conjugated diene compound and a vinyl aromatic compound.
The method of the addition reaction includes conventionally known techniques, and includes a method of producing a solution containing a radical initiator, a polymer, and an epoxy group-containing compound by reacting them with each other; a method for producing a polymer by reacting a radical initiator with a polymer and an epoxy group-containing compound under heating and melting; a method for producing a polymer by reacting an epoxy group-containing compound under heating and melting conditions without containing a radical initiator; a method for producing a compound which is formed by reacting with either a polymer or an epoxy group-containing compound and is bonded to the polymer, a method for producing a compound which is formed by reacting a polymer and an epoxy group-containing compound in a solution containing them or under heating and melting; etc.
Further, there is also a method of epoxidizing a diene portion of a polymer having carbon bonding and/or a copolymer of a polymer having carbon bonding and another polymerizable compound by oxidizing.
From the aspect of polymerizability, the polymerizable compound containing an epoxy group is preferably an unsaturated compound containing an epoxy group, and more preferably glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, or glycidyl ether of polyalkylene glycol (meth) acrylate.
By increasing the affinity of the polymer having an epoxy group (component (III)) and the modified conjugated diene polymer (component (II)), stress is easily concentrated in the dispersed phase (B) of the resin composition of the present embodiment. The polymer having an epoxy group (component (III)) is more preferably an elastomer having an epoxy group as a copolymer of the above-mentioned epoxy group-containing polymerizable compound (epoxy group-containing polymerizable monomer) and an unsaturated hydrocarbon compound, and further preferably an olefin elastomer having an epoxy group, from the viewpoint of affinity with the modified conjugated diene polymer (component (II)).
By making the polymer (component (III)) an olefin elastomer having an epoxy group, an effect of improving toughness and/or impact resistance by shear yield, which is caused by concentration of stress at the resin interface with component (I), and further an effect of suppressing elongation of microcracks and/or cracks generated under stress, and further an effect of bridging microcracks and/or cracks by component (II) and component (III), and further an effect of improving toughness and/or impact resistance, can be obtained. In particular, in applications where the resin composition is used at a low temperature, specifically at-30 ℃ or lower, the component (III) is an olefin elastomer having an epoxy group, and thus toughness and/or impact resistance at a low temperature tend to be further improved. Further, it is also expected to improve tracking resistance and to suppress deterioration of physical properties (thermal cycle characteristics) when exposed alternately to high to low temperatures.
By adjusting the affinity and reactivity of the components, the compatibility can be controlled, and these effects can be improved.
In addition, as for the polymer having an epoxy group as the component (III), the polymerizable compound such as styrene, acrylonitrile and the like, vinyl acetate, (meth) acrylic acid ester, vinyl alcohol, vinyl acetate and the like may be copolymerized with the unsaturated hydrocarbon compound and the epoxy group-containing polymerizable compound, and when the component (I) is a polyphenylene sulfide resin, it is more preferable to copolymerize (meth) acrylic acid ester, vinyl acetate, and further preferable to copolymerize (meth) acrylic acid ester and/or vinyl acetate in terms of affinity with the polyphenylene sulfide resin.
Examples of the unsaturated hydrocarbon compound include ethylene, propylene, and an α -olefin having 3 to 8 carbon atoms.
(proportion of polar resin (I), modified conjugated diene Polymer (II), and Polymer (III))
In the resin composition of the present embodiment, the polar resin (component (I)) and the modified conjugated diene polymer (component (II)) are represented by the mass ratio of component (I) to component (II) in terms of exhibiting heat resistance, impact resistance and toughness of the resin composition of the present embodiment and having a number average dispersion particle diameter of a dispersed phase (B) described later of 1.5 μm or less: component (II) =50/50 to 99/1, preferably 55/45 to 98/2, more preferably 60/40 to 95/5.
In the case where the resin composition of the present embodiment contains the polar resin (component (I)), the modified conjugated diene polymer (component (II)), and the polymer (component (III)), the mass ratio of the component (II) to the component (III) is preferably component (II) in terms of the number average dispersion particle diameter of the dispersed phase (B) being 1.5 μm or less: component (III) =1/99 to 99/1, more preferably 5/95 to 95/5, still more preferably 10/90 to 90/10, still more preferably 15/85 to 85/15.
In the resin composition of the present embodiment, the mass ratio of the total amount of the component (I), the component (II) and the component (III) is preferably the component (I) in terms of exhibiting the heat resistance, impact resistance and toughness of the resin composition of the present embodiment and making the number average dispersion particle diameter of the dispersed phase (B) to be described later 1.5 μm or less: (component (II) +component (III))=50/50 to 99/1, more preferably 60/40 to 97/3, still more preferably 65/35 to 95/5.
(dispersed state)
The resin composition of the present embodiment includes a continuous phase (a) of a polar resin (component (I)) and a dispersed phase (B) containing a modified conjugated diene polymer (component (II)) dispersed in the continuous phase (a).
By making the polar resin (component (I)) into the continuous phase (a), excellent heat resistance and rigidity can be obtained in the resin composition of the present embodiment.
In addition, the presence of the dispersed phase (B) contributes to improvement in impact resistance and toughness by causing fine cracks due to concentration of stress in the dispersed phase (B) when stress is applied to the molded article made of the resin composition.
The dispersed phase (B) may be a phase containing the component (II), and in the case of containing the component (III) as a polymer having a polar group reactive with the component (II), the component (II) modified conjugated diene polymer may be a phase compatible with the component (III), and the component (III) may be in a state of being biased around the component (II) or in a state of being biased around the component (III). In addition, component (III) may be compatible with 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. As described above, the dispersed phase (B) is in a state of containing both the component (II) and the component (III) or in a state in which the component (II) is dispersed alone, and thus the number average dispersion particle diameter of the dispersed phase (B) is a phenomenon corresponding to an improvement in impact resistance and/or toughness. Therefore, the resin composition of the present embodiment has a continuous phase (a) of the polar resin (component (I)) and a dispersed phase (B) containing the modified conjugated diene polymer (component (II)).
A method for confirming the dispersed state of the continuous phase (a) and the dispersed phase (B) will be described.
(1) determination of the Components contained in the resin composition
First, it is useful to determine the number-average particle diameter of the dispersed phase (B) of the components contained in the resin composition of the present embodiment.
The polar resin of component (I) is generally known to have excellent chemical resistance. When the component (II) modified conjugated diene polymer and the component (III) polymer are contained, the undissolved component (I), the unreacted component (II) and the unreacted component (III) can be extracted because the resin composition is excellent in chemical resistance even when the component (III) is mixed in a solvent in which the component (III) can be dissolved. In particular, when the polyphenylene sulfide resin is used as the component (I), since there is no solvent for dissolving the polyphenylene sulfide resin at 200℃or lower, the undissolved component (I), the unreacted component (II) and the unreacted component (III) can be extracted by mixing the solvent with the resin composition at 50 to 200 ℃.
When component (II) and component (III) are contained, examples of the solvent capable of dissolving component (III) include toluene, cyclohexane, xylene, tetrahydrofuran, chloroform, nitroethane, nitropropane, ethylbenzene, and the like, and chloroform, nitroethane, nitropropane, ethylbenzene, and toluene are preferable from the viewpoint of solubility.
After extraction, undissolved component (I) is removed by filtration or the like, and liquid chromatography is performed using the filtrate, whereby component (II) and component (III) can be separated.
In the case where the solubility of the component (II) is different from that of the component (III), the following method may be employed: the component (II) and the component (III) are separated by using a solvent which dissolves the component (II) but does not dissolve the component (III), removing the solvent from the filtrate by vacuum drying or the like, and mixing the thus obtained mixture of the component (II) and the component (III) again in an appropriate solvent.
In general, the solvent having high solubility of the component (II) includes toluene, cyclohexane, and tetrahydrofuran.
The constituent unit of the component (III) which is insoluble in the solvent is a polymer unit of an unsaturated hydrocarbon compound, and particularly, ethylene, propylene, and an alpha-olefin having 3 to 8 carbon atoms are exemplified.
The identification of the component (II) and the component (III) can be performed by Nuclear Magnetic Resonance (NMR), infrared absorption spectroscopy (IR), gas chromatography (GS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), or the like. The type and structure of the polar group bonded to the component (II) or the component (III) may be identified.
In the case where the resin composition of the present embodiment contains components such as additives which are soluble in the solvent in the extraction step, the components can be separated by a difference in molecular weight and polarity by liquid chromatography or the like, and can be identified by NMR, IR, GS, TOF-SIMS or the like.
When the unreacted amounts of the component (II) and the component (III) and the component (I) are very small and separation of the component (II) and the component (III) is difficult, the structural units of the component (II) and the component (III) and the types of the polar groups bonded to the component (II) and the component (III) may be determined from the infrared absorption spectrum obtained by observation with an Atomic Force Microscope (AFM). Examples of the test piece for AFM measurement include a precise cross section of a resin composition produced by an ultra-thin microtome or the like.
