JP2024162024A - Block copolymer, composition, molded article, and methods for producing the same - Google Patents

Abstract

To provide a method for simply producing a block copolymer containing polyarylene sulfide resin segments, enabling the application of various copolymerization components, as well as a block copolymer, a composition and a molded product.SOLUTION: A block copolymer contains a polyarylene sulfide block made from a cyclic polyarylene sulfide (A), and another block made from a thermoplastic resin (B) other than the polyarylene sulfide, where the thermoplastic resin (B) other than the polyarylene sulfide does not have cyclic structures.SELECTED DRAWING: Figure 1

Description

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

In recent years, polymeric materials have been widely used in various fields and applications, and their applications span all industrial fields, including not only everyday products but also automobiles, aircraft, electronic devices, medical devices, etc. One of the reasons for this is that polymeric materials can flexibly respond to the needs of each field and application by controlling their primary and higher-order structures. Among them, polyarylene sulfides (PAS), represented by polyphenylene sulfide (PPS) resin, have properties suitable for engineering plastics, such as excellent heat resistance, flame retardancy, chemical resistance, dimensional stability, rigidity, and electrical insulation, and are therefore used mainly for injection molding applications, as well as for various automobile parts, machine parts, and electrical and electronic parts.

Compared to engineering plastics such as polyamide resins and polybutylene terephthalate resins, PAS resins are inferior in terms of toughness, moldability, and secondary processability such as adhesion and plating, and various methods have been considered to improve these. For example, polymer alloy technology, which blends PAS resin with other resins, is a technology that can bring out the advantages of each resin and compensate for their disadvantages, thereby enabling the resin to exhibit superior properties compared to a single resin. However, PAS resins have extremely low compatibility with other resins, and the effect of improving physical properties is insufficient. Polyphenylene sulfide resin compositions that are phase-separated using spinodal decomposition as a method of promoting compatibility have also been disclosed (see Patent Documents 1 and 2, etc.), but since the phase structure is fixed by thermal curing or crystallization, it can change over time or by remelting, making it difficult to control the physical properties of molded products and final products.

Copolymers in which PAS resin is chemically bonded to other resins are effective for fixing the structure of PAS resin and other resins. To date, copolymer components have been disclosed, such as polysulfone (see Patent Document 3, etc.), polycarbonate (see Patent Document 4, etc.), wholly aromatic polyether (see Patent Document 5, etc.), polyether ether ketone (see Patent Document 6, etc.), aromatic polyester (see Patent Document 7, etc.), and cyclic compounds (see Patent Document 8, etc.). However, since all of these obtain copolymers by polymerizing monomer raw materials, there are limitations on the monomer raw materials that can be applied to the polymerization conditions of PAS resin and the introduction ratio of each copolymerization component. In addition, a lot of effort and equipment installation was required for adjusting the polymerization reaction conditions and refining, such as removing the by-product homopolymer.

International Publication No. 2009/041335 Patent Publication 2008-231249 Japanese Patent Application Publication No. 61-225218 Japanese Patent Application Publication No. 6-220183 JP 2004-168834 A Unexamined Japanese Patent Publication No. 2-228325 Japanese Patent Application Publication No. 11-222527 International Publication No. 2014/136448

The problem that the present invention aims to solve is to provide a method for easily producing a block copolymer containing a PAS resin moiety that can be applied to various copolymerization components, as well as a block copolymer, a composition, and a molded article.

As a result of intensive research to solve the above problems, the inventors discovered that a PAS block copolymer can be easily produced by melt-kneading cyclic PAS and a thermoplastic resin other than polyarylene sulfide as essential components, and thus completed the present invention.

That is, the present disclosure provides a block copolymer including a PAS block made from a cyclic PAS (A) and another block made from a thermoplastic resin (B) other than the PAS,
The present invention relates to a block copolymer, wherein the thermoplastic resin (B) other than PAS does not have a cyclic structure.

The present disclosure also provides a method for producing a block copolymer, comprising a step of blending a cyclic PAS (A) and a thermoplastic resin other than PAS (B) as essential components, and melt-kneading the blend at a temperature equal to or higher than the melting point of the cyclic PAS (A) and the flow temperature of the thermoplastic resin other than PAS (B),
The present invention relates to a method for producing a block copolymer, characterized in that the blending amount of the thermoplastic resin (B) other than the PAS is 0.1 to 1000 parts by mass per 1 part by mass of the cyclic PAS (A).