(2) measurement of dispersed particle size
[ (1) AFM (particle size measurement of soft phase in elastic modulus mapping) ]
The component (I) polar resin has a melting point generally high temperature, and has higher rigidity than the component (II) at normal temperature, particularly at low temperature, and when the component (III) is contained, has higher rigidity than the component (III).
Further, it was confirmed that the rigidity of the component (II) and the component (III) was relatively lower than that of the component (I) by identifying the structural units of the component (II) and the component (III) after separating the component (II) and the component (III) or by measuring the rigidity of the separated component (including a mixture of the component (II) and the component (III)).
From the infrared absorption spectrum and/or the force curve of the viscoelasticity and elastic modulus obtained by the AMF observation, it was confirmed that the component (I) had high rigidity relative to the components (II) and (III).
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) in the morphology of the resin composition forms "sea". As described above, since the component (I) has a difference in rigidity from the component (II) and the component (III), the portion corresponding to the "island" can be determined as the component (II) and/or the component (III) as long as the "island" portion observed by AFM is softer than the "sea" portion in the elastic modulus map. Therefore, the number average dispersion particle diameter of the dispersed phase (B) can be calculated by obtaining the average value of the particle diameter of the soft portion in the elastic modulus map by the method described in examples described later.
In general, in the measurement of the elastic modulus based on the AFM observation, the upper limit of the force applied to the probe and the sample at the tip of the cantilever of the AFM is set, and the force is applied in the vertical direction, whereby the relation between the load and the deformation amount of the sample is calculated. Therefore, in order to show the degree of deformation of each dispersed phase with respect to the load, the distribution of the components having different elastic moduli can be observed in the form of an image.
In general, the melting temperature when component (I) and component (II) and, if necessary, component (III) are mixed in a molten state is extremely high. Therefore, the low molecular weight compound generated during kneading or the like may bleed out, and a clear elastic modulus map may not be obtained. In this case, as described in examples to be described later, as a stage before the production of the precise cross section for the AFM observation, it is preferable to perform ultrasonic cleaning in a solvent such as ethanol to remove the low molecular compound and the like, and then produce the precise cross section by an ultra-thin microtome and the like.
[ (2) determination of disperse phase based on dyeing ]
In the case where the structural units of the component (II) and the component (III) are identified after the separation of the component (II) and the component (III), the following method can be adopted: the number average dispersion particle diameter of the dispersed phase (B) is calculated by a combination of the structures of the component (I), the component (II), and the component (III), by oxidizing each component with an appropriate heavy metal, and fixing the components by dyeing, using an electron microscope such as a Transmission Electron Microscope (TEM) or a Scanning Electron Microscope (SEM).
The test piece for observation by an electron microscope is an ultrathin slice of the resin composition produced by a low-temperature slice or the like, and may be produced after the above-mentioned dyeing, or may be dyed after the production.
For example, when the amount of the aromatic skeleton of the component (I) is smaller than that of the component (II), or when the component (III) does not have an aromatic ring skeleton, ruthenium tetroxide can be used as the heavy metal of the colorant for the component (II). The coloring agent has a tendency to oxidize the vinyl aromatic monomer unit of the component (II) to the greatest extent, and then oxidize the aromatic ring skeleton of the polar resin of the component (I) so that the component (III) is not oxidized. Since an image in which the component (I) is lightly dyed, the component (II) is darkly dyed, and the component (III) is not dyed is obtained from an electron microscopic observation of the resin composition dyed with the oxidizing agent, the number average dispersion particle diameter of the dispersed phase (B) in the resin composition can be calculated by binarizing the image using image analysis software or the like described in examples described later.
In the above-mentioned binarized image, when the dispersed phase (B) contains a large number of phases other than circles such as ellipses, it is preferable to increase the measurement range in the above-mentioned AFM observation for binarization to about 10 μm×10 μm. In the case where the particles of the dispersed phase (B) are located at the edge of the image obtained in the above visual field, the number average dispersed particle diameter of the dispersed phase (B) is preferably calculated by defining a value 2 times the particle diameter of the particles as the feret diameter described in the example.
The number average dispersion particle diameter 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, even more preferably 0.9 μm or less, from the viewpoint of further concentrating stress on the dispersed phase (B) and exhibiting sufficient impact resistance and toughness in the resin composition of the present embodiment.
The lower limit of the number-average particle diameter of the dispersed phase (B) is not particularly limited, and when the number-average particle diameter is 0.01 μm or more, the rigidity of the resin composition of the present embodiment tends to be easily maintained.
In the resin composition of the present embodiment, as a method for maintaining practically sufficient rigidity, a method of adding a filler or the like described later is also mentioned, and in general, when the number average particle diameter of the dispersed phase (B) is made smaller than 0.01 μm by increasing the amount of polar groups bonded to the component (II) and the component (III), there is a tendency that the amount of side reactions in the step of adding polar groups increases and the impact resistance and toughness of the resin composition decrease, and therefore the number average particle diameter of the dispersed phase (B) is preferably 0.01 μm or more.
The modified conjugated diene polymer (component (II)) exhibits high affinity and/or reactivity with the polar group of the polar resin (component (I)) and the epoxy group of the polymer having an epoxy group (component (III)) by having at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an epoxy group, an oxetanyl group and an amino group.
The polar groups of component (II) and component (III) have affinity and/or reactivity with the polar resin (component (I)). Thus, the affinity and/or reactivity with component (I) depends on the amount of polar groups bonded to component (II) and component (III).
As described above, the amount of the polar group bonded to the modified conjugated diene polymer (II) is preferably 0.3m omicron/chain or more, more preferably 0.5m omicron/chain or more, still more preferably 0.6m omicron/chain or more, from the viewpoint of improving the reactivity of the component (I), the component (II), and the component (III) and making the number average dispersion particle diameter of the dispersed phase (B) 1.5 μm or less. If the amount of the polar group in the component (II) is less than 0.3 mol/chain, the amount of the component (II) which is not reactive with the component (I) and the component (III) is 70mol% or more relative to the total amount of the component (II) in the resin composition, and dispersibility tends to be significantly reduced.
As described above, the mass ratio of the component (II) to the component (III) is preferably the component (II) in terms of making the number average dispersion particle diameter of the dispersed phase (B) 1.5 μm or less: component (III) =1/99 to 99/1, more preferably 5/95 to 95/5, still more preferably 10/90 to 90/10, still more preferably 15/85 to 85/15.
In the case of using a polyphenylene sulfide resin as the component (I), the polar group bonded to the component (II) is preferably at least one selected from the group consisting of a hydroxyl group and a carboxyl group in terms of reactivity with the polyphenylene sulfide resin (which is a polar resin excellent in terms of rigidity, chemical resistance and heat resistance).
The polar group bonded to the component (III) is preferably reactive with the polar group of the component (I) and the polar group of the component (II), and thus is preferably at least one selected from the group consisting of an epoxy group, an oxazoline group, and an oxetane group, and more preferably an epoxy group.
In the case where the component (III) is a polymer having an epoxy group, when the component (I) is a polyphenylene sulfide-based resin, the epoxy group has high affinity and/or reactivity with the polar groups of the component (I) and the component (II), particularly with the polyphenylene sulfide-based resin (component (I)). The content of the epoxy group in the component (III) is preferably 1.0 mol/chain or more, more preferably 2.0 mol/chain or more, still more preferably 3.0 mol/chain or more, from the viewpoint of improving the affinity and/or reactivity of the component (III) with the polyphenylene sulfide resin (component (I)) and the component (II) and making the number average dispersion particle diameter of the dispersed phase (B) 1.5 μm or less.
(additive)
The resin composition of the present embodiment preferably further contains various additives, for example, a filler, in order to improve the strength (rigidity) of the molded article.
In the resin composition of the present embodiment, a fibrous filler is preferable as the filler.
Examples of the fibrous filler include, but are not limited to, fibrous inorganic fillers such as glass fibers, carbon fibers, cellulose nanofibers, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, sepiolite, xonotlite, and zinc oxide whiskers.
Among these, glass fibers, carbon fibers, cellulose nanofibers and wollastonite are preferable because strength (rigidity) and heat resistance of the molded article can be easily improved.
The fibrous filler may be surface-treated with a compound having an affinity group or a reactive group for the polar resin (component (I)).
The fibrous filler may contain only 1 kind, or may contain 2 or more kinds.
Examples of the other additives include, but are not limited to, additives such as oils, fillers, heat stabilizers, ultraviolet absorbers, nucleating agents, antioxidants, weather-proofing agents, light stabilizers, plasticizers, antistatic agents, flame retardants, slipping agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, dispersants, copper inhibitors, neutralizing agents, antifoaming agents, weld strength improvers, natural oils, synthetic oils, and waxes. Other elastomers and thermoplastic resins may be used as the additive in any ratio.
These additives may be used in an amount of 1 or 2 or more.
In addition, an auxiliary agent for improving the affinity or reactivity of 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 above-mentioned 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 preferable.
[ method for producing resin composition ]
The method for producing the resin composition of the present embodiment is not particularly limited, and a known method can be used.
For example, the following method is used: a method in which 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)) are melt kneaded using a common mixer such as a banbury mixer, a single-screw extruder, a twin-screw extruder, a worm kneader, or a multi-screw extruder; a method of dissolving or dispersing the components and mixing them, and then heating to remove the solvent; etc.