The present disclosure also relates to a block copolymer composition containing the block copolymer described above and other materials.

The present disclosure also relates to a method for producing a block copolymer composition, which includes a step of blending the block copolymer obtained by the above-described method for producing a block copolymer with other materials and melt-kneading the mixture.

The present disclosure also relates to a molded article obtained by melt molding the block copolymer described above.

The present disclosure also relates to a method for producing a molded article, which includes a step of melt-molding a block copolymer composition obtained by the method for producing a block copolymer composition described above.

In this disclosure, a compound having 4 to 40 repeating units (a mixture of tetramers to 40mers) may be referred to as an "oligomer."

The present invention provides a method for easily producing a block copolymer containing a PAS resin moiety that can be applied to various copolymerization components, as well as a block copolymer, a composition, and a molded article.

1 is an image obtained by scanning electron microscope observation of the resin composition of Example 1. No phase separation structure is observed, and the resin composition is in a homogeneous state.

1 is an image obtained by observing the resin composition of Comparative Example 1 with a scanning electron microscope, in which a sea-island phase separation structure is observed.

The following describes in detail an embodiment of the present invention, but the scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present invention. In addition, when multiple upper and lower limit values are listed for a specific parameter, any of these upper and lower limit values can be combined to create a suitable numerical range.

<Block copolymer>
The block copolymer according to this embodiment is a block copolymer including a PAS block made from a cyclic PAS (A) and another block made from a thermoplastic resin other than PAS (B), and is characterized in that the thermoplastic resin other than PAS (B) does not have a cyclic structure, as described below.

The polyarylene sulfide block (hereinafter, PAS block) made from the cyclic PAS (A) is a block having repeating units derived from the cyclic PAS (A).

The other block (hereinafter simply referred to as "other block") made from a thermoplastic resin (B) other than PAS is a block having repeating units derived from a thermoplastic resin other than PAS and not having a cyclic structure.

In the block copolymer according to this embodiment, the PAS block and the other block may be directly linked to each other via the terminal structures derived from the repeating units of each block, or may be linked via a structure other than the repeating units of each block. In addition, the number of repeats of each block is not particularly limited, and there may be a portion in the structure where the same block is repeated.

In the block copolymer according to this embodiment, the ratio of the PAS block to the other blocks is not particularly limited, but for example, the mass ratio of the PAS block to the other blocks can be 1/0.1 or more, preferably 1/0.5 or more, and more preferably 1/1 or more. Also, the mass ratio can be 1/1000 or less, preferably 1/800, more preferably 1/600, and even more preferably 1/400.

・Cyclic PAS (A)
In the block copolymer according to the present embodiment, the cyclic PAS (A) (hereinafter referred to as "component (A)") serving as the raw material of the PAS block has a cyclic resin structure having a repeating unit in which an aromatic ring and a sulfur atom are bonded, and specifically, the cyclic PAS (A) is represented by the following general formula (1):

（式中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１～４の範囲のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、エトキシ基を表す。）で表される構造部位を繰り返し単位とするポリマーである。

(wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group) as a repeating unit.

Here, the structural portion represented by the general formula (1) is preferably a hydrogen atom, particularly ^R1 and ^R2 in the formula, from the viewpoint of the mechanical strength of the PAS block, and in that case, is bonded at the para position represented by the following formula (2).

The (A) component may include not only the structural moieties represented by the general formulas (1) and (2) but also the structural moieties represented by the following structural formulas (3) to (6)

で表される構造部位を、前記一般式（１）と一般式（２）で表される構造部位との合計の３０モル％以下で含んでいてもよい。特に本開示では上記一般式（３）～（６）で表される構造部位は１０モル％以下であることが、ＰＡＳブロックが呈するの耐熱性、機械的強度の点から好ましい。前記（Ａ）成分中に、上記一般式（３）～（６）で表される構造部位を含む場合、それらの結合様式としては、ランダム共重合体、ブロック共重合体の何れであってもよい。

The structural moiety represented by the general formula (1) and the structural moiety represented by the general formula (2) may be contained in an amount of 30 mol % or less of the total of the structural moieties represented by the general formula (1) and the general formula (2). In particular, in the present disclosure, it is preferable that the structural moieties represented by the general formulae (3) to (6) are 10 mol % or less in terms of the heat resistance and mechanical strength of the PAS block. When the structural moieties represented by the general formulae (3) to (6) are contained in the component (A), the bonding mode thereof may be either a random copolymer or a block copolymer.

The (A) component may also have naphthyl sulfide bonds in its molecular structure, but this is preferably 3 mol % or less, and more preferably 1 mol % or less, relative to the total number of moles including other structural parts.

The number of repetitions of the structural portion represented by the general formula (1) of the component (A) is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of excellent reactivity, it is preferably a 4-40 mer, more preferably a 5-25 mer, and even more preferably a 6-17 mer. The component (A) may be either a cyclic PAS having a single repetition number or a mixture of cyclic PAS having different repetition numbers. The number of repetitions of the structural portion represented by the general formula (1) can be determined from structural analysis by NMR and mass spectrometry.

The weight average molecular weight of the (A) component is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of excellent reactivity exhibited by the PAS block, it is preferably 200 or more. More preferably, it is 400 or more, and even more preferably, it is 600 or more. From the same viewpoint, it is preferably 3000 or less, more preferably 2500 or less, and even more preferably 1700 or less. The weight average molecular weight in this disclosure can be determined by gel permeation chromatography.

(Method for producing cyclic PAS (A))
The method for producing the component (A) having the above-mentioned structure and properties is not particularly limited as long as it does not impair the effects of the present invention. For example, the component (A) can be produced by a method including the steps of: reacting a polyhalo aromatic compound with (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in an organic polar solvent to obtain a crude reaction mixture containing at least a PAS resin, a cyclic PAS, a linear PAS oligomer, an alkali metal halide and an organic polar solvent; removing solid phase components from the crude reaction mixture by solid-liquid separation to obtain a liquid phase component containing at least a cyclic PAS and a linear PAS oligomer; and obtaining a cyclic PAS from the liquid phase component.

-Step (1)-
Step (1) is a step of reacting a polyhalo aromatic compound with (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in an organic polar solvent to obtain a crude reaction mixture containing at least a PAS resin, a cyclic PAS, a linear PAS oligomer, an alkali metal halide and an organic polar solvent.

The polyhalo aromatic compound is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic ring. Specific examples include dihalo aromatic compounds such as p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dibromobenzene, diiodobenzene, tribromobenzene, dibromonaphthalene, triiodobenzene, dichlorodiphenylbenzene, dibromodiphenylbenzene, dichlorobenzophenone, dibromobenzophenone, dichlorodiphenyl ether, dibromodiphenyl ether, dichlorodiphenyl sulfide, dibromodiphenyl sulfide, dichlorobiphenyl, and dibromobiphenyl, and mixtures thereof. These compounds may be block copolymerized. Among these, dihalogenated benzenes are preferred, and those containing 80 mol% or more of p-dichlorobenzene are particularly preferred.

Examples of polyhalo aromatic compounds having a nitro group include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; dihalonitrodiphenyl ethers such as 2-nitro-4,4'-dichlorodiphenyl ether; dihalonitrodiphenyl sulfones such as 3,3'-dinitro-4,4'-dichlorodiphenyl sulfone; mono- or dihalonitropyridines such as 2,5-dichloro-3-nitropyridine and 2-chloro-3,5-dinitropyridine; and various dihalonitronaphthalenes.

In addition, in the above manufacturing method, an alkali metal sulfide or an alkali metal hydrosulfide and an alkali metal hydroxide (hereinafter sometimes referred to as a sulfidizing agent) are used as raw materials.

The alkali metal sulfides include lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. The alkali metal sulfides can be used as hydrates, aqueous mixtures, or anhydrides. The alkali metal sulfides can also be derived by reacting an alkali metal hydrosulfide with an alkali metal hydroxide. Note that a small amount of an alkali metal hydroxide may be added to react with the alkali metal hydrosulfide and alkali metal thiosulfate that are usually present in trace amounts in the alkali metal sulfide.

The alkali metal hydrosulfides include lithium hydrogen sulfide, sodium hydrogen sulfide, rubidium hydrogen sulfide, cesium hydrogen sulfide, and mixtures thereof. Such alkali metal hydrosulfides can be used as hydrates, aqueous mixtures, or anhydrous forms.

The alkali metal hydrosulfide is used together with the alkali metal hydroxide. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. These may be used alone or in combination of two or more. Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferred because of their ease of availability, and sodium hydroxide is particularly preferred.