The method of melt kneading is preferable in that the number average particle diameter of the dispersed phase (B) is controlled to 1.5 μm or less.
As the method for producing the resin composition of the present embodiment, a method of melt-kneading the components using an extruder is preferable in terms of productivity and good kneading property. In particular, by kneading the components by a twin screw or more and sufficiently imparting shear energy, the interface between the polar resin and the modified conjugated diene polymer increases, and a dispersed phase (B) is formed.
The resin temperature during kneading may be any temperature at which the polar resin (I), the modified conjugated diene polymer (II) and the polymer (III) melt, and is preferably 270℃to 450 ℃.
The temperature of the polar resin (I), the modified conjugated diene polymer (II) and the polymer (III) is more preferably 400℃or lower, in order to suppress deterioration of the polar resin (I), the modified conjugated diene polymer (II) and the polymer (III) due to heat.
In order to suppress oxidation of the modified conjugated diene polymer (II), melt kneading may be performed under an inert gas such as nitrogen.
In the case of producing the resin composition of the present embodiment using an extruder, the filler positions and the order of the polar resin (I) and the modified conjugated diene polymer (II), and other components are not particularly limited.
When a thermosetting resin is used as the component (I), the component (II) dissolved in an appropriate solvent, the component (III) if necessary, and the above-mentioned additives may be added to the thermosetting resin in a solution state and/or the thermosetting resin in a solid state, and the mixture may be mixed, and then an appropriate curing agent may be further added thereto, and the mixture may be mixed again to obtain the resin composition of the present embodiment.
Before the addition of the curing agent, the solvent in which the component (II) and the component (III) are dissolved may be removed by vacuum drying or the like.
Examples of the solvent include toluene, methyl ethyl ketone, cyclohexane, cyclohexanone, chloroform, and tetrahydrofuran.
In the case of using an epoxy resin (which is a polar resin excellent in heat resistance) as the component (I), the curing agent is not particularly limited as long as it has a function of curing the polar resin (I), and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate-based curing agent, and a carbodiimide-based curing agent. The curing agent may be used alone or in combination of 2 or more.
In addition, a curing accelerator may be added as needed. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators.
As a method for molding the resin composition of the present embodiment, the following methods can be mentioned: the resin composition is injected into any mold, and the mold is heated at any time and temperature to obtain a cured product.
The temperature of the mold is preferably 30 to 300 ℃, more preferably 50 to 250 ℃, from the viewpoint of productivity. The heating time is preferably 1 minute to 5 hours, more preferably 10 minutes to 3 hours, from the viewpoint of productivity.
In the case where a polyphenylene sulfide resin is used as the component (I), a material containing a mercapto group or a carboxyl group is preferably used for the polyphenylene sulfide resin, in terms of intermolecular force or chemical bonding between the polyphenylene sulfide resin and the modified conjugated diene polymer (component (II)).
In the step of producing the resin composition of the present embodiment, the shape thereof is not particularly limited, and may be any of pellet, sheet, strand, chip, and the like.
(preferred embodiment of the method for producing a resin composition)
A preferred embodiment of the method for producing a resin composition according to the present embodiment is as follows.
The method comprises a step of kneading a component (II) which is a modified conjugated diene polymer having a polymer block (A) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and at least 2 polymer blocks selected from a random polymer block (C) composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit, and a component (I) which is a resin having a polar group selected from the group consisting of a polyphenylene sulfide resin, a polyethylene terephthalate resin, and a polybutylene terephthalate resin, and a component (III) which is an olefin elastomer having a polar group selected from the group consisting of an epoxy group, an oxazoline group, and an oxetane group, wherein the polar group-containing resin (I)) and the modified conjugated diene polymer (II) have a polar group ratio by mass: modified conjugated diene polymer=50/50 to 99/1, and the mass ratio of the modified conjugated diene polymer to the polar-group-containing olefin elastomer is set to be the modified conjugated diene polymer: olefinic elastomer having polar group=1/99 to 99/1; the method comprises a step of providing the resin composition with a continuous phase (A) of the resin having a polar group (component (I)) and a dispersed phase (B) containing the modified conjugated diene polymer (component (II)) dispersed in the continuous phase (A), and a step of dispersing the dispersed phase (B) to a number average particle diameter of 1.5 [ mu ] m or less.
According to the above production method, a resin composition excellent in impact resistance and toughness can be obtained.
[ molded article ]
The molded article of the present embodiment is the molded article of the resin composition of the present embodiment described above.
The molded article of the present embodiment can be produced by a conventionally known method using the resin composition of the present embodiment, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, blow molding, compression molding, vacuum molding, rotational molding, powder slush molding, foam molding, lamination molding, calender molding, blow molding, or the like.
Further, foaming, powder, stretching, adhesion, printing, coating, plating, and the like may be performed as needed.
The molding method can be effectively used as a sheet, a film, injection molded articles of various shapes, hollow molded articles, pressure air molded articles, vacuum molded articles, extrusion molded articles, foam molded articles, nonwoven fabric or fibrous molded articles, synthetic leather, and other molded articles. These molded articles can be used for automobile interior and exterior materials, construction materials, toys, household electrical appliance parts, medical appliances, industrial parts, various hoses, various housings, various module housings, various power control unit parts, substrates for other miscellaneous goods and electronic devices, housings, sheets, packages, and the like.
The molded article of the present embodiment is preferably used for a non-porous member in view of stably exhibiting impact resistance and toughness. The term "porous" as used herein means that pores penetrating the material are not porous, and bubbles generated by foaming are not through-holes.
(preferred mode of molded article)
The molded article of the present embodiment is a molded article of a resin composition containing, in particular, component (I), component (II) and component (III),
the component (I) is at least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins,
the component (II) is a modified hydrogenated conjugated diene polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, a random polymer block (C) mainly composed of vinyl aromatic monomer units and conjugated diene monomer units,
component (III) is an elastomer having an epoxy group,
wherein,
the modified conjugated diene polymer (component (II)) has at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group,
The above-mentioned molded article satisfies the following conditions (I-1) to (II-1), and in this case, the molded article is preferable in applications requiring high impact resistance and toughness.
Examples of applications requiring high impact resistance and toughness include vehicle pipes such as automobiles, industrial piping, connectors, sockets, resistors, relay housings, switches, bobbins, capacitors, variable capacitor housings, optical pickup devices, resonators, various terminal plates, transformers, plugs, electronic equipment-related members such as printed boards, and the like. They are molded articles used under a wide range of temperature conditions from low temperatures to high temperatures.
< condition (I-1) >
In a long test piece having a width of 10mm, a length of 170mm, and a thickness of 2mm, which was obtained from the molded article, the tensile elongation at break at room temperature under the condition of a tensile speed of 5mm/min was 25% or more.
< conditions (II-1)
In a long test piece having a length of about 80mm, a width of about 10mm and a thickness of 4mm obtained from the molded article, the Charpy impact value in the Charpy impact test at a temperature of-30℃was 15kJ/m 2 。
The molded article of the present embodiment can be processed into a desired shape. For example, dumbbell-shaped test pieces and long test pieces can be produced by cutting out test pieces from a portion of a molded body near a plane. The test piece is not necessarily completely planar, and may be flat to such an extent that the tensile elongation at break and viscoelasticity can be measured. For example, a tubular molded article may be used to prepare a measurable test piece by cutting the test piece in the longitudinal direction, although the tubular molded article is also dependent on the tubular diameter of the tubular molded article. In this case, a portion having a thickness of 2mm or more may be removed by a file or the like, and the elongation at break and the viscoelasticity may be measured by using a test piece which is as flat as possible and has a thickness of 2 mm.
The molded article of the present embodiment is preferably in a state in which the modified conjugated diene polymer (component (II)) is dispersed in a resin having a polar group such as a polyphenylene sulfide resin (component (I)), and the average dispersion particle diameter of the modified conjugated diene polymer (component (II)) is 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.2 μm or less, and even more preferably 1.1 μm or less, with respect to the dispersed state of the modified conjugated diene polymer (component (II)) in the resin having a polar group (component (I)).
In the molded article of the present embodiment, the average particle diameter of the dispersed modified conjugated diene polymer (component (II)) can be measured by the method described in examples below.
In the resin composition constituting the molded article of the present embodiment, the additive such as a filler may be contained in an amount of 1 to 50 parts by mass, preferably 5 to 30 parts by mass, relative to 100 parts by mass of the resin composition for the purpose of improving the strength. In order to add functions such as flame retardancy and tracking resistance in addition to toughness and impact resistance, other additives such as flame retardant may be contained in an amount of 1 to 70 parts by mass based on 100 parts by mass of the resin composition, and 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 10kJ/m 2 The above.
[ method of analyzing resin composition ]
The method for analyzing the components of the resin composition according to the present embodiment is shown below.
When the modified conjugated diene polymer (component (II)) and the resin having a polar group (component (I)) are kneaded, it is considered that the polar group of the modified conjugated diene polymer (component (II)) used in the resin composition of the present embodiment reacts with the polar group of the component (I), which contributes to the reduction of the particle size of the dispersed phase (B), but it is estimated that the polar group of the modified conjugated diene polymer (component (II)) may remain in the resin composition in many cases. It is also considered that, although the polar group of the predetermined polymer (component (III)) is also reactive with component (I) and/or component (II), unreacted polar groups remain in the resin composition.
In order to characterize the modified conjugated diene polymer (component (II)) having at least 1 selected from the group consisting of hydroxyl groups and carboxyl groups and the elastomer having an epoxy group (component (III)) in the molded article of the present embodiment, a solvent in which the modified conjugated diene polymer (component (II)), the elastomer having an epoxy group (component (III)) but not the polyphenylene sulfide resin, the polyethylene terephthalate resin, and the polybutylene terephthalate resin (component (I)) as a matrix resin are dissolved is first used in combination with the resin composition, and the unreacted modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) are extracted. When the base resin is a polyphenylene sulfide resin, since there is no solvent for dissolving the polyphenylene sulfide resin at 200 ℃ or lower, the solvent and the resin composition are mixed at a temperature of 50 to 200 ℃ to extract the unreacted polyphenylene sulfide resin (component (I)), the unreacted modified conjugated diene polymer (component (II)), and the unreacted elastomer having an epoxy group (component (III)).
Examples of the solvent include toluene, cyclohexane, xylene, tetrahydrofuran, chloroform, nitroethane, nitropropane, and ethylbenzene, and chloroform, nitroethane, nitropropane, ethylbenzene, and toluene are preferable from the viewpoint of solubility.
After the extraction, the unreacted modified conjugated diene polymer (component (II)) and the unreacted elastomer having an epoxy group (component (III)) can be separated by removing the undissolved matrix resin by filtration or the like and subjecting the filtrate to liquid chromatography.
In the case where the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) have different solubilities, the following method may be employed: the unreacted modified conjugated diene polymer (component (II)) and the unreacted elastomer having an epoxy group (component (III)) are separated by using a solvent in which the modified conjugated diene polymer (component (II)) but the elastomer having an epoxy group (component (III)) cannot be dissolved, removing the solvent from the filtrate by vacuum drying or the like, and mixing the thus obtained mixture of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) again in an appropriate solvent.
In general, examples of the solvent having high solubility of the modified conjugated diene polymer (component (II)) include toluene, cyclohexane, and tetrahydrofuran.
The identification of the epoxy group of the modified conjugated diene polymer (component (II)), the elastomer having an epoxy group (component (III)) can be performed by Nuclear Magnetic Resonance (NMR), infrared absorption spectroscopy (IR), gas chromatography (GS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), or the like.
In the case where the resin composition contains components such as additives which are described later and which are soluble in the solvent in the above-mentioned extraction step, the components can be separated by utilizing differences in molecular weight and polarity by liquid chromatography or the like, and can be identified by the above NMR, IR, GS, TOF-SIMS or the like.
As an analysis method without using a solvent, the structural unit of the unreacted modified conjugated diene polymer (component (II)), the unreacted elastomer having an epoxy group (component (III)), the kind of the polar group bonded to the unreacted modified conjugated diene polymer, and the kind of the polar group bonded to the unreacted elastomer having an epoxy group may be determined based on the infrared absorption spectrum obtained by observation with an Atomic Force Microscope (AFM).
Examples of the test piece for AFM measurement include a precise cross section of a resin composition produced by an ultra-thin microtome or the like.
Further, image stacking data may be obtained by using a scanning transmission X-ray microscope, a spectrum may be extracted from a characteristic region of the image stacking data, and a map may be prepared by component-by-component decomposition using the spectrum as a specific value of a reference spectrum, whereby a structural unit of an unreacted modified conjugated diene polymer (component (II)), an unreacted elastomer having an epoxy group (component (III)), a polar group species bonded to the unreacted modified conjugated diene polymer, and a polar group species bonded to the unreacted elastomer having an epoxy group may be determined.
Regarding the content ratio of the polar group-containing resin (component (I)), the modified conjugated diene polymer (component (II)), and the epoxy group-containing elastomer (component (III)) in the resin composition of the present embodiment, the content ratio of the polar group-containing resin (component (I)) to the modified conjugated diene polymer (component (II)) and the epoxy group-containing elastomer (component (III)) can be calculated by observing the dispersed state of the polar group-containing resin (component (I)) and the epoxy group-containing elastomer (component (III)) using an electron microscope such as the AFM, TEM, or SEM, and binarizing or binarizing each layer using image analysis software or the like on the obtained image.
The content ratio of the modified conjugated diene polymer (component (II)) and the elastomer having an epoxy group (component (III)) can be calculated from the infrared absorption spectrum obtained by the AFM, the peak intensity of the skeleton (specifically, the vinyl aromatic monomer unit skeleton) of the modified conjugated diene polymer (component (II)) alone, and the ratio of the amount of the vinyl aromatic monomer unit to the conjugated diene monomer unit in the modified conjugated diene polymer calculated by separating the modified conjugated diene polymer by NMR, IR, GS, TOF-SIMS, and the like.
The molded article of the present embodiment can be formed into any shape according to the application. Examples thereof include various containers, cylindrical containers, and cases.
Specifically, there may be mentioned: the present invention relates to an electronic/electric component such as a protection/support member for a box-type electronic/electric component integrated module, a plurality of independent semiconductor or module, a sensor, an LED lamp, a connector, a socket, a resistor, a relay case, a switch, a bobbin, a capacitor, a variable capacitor case, an optical pickup device, a resonator, various terminal boards, a transformer, a plug, a printed board, a tuner, a speaker, a microphone, an earphone, a small motor, a magnetic head base, a power module, a terminal block, a semiconductor, a liquid crystal, an FDD bracket, an FDD chassis, a motor brush holder, a parabolic antenna, and a computer-related component.
Further, there may be mentioned household and office electrical product parts such as a VTR part, a television part, an iron, a blower, an electric cooker part, a microwave oven part, an audio part, a voice device part such as an audio/laser video disc (registered trademark), an optical disc, a lighting part, a refrigerator part, an air conditioner part, a typewriter part, a word processor part, and a water circulation device part such as a hot water supply or a hot water supply for bath, a temperature sensor, and the like.
Further, there may be mentioned office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, washing jigs, motor parts, recorders, typewriters, and other mechanical-related parts.
Further, optical devices such as microscopes, binoculars, cameras, and watches, and precision machinery related parts can be mentioned.
Further, there may be mentioned various valves such as alternator terminals, alternator connectors, IC controllers, dimmer potentiometer mounts, relay boxes, inhibitor switches, exhaust valves, various pipes of fuel-related and exhaust systems and intake systems, intake nozzle ventilation pipes, intake manifolds, fuel pumps, engine cooling water joints, carburetor bodies, carburetor gaskets, exhaust gas sensors, cooling water sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crank shaft position sensors, air flow meters, brake pad wear sensors, air conditioner thermostat bases, heating hot air flow control valves, radiator motor brush holders, water pump impellers, turbine blades, wiper-related parts, dispensers, starter switches, ignition coils, motor insulators, motor rotors, motor cores, starter relays, power transmission wire harnesses, wiper nozzles, air conditioner panel switch boards, fuel-related solenoid valve coils, fuse joints, horn posts, electric component insulating boards, stepping motor rotors, lamp holders, lamp reflectors, lamp housings, brake pistons, solenoids, engine oil filters, vehicle housings, vehicle-related parts, etc.
The use of the molded article of the present embodiment is not limited to the above-described use.
Examples
The present embodiment will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the examples and comparative examples.
The structures of the modified conjugated diene polymers in examples and comparative examples and the methods for measuring and evaluating physical properties of the resin compositions are as follows.
[ measurement and evaluation of Structure of modified conjugated diene Polymer and physical Properties of resin composition ]
((1) vinyl bond content before hydrogenation of the modified conjugated diene Polymer)
Regarding the vinyl bond amount of the modified conjugated diene polymer, a polymer sampled during the polymerization of the polymer block containing the conjugated diene monomer in each step of the polymerization process of the modified conjugated diene polymer before hydrogenation is used, and the polymer is obtained by proton nuclear magnetic resonance [ ] 1 H-NMR) method.
The measurement apparatus used ECS400 (manufactured by JEOL), deuterated chloroform as a solvent, 50mg/mL as a sample concentration, 400MHz as an observation frequency, and tetramethylsilane as a chemical shift reference were used, and the measurement was performed at a pulse delay of 2.904 seconds, a number of scans of 64 times, a pulse width of 45℃and a measurement temperature of 26 ℃.
The vinyl bond amount was calculated from the integral value of the signal belonging to the 1, 4-bond and the 1, 2-bond, the integral value of each 1H of each bonding system was calculated, and then the ratio of the 1, 4-bond to the 1, 2-bond was calculated, and the calculation was performed by the following formula.