The above-mentioned manufacturing method can also use a hydrous sulfidizing agent as a raw material. In that case, it is preferable to subject the hydrous sulfidizing agent to a polymerization reaction of the PAS resin after a process of dehydrating the agent in the presence of at least an aprotic polar solvent. In addition, when the amount of aprotic polar solvent charged is small, for example, less than 1 mole per mole of sulfur atoms in the sulfidizing agent, it is preferable to dehydrate the hydrous sulfidizing agent and the aprotic polar solvent in the presence of a polyhalo aromatic compound.

The dehydration step of the hydrous sulfidizing agent is carried out by charging at least an aprotic polar solvent and a hydrous alkali metal sulfide or a hydrous alkali hydrosulfide and an alkali metal hydroxide as the hydrous sulfidizing agent into a reaction vessel equipped with a distillation apparatus, heating to a temperature at which water is removed by azeotropy, specifically, in the range of 300°C or less, preferably in the range of 80 to 220°C, more preferably in the range of 100 to 200°C, and discharging water by distillation out of the system. In the dehydration step, dehydration is preferably carried out until the amount of water in the system in which the polymerization reaction is carried out is 5 moles or less, more preferably in the range of 0.01 to 2.0 moles per mole of sulfur atoms in the sulfidizing agent.

Examples of the organic polar solvent include amides, ureas and lactams such as formamide, acetamide, N-methylformamide, N,N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactam, ε-caprolactam, hexamethylphosphoramide, N-dimethylpropyleneurea, and 1,3-dimethyl-2-imidazolidinoic acid; sulfolanes such as sulfolane and dimethylsulfolane; nitriles such as benzonitrile; ketones such as methylphenylketone, and mixtures thereof. Among these, amides having an aliphatic cyclic structure such as N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactam, ε-caprolactam, hexamethylphosphoramide, N-dimethylpropyleneurea, and 1,3-dimethyl-2-imidazolidinoic acid are preferred, and N-methyl-2-pyrrolidone is even more preferred.

In the PAS polymerization step, the polymerization reaction of the PAS resin is carried out by reacting the alkali metal sulfide as a sulfidizing agent with a polyhaloaromatic compound in the presence of these organic polar solvents. Alternatively, the polymerization reaction of the PAS resin is carried out by reacting the alkali metal hydrosulfide and alkali metal hydroxide as sulfidizing agents with a polyhaloaromatic compound in the presence of these organic polar solvents. The polymerization conditions are generally a temperature in the range of 200 to 330°C, and a pressure in the range that keeps the polymerization solvent and the polyhaloaromatic compound, which is the polymerization monomer, substantially in the liquid phase, and is generally selected from the range of 0.1 to 20 MPa, preferably 0.1 to 2 MPa. The amount of the polyhaloaromatic compound charged is adjusted to be in the range of 0.2 to 5.0 moles, preferably 0.8 to 1.3 moles, and more preferably 0.9 to 1.1 moles, per mole of sulfur atom of the sulfidizing agent. The amount of the aprotic polar solvent is adjusted to be in the range of 1.0 to 6.0 moles, preferably 2.5 to 4.5 moles, per mole of sulfur atom in the sulfidizing agent. The polymerization reaction is preferably carried out in the presence of a small amount of water, and the ratio is preferably adjusted appropriately in consideration of the polymerization method, the molecular weight of the resulting polymer, and the productivity. Specifically, the dehydration operation is carried out so that the amount of water is 2.0 moles or less, preferably 1.6 moles or less, per mole of sulfur atom in the sulfidizing agent. However, when the dehydration operation is further carried out in the presence of a polyhalo aromatic compound (for example, the method of "5)" in the specific embodiment below), the dehydration operation may be carried out so that the amount of water is 0.9 moles or less, preferably 0.05 to 0.3 moles, more preferably 0.01 to 0.02 moles or less.