Vinyl bond amount= (1, 2-bond/(1, 4-bond+1, 2-bond))
((2) hydrogenation Rate of unsaturated bond of conjugated diene monomer unit based on modified conjugated diene Polymer)
Regarding the hydrogenation rate of the modified conjugated diene polymer,modified conjugated diene polymer after hydrogenation is used, and proton nuclear magnetic resonance is adopted 1 H-NMR).
The measurement conditions and the measurement data processing method are the same as those of (1) above.
Regarding the hydrogenation ratio, the integral value of the signal derived from the residual double bond and the signal derived from the hydrogenated conjugated diene at 4.5 to 5.5ppm was calculated, and the ratio thereof was calculated.
((3) butene amount (vinyl hydrogenation ratio) of the modified conjugated diene polymer with respect to the total of 100mol% of 1, 2-linkage and 1, 4-linkage based on conjugated diene monomer units)
Regarding the butene content of the modified conjugated diene polymer, which is 100mOl% based on the total of 1, 2-linkage and 1, 4-linkage based on the conjugated diene compound unit, the hydrogenated modified conjugated diene polymer was used, and the modified conjugated diene polymer was subjected to proton nuclear magnetic resonance [ (] 1 H-NMR).
The measurement conditions and the measurement data processing method are the same as those of (1) and (2) above.
The signal derived from the total amount of conjugated diene monomer units and the integral value derived from the butene amount in the hydrogenated modified conjugated diene polymer were calculated, and the ratio thereof was calculated.
In the calculation of the above ratio, the integral value of the signal belonging to butene (hydrogenated 1, 2-bond) in 0 to 2.0ppm of the spectrum is used. The amount of butene in the total of 100mol% based on the 1, 2-linkage and 1, 4-linkage of the conjugated diene monomer units is the vinyl hydrogenation rate.
((4) content of vinyl aromatic monomer unit of modified conjugated diene-based polymer (hereinafter also referred to as "styrene content"))
Regarding the content of vinyl aromatic monomer units, a modified conjugated diene polymer is used, and the modified conjugated diene polymer is prepared by proton nuclear magnetic resonance 1 H-NMR) method.
The measurement apparatus used ECS400 (manufactured by JEOL), the solvent used deuterated chloroform, the sample concentration was 50mg/mL, the observation frequency was 400MHz, and the chemical shift reference used tetramethylsilane, and the measurement was performed at a pulse delay of 2.904 seconds, a scan number of 64 times, a pulse width of 45℃and a measurement temperature of 26 ℃.
Regarding the styrene content, the calculation was performed using the integrated value of the total styrene aromatic signal in the spectrum of 6.2 to 7.5 ppm.
Further, the styrene content can be confirmed by calculating the content of the vinyl aromatic monomer unit for each polymer sampled at every step in the polymerization process of the modified conjugated diene polymer before hydrogenation.
((5) weight average molecular weight and molecular weight distribution of modified conjugated diene Polymer)
By GPC [ means: HLC8220 (east Cao Zhizao), column: TSKgelSUPER-HZM-N (4.6 mm. Times.30 cm) ] the weight average molecular weight and molecular weight distribution of the modified conjugated diene polymer were measured.
The solvent was determined using tetrahydrofuran.
The weight average molecular weight was determined from the peak molecular weight of the chromatogram using a calibration curve obtained by measuring a commercially available standard polystyrene (prepared by using the peak molecular weight of the standard polystyrene).
The weight average molecular weight was obtained from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak of the chromatogram) in the case where the chromatogram had a plurality of peaks.
The molecular weight distribution was calculated from the ratio of the obtained weight average molecular weight (Mw) to the number average molecular weight (Mn).
((6) modification ratio of modified conjugated diene Polymer)
The characteristic that the modified component is adsorbed by a GPC column using silica gel as a filler is applied to a sample solution containing a modified conjugated diene polymer and a low molecular weight internal standard polystyrene, and the ratio of the modified conjugated diene polymer to the standard polystyrene in the chromatogram measured in (5) is as follows: LC-10 (manufactured by shimadzu corporation), column: the ratio of the modified conjugated diene polymer to the standard polystyrene in the chromatogram measured by Zorbax (DuPont) was compared, and the amount of adsorption on the silica column was measured based on the difference between the ratios, and the ratio was used as the modification ratio. The modification ratio (%) of the amino group having a specific structure at the end was calculated by the following formula.
[ number 1]
a: area of the whole polymer measured by polystyrene gel (PLgel) (%)
b: area (%)
c: area of the whole polymer measured by silica column (Zorbax) (%)
d: area (%)
((7) glycidyl methacrylate ester bond content)
The modified conjugated diene polymer is refluxed in acetone at 60 ℃ for more than 1 hour, and unreacted glycidyl methacrylate is removed. The modified conjugated diene polymer after the reflux is dissolved in toluene, hydrochloric acid 2mol times as much as the amount of glycidyl methacrylate added during the extrusion reaction is added, and the reflux is performed at 60 ℃ for 30 minutes or more, whereby the epoxy group of glycidyl methacrylate is reacted with hydrochloric acid. The unreacted hydrochloric acid was quantified by titrating the toluene solution after the reaction with potassium hydroxide having a coefficient of 1±0.05, and the amount of glycidyl methacrylate bonded to the modified conjugated diene polymer was calculated from the amount of hydrochloric acid reacted.
((8) maleic anhydride-bonded amount)
The modified conjugated diene polymer was dissolved in toluene, and titration was performed with a methanol solution of sodium methoxide having a coefficient of 1±0.05 to calculate the maleic anhydride-bonded amount.
((9) toughness of resin composition)
According to ISO527, a tensile tester [ apparatus: the tensile elongation at break of the resin composition was measured for TG-5kN (manufactured by Minebea Mitsumi).
In the case where polyethylene terephthalate and polyphenylene sulfide resins as thermoplastic resins were used as the component (I), the test piece was measured at a tensile test speed of 50 mm/min using ISO-527-2-1A dumbbell-shaped test pieces molded by a benefit injection molding machine.
For each composition, 3 or more test pieces were tested, and the average value thereof was used as a physical property value.
When an epoxy resin as a thermosetting resin was used as the component (I), a test piece defined in JIS K6911.18.1 (2) was produced and the tensile test speed was measured at 5 mm/min.
((10) Charpy impact value)
When polyethylene terephthalate and polyphenylene sulfide resin are used as the component (I), notched Charpy impact strength is measured in accordance with JIS K7111-1, and evaluated. The test piece was cut at both ends of the above-mentioned ISO dumbbell-shaped test piece, and a strip-shaped test piece having a length of about 80mm, a width of about 10mm, and a thickness of about 4mm was produced in parallel, and the shape of the notch was A and the striking direction was along the edge.
When an epoxy resin as a thermosetting resin was used as the component (I), a test piece defined in JIS K6911.5.20.2 was prepared, the notch shape was defined as a, and the striking direction was defined as a side.
The measurement temperature was set at normal temperature (23 ℃) and-30 ℃. In kJ/m 2 。
((11) processability (flowability of resin composition))
When polyethylene terephthalate or polyphenylene sulfide resin is used as the component (I), the spiral flow length of the resin composition is measured by the following method, and the processability is evaluated.
The longer the spiral flow length, the higher the flowability and the better the processability.
The resin composition was put into an injection molding machine (mold clamping pressure 18tf, screw system Φ16, SL screw) having a barrel temperature set at 300 to 320 ℃ (feed hopper side to nozzle side), and injection molding was performed at a filling rate of 50mm/s and an injection pressure of 100MPa in a screw flow measuring mold having a screw width of 5mm, a screw thickness of 3mm, a screw longest length of 850mm, and an imprint width of 10mm under conditions of a screw rotation speed of 150rpm, a back pressure of 2MPa, and a metering completion position of 55 mm. The spiral flow length (cm) was measured with a cooling time of 20 s.
((12) observation of the phase Structure of the resin composition, measurement of the number-average particle diameter of the dispersed phase)
Regarding the phase structure in the resin composition, a molded article for test (ISO-527-2-1A) of the resin composition described later was subjected to ultrasonic cleaning in ethanol for about 1 hour, and was cut with an ultra-thin microtome, and the cross section was cut out for observation. The cutting was performed by using a glass cutter and a diamond cutter at-150 ℃ to thereby produce a precise cross section for AFM observation.
AFM was performed using a product manufactured by Bruker, inc., and probe was performed using SCANASYST-AIR.
The precise cross-section sample was fixed to a dedicated sample fixing stage, the measurement Mode was QMN Mode in Air, the resolution was 512×256 pixels, the measurement range was 10×10 μm, the maximum press-in load was 500pN, and the Scan speed was 1.0Hz, and an elastic modulus map was prepared from the obtained elastic modulus force curve. The elastic modulus map is an image in which a high elastic modulus is represented as bright and a low elastic modulus is represented as dark, and is output at 512×512 pixels. In order to remove noise, a 2-point moving average filter process is performed to create a binary image. The binarization treatment uses the Ojin method.
In the above particle analysis of the binarized image, the feret diameter was calculated for each particle of the dispersed phase (B) using Analyze Partickles of ImageJ.
For each resin composition, observation and calculation of the feret diameter were performed on 3 molded articles, and the average value of the feret diameters was used as the number average dispersion diameter of the dispersed phase (B).
[ production of resin composition ]
Component (I) resin having polar group
Component (I): as the resin having a polar group, the following polar resin is used.
Polyphenylene sulfide resin: a900 (Dongli Co., ltd.)
Polyethylene terephthalate resin: TRF-8550FF (manufactured by Di ren Co., ltd.)
Epoxy resin: bisphenol A type EXA-850CRP (manufactured by DIC Co., ltd.)
(component (II))
The component (II) is produced by a method for producing a modified conjugated diene polymer described later.
The modifier, other components and hydrogenation catalyst used in the production are as follows.
[ modifier ]
The following compounds were used as the modifiers for producing the modified conjugated diene polymers.
Maleic anhydride (manufactured by Hibiscus 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 Nipple Co., ltd.)
[ other Components ]
Curing agent for epoxy resin: cresol novolac resin LF-6161 (DIC corporation)
[ hydrogenation catalyst ]
A hydrogenation catalyst used in the hydrogenation reaction of the modified conjugated diene polymer is prepared by the following method.
To the reaction vessel subjected to nitrogen substitution, 1L of cyclohexane which had been dried and purified was added, 100 mmol of bis (. Eta.5-cyclopentadiene) titanium dichloride was added, and while stirring sufficiently, a solution of n-hexane containing 200 mmol of trimethylaluminum was added, and the mixture was reacted at room temperature for about 3 days to obtain a hydrogenation catalyst.
< production of modified conjugated diene Polymer (1) >
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, a cyclohexane solution (concentration: 20 mass%) containing 10 parts by mass of styrene was charged.
Then, 0.11 parts by mass of n-butyllithium and 0.4 momicron of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and the mixture was polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 80 parts by mass of butadiene was added thereto, and polymerization was carried out at 70℃for 45 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 10 parts by mass of styrene was charged, and polymerization was carried out at 70℃for 20 minutes.
Then, 1, 3-dimethyl-2-imidazolidinone (hereinafter also referred to simply as "DMI") was added in an equimolar amount to 1 mole of n-butyllithium, and the mixture was reacted at 70℃for 10 minutes. After the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (1-A) thus obtained had a styrene content of 20% by mass and a weight-average molecular weight of 12.2X10 4 The molecular weight distribution was 1.10, the vinyl bond content was 44%, and the modification ratio was 70% (the number of modifying groups per 1 polymer chain was 0.70).
Further, to the obtained terminal amine-modified conjugated diene polymer (1-A), 50ppm of the hydrogenation catalyst prepared as described above based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (1-A) was added, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7MPa and a temperature of 80℃for about 2.0 hours.
Then, 0.25 part by mass of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (1-A), to obtain a terminal amine-modified hydrogenated conjugated diene polymer (1-B). The hydrogenation ratio of the obtained terminal amine-modified hydrogenated conjugated diene polymer (1-B) was 73% and the vinyl hydrogenation ratio was 96%.
The terminal amine-modified hydrogenated conjugated diene polymer (1-B) obtained as described above is mixed with maleic anhydride, and then fed to a twin screw extruder in which the temperature of the whole length region of the extruder is set to 150 to 200℃to be compounded, whereby the terminal carboxyl group-modified conjugated diene polymer (1-C) is obtained.
GPC measurement of the obtained terminal carboxyl group-modified conjugated diene polymer (1-C) under the above conditions revealed that adsorption of amino groups on the column did not occur.
That is, it means that the total amount of amino groups reacts with maleic anhydride, and the number of modified groups per 1 polymer chain is 0.70, as in the amino groups.
< modified conjugated diene Polymer (2) >)
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, a cyclohexane solution (concentration: 20 mass%) containing 10 parts by mass of styrene was charged.
Then, 0.11 parts by mass of n-butyllithium and 0.4 momicron of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and the mixture was polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 80 parts by mass of butadiene was added thereto, and polymerization was carried out at 70℃for 45 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 10 parts by mass of styrene was charged, and polymerization was carried out at 70℃for 20 minutes.
1.1 mol of 1, 3-dimethyl-2-imidazolidinone (hereinafter also referred to simply as "DMI") was then added to 1 mol of n-butyllithium, and the mixture was reacted at 70℃for 15 minutes. After the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (2-A) thus obtained had a styrene content of 20% by mass and a weight-average molecular weight of 12.1X10 4 The molecular weight distribution was 1.10, the vinyl bond content was 45%, and the modification ratio was 80% (the number of modifying groups per 1 polymer chain was 0.80).
Further, to the obtained terminal amine-modified conjugated diene polymer (2-A), 50ppm of the hydrogenation catalyst prepared as described above based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (2-A) was added, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7MPa and a temperature of 80℃for about 2.0 hours.
Then, 0.25 part by mass of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (2-A), to obtain a terminal amine-modified hydrogenated conjugated diene polymer (2-B).
The hydrogenation ratio of the obtained terminal amine-modified hydrogenated conjugated diene polymer (2-B) was 74% and the vinyl hydrogenation ratio was 96%.
The terminal amine-modified hydrogenated conjugated diene polymer (2-B) obtained as described above is mixed with maleic anhydride, and then fed to a twin screw extruder in which the temperature of the whole length region of the extruder is set to 150 to 200℃to be compounded, whereby the terminal carboxyl group-modified conjugated diene polymer (2-C) is obtained.
GPC measurement of the obtained terminal carboxyl group-modified conjugated diene polymer (2-C) under the above conditions revealed that adsorption of amino groups on the column did not occur.
That is, it means that the total amount of amino groups reacts with maleic anhydride, and the number of modified groups per 1 polymer chain is 0.80, as in the amino groups.
< modified conjugated diene Polymer (3) >)
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, 15 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged.
Then, 0.11 parts by mass of n-butyllithium and 0.4 momicron of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and the mixture was polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 70 parts by mass of butadiene was added thereto, and polymerization was carried out at 70℃for 45 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 15 parts by mass of styrene was charged, and polymerization was carried out at 70℃for 20 minutes.
1.1 mol of 1, 3-dimethyl-2-imidazolidinone (hereinafter also referred to simply as "DMI") was then added to 1 mol of n-butyllithium, and the mixture was reacted at 70℃for 15 minutes. After the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (3-A) thus obtained had a styrene content of 30% by mass and a weight-average molecular weight of 12.0X10 4 The molecular weight distribution was 1.09, the vinyl bond content was 43%, and the modification ratio was 79% (the number of modifying groups per 1 polymer chain was 0.79).
Further, to the obtained terminal amine-modified conjugated diene polymer (3-A), 50ppm of the hydrogenation catalyst prepared as described above based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (3-A) was added, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7MPa and a temperature of 80℃for about 2.0 hours.
Then, 0.25 part by mass of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (3-A), to obtain a terminal amine-modified hydrogenated conjugated diene polymer (3-B).
The hydrogenation ratio of the obtained terminal amine-modified hydrogenated conjugated diene polymer (3-B) was 75%, and the vinyl hydrogenation ratio was 96%.
The terminal amine-modified hydrogenated conjugated diene polymer (3-B) obtained as described above is mixed with maleic anhydride, and then fed to a twin screw extruder in which the temperature of the whole length region of the extruder is set to 150 to 200℃to be compounded, whereby the terminal carboxyl group-modified conjugated diene polymer (3-C) is obtained.
GPC measurement of the obtained terminal carboxyl group-modified conjugated diene polymer (3-C) under the above conditions revealed that adsorption of amino groups on the column did not occur.
That is, it means that the total amount of amino groups reacts with maleic anhydride, and the number of modified groups per 1 polymer chain is 0.79, as in the amino groups.
< modified conjugated diene Polymer (4) >)
The reaction was carried out in the same manner as above except that tetramethyl ethylenediamine (TMEDA) was added in an amount of 0.2 m.omic. l relative to 1 mol of n-butyllithium <Modified conjugated diene Polymer (2)>The same procedure gives the terminal carboxyl groupsThe base-modified conjugated diene polymer (4-C). The resulting carboxyl-terminated modified conjugated diene copolymer (4-C) had a styrene content of 20% by mass and a weight-average molecular weight of 12.2X10 4 The molecular weight distribution was 1.09, the vinyl bond content was 24%, the hydrogenation rate was 78%, the vinyl hydrogenation rate was 96%, and the modification rate was 80% (the number of modified groups per 1 polymer chain was 0.79).
< modified conjugated diene Polymer (5) >)
The same procedure as described above was conducted except that 0.09 parts by mass of n-butyllithium was added to 100 parts by mass of the whole monomer<Modified conjugated diene Polymer (2)>The same procedure was conducted to obtain a carboxyl-terminated modified conjugated diene polymer (5-C). The resulting carboxyl-terminated modified conjugated diene copolymer (5-C) had a styrene content of 20% by mass and a weight-average molecular weight of 10.1X10 4 The molecular weight distribution was 1.10, the vinyl bond content was 43%, the hydrogenation rate was 78%, the vinyl hydrogenation rate was 96%, and the modification rate was 80% (the number of modifying groups per 1 polymer chain was 0.80).