Specific examples of the polymerization of a sulfidizing agent and a polyhaloaromatic compound in the presence of the aprotic polar solvent include, for example,
1) A method using a polymerization aid such as an alkali metal carboxylate or a lithium halide,
2) A method using a branching agent such as an aromatic polyhalogen compound.
3) A method in which a polymerization reaction is carried out in the presence of a small amount of water and then water is added to further polymerize;
4) A method in which the gas phase portion of the reaction vessel is cooled during the reaction of the alkali metal sulfide with the aromatic dihalogen compound, and a part of the gas phase in the reaction vessel is condensed and refluxed to the liquid phase;
5) A method for producing a PAS resin, which includes, as essential production steps, a step of reacting an alkali metal sulfide, or a hydrous alkali metal hydrosulfide and an alkali metal hydroxide, with an amide, urea or lactam having an aliphatic cyclic structure, while dehydrating, in the presence of a polyhalo aromatic compound, to produce a slurry containing a solid alkali metal sulfide; a step of further adding a polar organic solvent such as NMP after producing the slurry, and distilling off water to perform dehydration; and a step of reacting a polyhalo aromatic compound, an alkali metal hydrosulfide, and an alkali metal salt of a hydrolyzate of the amide, urea or lactam having an aliphatic cyclic structure in the slurry obtained through the dehydration step, at a water content of 0.02 mol or less in the reaction system per 1 mol of the polar organic solvent such as NMP, to perform polymerization.

In this way, by polymerizing a dihaloaromatic compound with (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in an organic polar solvent, a mixture of PAS resin, cyclic PAS, chain-like PAS oligomers, etc. is obtained as a product. Other substances contained after the reaction may include by-products such as alkali metal-containing inorganic salts, carboxyalkylamino group-containing compounds, and terminal SH group-containing compounds, unreacted raw materials, and water.

-Step (2)-
Step (2) is a step of removing a solid phase component from the crude reaction mixture by solid-liquid separation to obtain a liquid phase component containing at least cyclic PAS and linear PAS oligomers.

The solid-liquid separation can be broadly divided into two types: the flash method and the quench method, which will be described later, with the quench method being preferred.

The quench method is a method of separating particulate PAS resin by slowly cooling the crude reaction mixture. In general, the crude reaction mixture is gradually cooled from a high-temperature, high-pressure state to crystallize the PAS resin in the reaction system, and then the solid content containing the PAS resin is separated as granules by solid-liquid separation by filtration or the like. Generally, as the molecular weight of the polymer increases, the interaction between the polymers becomes stronger, and the solubility in the solvent decreases. Therefore, in this process, the PAS resin precipitates and becomes a solid, while the cyclic PAS and oligomers remain dissolved in the solvent. There is no particular limit to the cooling time in the quench, but a range of 0.1°C/min to 3°C/min is usually preferred. In addition, it is not necessary to cool at the same rate throughout the entire cooling process. It is also preferable to cool at a rate of 0.1°C/min to 1°C/min until the granular PAS resin crystallizes, and then at a rate of 1°C/min or more. Finally, it is preferable to cool to 70°C or higher, preferably 100°C or higher and 200°C or lower, and then remove the solid content including the PAS resin by solid-liquid separation. In the quench method, solid-liquid separation can be performed by separating using a centrifuge such as a filter or a screw decanter, adding water directly to the obtained filtration residue to form a slurry, and then repeatedly performing solid-liquid separation, or by heating the obtained filtration residue in a non-oxidizing atmosphere to remove the remaining solvent.

At that time, if necessary, a step of removing a part or most of the organic polar solvent in the crude reaction mixture by distillation may be included, and after carrying out this step, the crude reaction mixture may be subjected to a solid-liquid separation operation by filtration to remove solid phase components. In addition, a step of washing the crude reaction mixture, or preferably the solid fraction (slurry) obtained after solid-liquid separation, by contacting it with water or an organic polar solvent may be included.

-Step (3)-
Step (3) is a step of obtaining cyclic PAS from the liquid phase component. The method of obtaining cyclic PAS from the liquid phase component is not particularly limited and can be a known method as long as it does not impair the effects of the present invention. For example, a method of removing an organic polar solvent by heating, washing the residue with an organic solvent or water, and further extracting and purifying the cyclic PAS using an organic solvent (see JP 2020-007490 A), or a method of removing an organic polar solvent using a membrane, washing the residue with an organic solvent or water, and further extracting and purifying the cyclic PAS using an organic solvent, and the like.

When removing the organic polar solvent, it is desirable to remove the solvent so that the proportion of non-volatile matter is in the range of 20 to 100% by mass, preferably 20 to 99.99% by mass, and more preferably 30 to 90% by mass. The temperature when removing the solvent by heating depends on the characteristics of the solvent used and cannot be uniquely limited, but can usually be selected in the range of 20 to 150°C, preferably 40 to 120°C. In addition, the pressure at which the solvent is removed is preferably normal pressure or lower, which makes it possible to remove the solvent at a lower temperature.

The purity of the cyclic PAS thus obtained is preferably 90% by mass or more, more preferably 96% by mass or more, and even more preferably 98% by mass or more, and is preferably 100% by mass or less, and more preferably 99.99% by mass or less. In this range, the reaction efficiency is excellent when producing the copolymer, and by-products can be reduced.

Thermoplastic resin other than polyarylene sulfide (B)
In the block copolymer according to this embodiment, a thermoplastic resin (B) other than PAS (hereinafter referred to as "component (B)") is used as a raw material for the other block. The component (B) is not particularly limited as long as it does not impair the effects of the present invention, and any known thermoplastic resin other than PAS resin can be used. In addition, from the viewpoint of reactivity with component (A), it is preferable to use a thermoplastic resin having a reactive functional group (e.g., a functional group containing an oxygen atom or a nitrogen atom) in the structure, or a thermoplastic resin that generates a reactive functional group or a polymerizable functional group at the end by thermal decomposition. For example, a thermoplastic resin obtained by condensation polymerization, addition polymerization, or ring-opening polymerization using a monomer containing an acid anhydride group, an epoxy group, an amino group, an ester group, an amide group, a hydroxyl group, a carboxyl group, an acid chloride group, an isocyanate group, a vinyl group, or the like can be mentioned.

Examples of the (B) component that can be used in this embodiment include polyolefin resins such as polyethylene, polypropylene, poly(4-methyl-1-pentene), and poly(1-butene); polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamide resins such as polyamide-6 (nylon-6), polyamide-66 (nylon-66), and polymetaxylene adipamide; ethylene-unsaturated ester copolymers such as ethylene-vinyl ester copolymers and ethylene-unsaturated carboxylic acid ester copolymers; ethylene-unsaturated carboxylic acid copolymers or ionomer resins thereof; poly(meth)acrylic resins such as poly(meth)acrylic acid ester resins; polystyrene resins; polyether ether ketone resins, polyether ketone resins, polyether sulfide sulfone resins, polyether sulfide resins, and polyphenyl ether resins; polycarbonate resins; polyvinyl acetate resins; polyacrylonitrile resins; thermoplastic elastomers; and liquid crystal polymers (LCPs). Depending on the purpose, one type selected from these thermoplastic resins may be used alone, two or more types may be used in combination, or a copolymer may be used. In particular, it is preferable to use polyamide-based resins, polyester-based resins, and polystyrene-based resins.

In addition, the (B) component that can be applied to this embodiment is preferably a thermoplastic resin that does not have a cyclic structure from the viewpoint of the mechanical properties and processability of the resulting copolymer. The (B) component may have a branched structure in its structure.

The properties of the (B) component that can be applied to this embodiment are not particularly limited as long as they do not impair the effects of the present invention, but for example, in the case of a crystalline resin, the melting point is preferably 80°C or higher, and more preferably 100°C or higher. Similarly, in the case of an amorphous resin, the glass transition point is preferably 80°C or higher, and more preferably 100°C or higher. In this range, decomposition during melt kneading is suppressed, and compatibility with the (A) component is excellent, resulting in excellent reaction efficiency.

<Method of producing block copolymer>
The method for producing a block copolymer according to the present embodiment includes a step of blending a cyclic PAS (A) and a thermoplastic resin other than PAS (B) as essential components, and melt-kneading the mixture at a temperature equal to or higher than the melting point of the cyclic PAS (A) and the flow temperature of the thermoplastic resin other than PAS (B), and is characterized in that the blending amount of the thermoplastic resin other than PAS (B) is 0.1 to 1000 parts by mass per part by mass of the cyclic PAS (A). The details will be described below.

The method for producing the block copolymer according to the present embodiment includes a step of blending the above-mentioned (A) and (B) components as essential components and melt-kneading them in a temperature range equal to or higher than the melting point of the (A) component and the flow temperature of the (B) component. In this disclosure, the flow temperature is the temperature at which the resin becomes soft and flowable when heated (the melting point in the case of a crystalline resin, or the glass transition point in the case of a non-crystalline resin). The method for producing the block copolymer used in the present embodiment is not particularly limited, but includes a method of blending the essential components and optional components as necessary and melt-kneading them, or more specifically, a method of uniformly dry-mixing them as necessary using a tumbler or Henschel mixer, and then feeding them into a twin-screw extruder and melt-kneading them.