< modified conjugated diene Polymer (6) >)
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, a cyclohexane solution containing 6.5 parts by mass of styrene (concentration: 20% by mass) was charged.
Then, 0.11 parts by mass of n-butyllithium and 0.35 mOl of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 87 parts by mass of butadiene was added, and polymerization was carried out at 70℃for 45 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 6.5 parts by mass of styrene was charged, and polymerization was carried out at 70℃for 20 minutes.
1.1 mol of 1, 3-dimethyl-2-imidazolidinone (hereinafter also referred to simply as "DMI") was then added to 1 mol of n-butyllithium, and the mixture was reacted at 70℃for 15 minutes. After the reaction, methanol was added.
Obtained as described aboveIn the terminal amine-modified conjugated diene polymer (6-A), the styrene content was 13% by mass and the weight-average molecular weight was 12.2X10 4 The molecular weight distribution was 1.09, the vinyl bond content was 35%, and the modification ratio was 81% (the number of modifying groups per 1 polymer chain was 0.81).
Further, to the obtained terminal amine-modified conjugated diene polymer (6-A), 90ppm of the hydrogenation catalyst prepared as described above based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (6-A) was added, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7MPa and a temperature of 80℃for about 2.0 hours.
Then, 0.25 part by mass of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (6-A), to obtain a terminal amine-modified hydrogenated conjugated diene polymer (6-B).
The hydrogenation ratio of the obtained terminal amine-modified hydrogenated conjugated diene polymer (6-B) was 80%, and the vinyl hydrogenation ratio was 98%.
The terminal amine-modified hydrogenated conjugated diene polymer (6-B) obtained as described above is mixed with maleic anhydride, and then fed to a twin screw extruder in which the temperature of the whole length region of the extruder is set to 150 to 200℃to be compounded, whereby the terminal carboxyl group-modified conjugated diene polymer (6-C) is obtained.
GPC measurement of the obtained terminal carboxyl group-modified conjugated diene polymer (6-C) under the above conditions revealed that adsorption of amino groups on the column did not occur.
That is, it means that the total amount of amino groups reacts with maleic anhydride, and the number of modified groups per 1 polymer chain is 0.81 as in the case of amino groups.
< modified conjugated diene Polymer (7) >)
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, 25 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged.
Then, 0.11 parts by mass of n-butyllithium and 0.4 momicron of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and the mixture was polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 50 parts by mass of butadiene was added thereto, and polymerization was carried out at 70℃for 45 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 25 parts by mass of styrene was charged, and polymerization was carried out at 70℃for 20 minutes.
1.1 mol of 1, 3-dimethyl-2-imidazolidinone (hereinafter also referred to simply as "DMI") was then added to 1 mol of n-butyllithium, and the mixture was reacted at 70℃for 15 minutes. After the reaction, methanol was added.
The terminal amine-modified conjugated diene polymer (7-A) thus obtained had a styrene content of 50% by mass and a weight-average molecular weight of 11.9X10 4 The molecular weight distribution was 1.11, the vinyl bond content was 43%, and the modification ratio was 79% (the number of modifying groups per 1 polymer chain was 0.79).
Further, the hydrogenation catalyst prepared as described above was added to the obtained terminal amine-modified conjugated diene polymer (7-A) in an amount of 50ppm based on Ti per 100 parts by mass of the terminal amine-modified conjugated diene polymer (7-A), and the reaction was carried out under a hydrogen pressure of 0.7MPa at a temperature of 80℃for about 2.0 hours.
Then, 0.25 part by mass of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the terminal amine-modified conjugated diene polymer (7-A), to obtain a terminal amine-modified hydrogenated conjugated diene polymer (7-B).
The hydrogenation ratio of the obtained terminal amine-modified hydrogenated conjugated diene polymer (7-B) was 77% and the vinyl hydrogenation ratio was 97%.
The terminal amine-modified hydrogenated conjugated diene polymer (7-B) obtained as described above is mixed with maleic anhydride, and then fed to a twin screw extruder in which the temperature of the whole length region of the extruder is set to 150 to 200℃to be compounded, whereby the terminal carboxyl group-modified conjugated diene polymer (7-C) is obtained.
GPC measurement of the obtained terminal carboxyl group-modified conjugated diene polymer (7-C) under the above conditions revealed that adsorption of amino groups on the column did not occur.
That is, it means that the total amount of amino groups reacts with maleic anhydride, and the number of modified groups per 1 polymer chain is 0.79, as in the amino groups.
< modified conjugated diene Polymer (8) >)
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, a cyclohexane solution (concentration: 20 mass%) containing 10 parts by mass of styrene was charged.
Then, 0.11 parts by mass of n-butyllithium and 0.35 mOl of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 80 parts by mass of butadiene was added thereto, and polymerization was carried out at 70℃for 45 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 10 parts by mass of styrene was charged, and polymerization was carried out at 70℃for 20 minutes.
Methanol was then added.
The conjugated diene polymer (8-A) obtained as described above had a styrene content of 30% by mass and a weight average molecular weight of 12.1X10 4 The molecular weight distribution was 1.10 and the vinyl bond content was 36%.
Further, to the obtained conjugated diene polymer (8-A), 70ppm of the hydrogenation catalyst prepared as described above based on 100 parts by mass of the conjugated diene polymer (8-A) was added, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7MPa and a temperature of 80℃for about 3.0 hours.
Then, 0.25 part by mass of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the conjugated diene polymer (8-A), to obtain a hydrogenated conjugated diene polymer (8-B).
The hydrogenation rate of the hydrogenated conjugated diene polymer (8-B) obtained was 97%, and the vinyl hydrogenation rate was 99%.
The hydrogenated conjugated diene polymer (8-B) obtained as described above was mixed with glycidyl methacrylate, and then fed into a twin screw extruder in which the temperature of the entire length region of the extruder was set to 150 to 220℃to prepare a main chain epoxy-modified conjugated diene polymer (8-C) by adding perox 25B from the middle of the extruder and compounding.
The resulting main chain epoxy group-modified conjugated diene polymer (8-C) was titrated by the above method, and as a result, the amount of glycidyl methacrylate ester bond was 1.2 mass%.
< modified conjugated diene Polymer (9) >)
Batch polymerization was carried out using a tank reactor (internal volume 10L) equipped with a stirring device and a jacket.
First, 15 parts by mass of a cyclohexane solution (concentration: 20% by mass) containing styrene was charged.
Then, 0.11 parts by mass of n-butyllithium and 0.35 mOl of tetramethyl ethylenediamine (TMEDA) were added to 100 parts by mass of the total monomers, and polymerized at 70℃for 20 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 70 parts by mass of butadiene was added thereto, and polymerization was carried out at 70℃for 45 minutes.
Then, a cyclohexane solution (concentration: 20 mass%) containing 15 parts by mass of styrene was charged, and polymerization was carried out at 70℃for 20 minutes.
Methanol was then added.
The conjugated diene polymer (9-A) obtained as described above had a styrene content of 30% by mass and a weight-average molecular weight of 12.2X10 4 The molecular weight distribution was 1.08 and the vinyl bond content was 37%.
Further, to the obtained conjugated diene polymer (9-A), 50ppm of the hydrogenation catalyst prepared as described above based on 100 parts by mass of the conjugated diene polymer (9-A) was added, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7MPa and a temperature of 80℃for about 2.0 hours.
Then, 0.25 part by mass of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the conjugated diene polymer (9-A), to obtain a hydrogenated conjugated diene polymer (9-B).
The hydrogenation rate of the hydrogenated conjugated diene polymer (9-B) obtained was 76% and the vinyl hydrogenation rate was 96%.
The hydrogenated conjugated diene polymer (9-B) obtained as described above, maleic anhydride, and an organic peroxide (PERCEXA 25B (manufactured by Nikko Co., ltd.) were mixed, and then fed to a twin-screw extruder having a temperature set to 150 to 220℃over the entire length of the extruder, and compounded, whereby a main chain acid anhydride group-modified conjugated diene polymer (9-C) was obtained.
The resulting main chain acid anhydride-modified conjugated diene polymer (9-C) was titrated by the method shown in the above ((8) maleic anhydride-bonded amount), and as a result, the maleic anhydride-bonded amount was 1.5 mass%.
< modified conjugated diene Polymer (10) >)
Conjugated diene polymer M1943 (Tuftec, manufactured by Asahi chemical Co., ltd.) was modified with a main chain acid anhydride group.
( Component (III): polymers having polar groups reactive with Components (I), (II) )
As component (III), the following polymer having an epoxy group was used.
Bondfast BF-7M (glycidyl methacrylate-ethylene-methyl acrylate copolymer, manufactured by Sumitomo chemical Co., ltd.)
Epofrind AT501 (epoxide of styrene-butadiene block copolymer, manufactured by Daicel, inc.)
ELVAOY TM PTW (ethylene-glycidyl methacrylate-butyl acrylate copolymer, manufactured by Dow Corp.)
Examples 1 to 15
Using the above components, resin compositions were produced by melt-kneading the components at a barrel set temperature of 300℃and a screw rotation speed of 200rpm and a discharge amount of 9 kg/hr using a twin-screw extruder ZSK28 (manufactured by Werner and Pfleiderer) in the composition ratios shown in Table 1 and Table 2.
Thereafter, a test piece (ISO-527-2-1A) was produced by injection molding using an injection molding machine under conditions of a barrel set temperature of 300℃and a mold temperature of 140 ℃.
Comparative examples 1 to 11
As the component (II), the modified conjugated diene polymers (1-B) and (1-C) are used.
Other materials and conditions were prepared in the same manner as in examples 1 to 15, except that resin compositions were prepared in the composition ratios shown in Table 3.
The number average dispersion particle diameter, toughness and impact resistance of the dispersed phase (B) of each resin composition are shown in tables 1 to 3.
In the table, "(1)" indicates that the test piece of the charpy impact test was not broken.
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Examples 16 to 22
Using the above-mentioned components (I) to (III), melt-kneading was performed at a barrel set temperature of 290℃and a screw rotation speed of 200rpm at a discharge amount of 9 kg/hr using a twin-screw extruder ZSK28 (manufactured by Werner and Pfleiderer) in the composition ratios shown in Table 4, to prepare a resin composition.
Thereafter, a test piece (ISO-527-2-1A) was produced by injection molding with an injection molding machine under conditions of a barrel set temperature of 290℃and a mold temperature of 120 ℃.
Comparative examples 12 to 15
As the component (II), a modified conjugated diene polymer (9-B) is used.
Other materials and conditions were prepared in the same manner as in examples 16 to 22, and resin compositions were prepared in the composition ratios shown in Table 5.
The number average dispersion particle diameter, toughness and impact resistance of the dispersed phase (B) of each resin composition are shown in tables 4 and 5.
Examples 23 to 27
Resin compositions were produced in the composition ratios shown in Table 6 using the above components.
In the case of kneading, when component (II) and component (III) are contained, component (III) is dissolved in toluene at a concentration of about 20 mass%, and added to the epoxy resin solution, followed by stirring.
Then, vacuum drying was performed at normal temperature to remove most of toluene. Next, a curing agent is added and stirred, thereby obtaining a resin composition in a solution state.
Next, the resin composition in the solution state was heated to 80 ℃, and then the resin composition in the solution state was injected into a mold having a shape defined by the toughness test and the charpy impact test, and compression molding was performed at 140 ℃ for 2 hours, thereby obtaining a cured product of the resin composition.
The number average dispersion particle diameter, toughness and impact resistance of the dispersed phase (B) of each resin composition are shown in table 6.
Comparative examples 16 to 21
As the component (II), a modified conjugated diene polymer (9-B) is used.
Other materials and conditions were prepared in the same manner as in examples 23 to 27, and resin compositions were prepared in the composition ratios shown in Table 7.
The number average dispersion particle diameter, toughness and impact resistance of the dispersed phase (B) of each resin composition are shown in tables 6 and 7.
As is clear from the results in tables 1 to 7, examples 1 to 27 were excellent in impact resistance and toughness.
The present application is based on japanese patent application (japanese patent application No. 2021-122776) filed by the japanese patent office at 7.7.month.27) and japanese patent application (japanese patent application No. 2021-153417) filed by the japanese patent office at 9.21.2021, the contents of which are incorporated herein by reference.
Industrial applicability
The resin composition of the present invention is useful as various molded articles such as sheets, films, injection molded articles of various shapes, hollow molded articles, pressure molded articles, vacuum molded articles, extrusion molded articles, foam molded articles, nonwoven fabric or fibrous molded articles, synthetic leather, etc., and has industrial applicability as automobile interior and exterior materials, building materials, toys, household electrical appliance parts, medical appliances, industrial parts, various hoses, various housings, various module housings, various power control unit parts, other miscellaneous goods, etc.

Claims (15)

1. A resin composition comprising component (I) and at least one component (II),
component (I): a resin having a polar group, excluding the following component (II);
component (II): a modified conjugated diene polymer obtained by bonding at least one polar group selected from the group consisting of an acid anhydride group, a hydroxyl group, a carboxyl group, a dicarboxylic group, an epoxy group, an oxetanyl group and an amino group to a block polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (A) mainly composed of a vinyl aromatic monomer unit, a polymer block (B) mainly composed of a conjugated diene monomer unit, and a random polymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
Wherein,
the resin composition comprises a continuous phase (A) of the component (I) and a dispersed phase (B) containing the component (II) dispersed in the continuous phase (A), wherein the number average dispersion particle diameter of the dispersed phase (B) is 1.5 [ mu ] m or less,
the mass ratio of the component (I) to the component (II) is as follows: component (II) =50/50 to 99/1.
2. The resin composition according to claim 1, wherein,
the resin composition further comprises component (III): a polymer having a polar group reactive with the component (I) and/or the component (II), excluding the components (I), (II),
the mass ratio of the component (II) to the component (III) is as follows: component (III) =1/99 to 99/1.
3. The resin composition according to claim 1, wherein the component (I) comprises 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.
4. The resin composition according to claim 2, wherein the component (I) comprises 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.
5. The resin composition according to claim 3 or 4, wherein the component (II) comprises a hydrogenated modified conjugated diene polymer obtained by hydrogenating an aliphatic double bond derived from a conjugated diene compound.
6. The resin composition according to claim 3 or 4, wherein the component (I) is a polyphenylene sulfide resin.
7. The resin composition according to claim 3 or 4, wherein the component (II) comprises a modified conjugated diene polymer to which at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group is bonded.
8. A resin composition according to claim 2 or 3, wherein 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 oxetane group.
9. A resin composition according to claim 2 or 3, wherein the component (III) is an olefin-based elastomer having an epoxy group.
10. The resin composition according to claim 5, wherein the hydrogenation rate of the hydrogenated modified conjugated diene polymer is 90% or less.
11. The resin composition according to claim 3 or 4, wherein the content of the vinyl aromatic monomer unit in the component (II) is 40% by mass or less.
12. The resin composition according to claim 2 or 3, wherein the component (III) is an elastomer having an epoxy group composed of a copolymer of a polymerizable monomer having an epoxy group and an unsaturated hydrocarbon compound.
13. The resin composition according to claim 2 or 3, wherein the component (III) is a copolymer of a polymerizable monomer having an epoxy group and an unsaturated hydrocarbon compound with (meth) acrylate and/or vinyl acetate.
14. A method for producing a resin composition, wherein,
comprises a step of kneading a component (II), a component (I) and a component (III) to obtain a resin composition,
the component (II) is a modified conjugated diene polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a random polymer block (C) mainly composed of vinyl aromatic monomer units and conjugated diene monomer units, and having at least one polar group selected from the group consisting of hydroxyl groups and carboxyl groups,
the component (I) is at least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins and polybutylene terephthalate-based resins,
The component (III) is an olefin elastomer having at least one polar group selected from the group consisting of an epoxy group, an oxazoline group and an oxetane group,
the mass ratio of the component (I) which is the resin having a polar group to the component (II) which is the modified conjugated diene polymer is set to be a resin having a polar group: modified conjugated diene polymer=50/50 to 99/1,
the mass ratio of the modified conjugated diene polymer to the polar-group-containing olefin elastomer is set to be the modified conjugated diene polymer: olefin elastomer having polar group=1/99 to 99/1,
the method for producing the resin composition comprises a continuous phase (A) comprising a component (I) which is the polar-group-containing resin, and a dispersed phase (B) comprising a component (II) which is the modified conjugated diene polymer dispersed in the continuous phase (A), wherein the number average particle diameter of the dispersed phase (B) is 1.5 [ mu ] m or less.
15. A molded article comprising a resin composition containing component (I), component (II) and component (III),
the component (I) is at least one resin having a polar group selected from the group consisting of polyphenylene sulfide-based resins, polyethylene terephthalate-based resins, and polybutylene terephthalate-based resins,
The component (II) is a modified conjugated diene polymer having at least 2 polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, a random polymer block (C) mainly composed of vinyl aromatic monomer units and conjugated diene monomer units,
the component (III) is an olefin elastomer having an epoxy group,
wherein,
the component (II) which is the modified conjugated diene polymer has at least one polar group selected from the group consisting of a hydroxyl group and a carboxyl group,
the molded article satisfies the following conditions (I-1) to (II-1),
< condition (I-1) >
A long test piece having a width of 10mm, a length of 170mm, and a thickness of 2mm, which is obtained from the molded article, has a tensile elongation at break of 25% or more at room temperature under a tensile speed of 5 mm/min;
< conditions (II-1)
A long test piece having a length of about 80mm, a width of about 10mm, and a thickness of about 4mm obtained from the molded article has a Charpy impact value of 15kJ/m in a Charpy impact test at a temperature of-30 DEG C 2 。
CN202280044175.5A 2021-07-27 2022-07-26 A resin composition method for producing resin composition and molded article Pending CN117545808A (en)

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JP2021153417 2021-09-21
JP2021-153417 2021-09-21
PCT/JP2022/028771 WO2023008424A1 (en) 2021-07-27 2022-07-26 Resin composition, method for producing resin composition, and molded body

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