The amount of component (B) is preferably 0.1 parts by mass or more per 1 part by mass of component (A), more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. Also, it is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, even more preferably 400 parts by mass or less, and particularly preferably 100 parts by mass or less. In this range, the reactivity during melt kneading is excellent, and the resulting block copolymer exhibits excellent processability and mechanical properties.

Melt kneading can be performed by heating to a temperature range in which the resin temperature is equal to or higher than the melting point of component (A) and the flow temperature of component (B), preferably equal to or higher than said temperature +10°C, more preferably equal to or higher than said temperature +10°C, even more preferably equal to or higher than said temperature +20°C, and preferably equal to or lower than said temperature +100°C, more preferably equal to or lower than said temperature +50°C. By melt kneading at a temperature equal to or higher than the melting point of component (A) and the flow temperature of component (B), each essential component flows sufficiently during kneading, resulting in excellent processability and reaction efficiency.

The melt kneader is preferably a twin-screw kneading extruder from the viewpoint of dispersibility and productivity. For example, it is preferable to melt knead while appropriately adjusting the resin component discharge rate in the range of 5 to 500 (kg/hr) and the screw rotation speed in the range of 50 to 500 (rpm), and it is even more preferable to melt knead under conditions where the ratio (discharge rate/screw rotation speed) is in the range of 0.02 to 5 (kg/hr/rpm). In addition, the components may be added and mixed in the melt kneader simultaneously or in separate portions.

In the method for producing the block copolymer according to this embodiment, after the melt kneading, the resin composition in a molten state is preferably extruded into a strand shape by a known method, for example, and then processed into pellets, chips, granules, powder, or other forms, and then pre-dried at a temperature range of 100 to 150°C as necessary.

In the method for producing a block copolymer of the present disclosure, at least a part of the (A) component and the (B) component form a copolymer in the melt-kneading process. This copolymer is maintained in the subsequent melt-molding process and in the use environment. The reason for forming the copolymer is not necessarily clear, but it is presumed to be due to the following mechanism. That is, by blending the above-mentioned (A) component and the above-mentioned (B) component as essential components and melt-kneading, the (A) component first opens a ring, and an end having a reactive functional group is formed accordingly. The reactive functional group reacts with the reactive functional group constituting the (B) component to form a bond, thereby forming a copolymer. It is considered that the reactive functional group derived from the (A) component may react with the reactive functional group present at the end of the (B) component, or may react with the reactive functional group in the main chain of the (B) component. As another mechanism, a part of the (B) component is thermally decomposed during melt-kneading to generate a reactive functional group or a polymerizable functional group, and the reactive functional group derived from the (A) component forms a bond thereto, thereby forming a copolymer. The above mechanism is merely speculative, and even if the effects of the present invention are achieved for other reasons, they are still within the scope of the present invention.

The fact that a block copolymer has been produced by the production method of the present disclosure can be confirmed by known methods, such as measuring the glass transition point using a differential scanning calorimeter or dynamic viscoelasticity measurement, observing the phase state using a scanning electron microscope (SEM) or the like, or identifying the chemical structure using a Fourier transform infrared spectrometer or nuclear magnetic resonance device. For example, when a differential scanning calorimeter is used, a single glass transition point is observed for a copolymer, so that the glass transition point can be measured as the temperature is increased to confirm the result.

The block copolymer obtained through the above steps can be melt molded as it is, or can be blended with the materials shown below (hereinafter sometimes simply referred to as "other materials") and further melt-kneaded to produce a block copolymer composition (hereinafter sometimes simply referred to as "composition").

<Block copolymer composition and method for producing block copolymer composition>
The resin composition according to this embodiment contains a block copolymer and other materials. The method for producing the resin composition according to this embodiment is characterized by having a step of blending the block copolymer obtained by the method for producing the block copolymer described above with other materials and melt-kneading them. Another embodiment of the present invention relates to a method for producing a resin composition having a step of blending a cyclic PAS (A), a thermoplastic resin other than PAS (B), and other materials and melt-kneading them. The method will be described in detail below.

In order to further improve the mechanical properties of the composition according to the present embodiment, a silane coupling agent can be blended as an optional component, if necessary. The silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but preferred examples include silane coupling agents having a functional group that reacts with a carboxy group, such as an epoxy group, an isocyanato group, an amino group, or a hydroxyl group. Examples of such silane coupling agents include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane; amino group-containing alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane; and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane.

The amount of the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but is preferably in the range of 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, to preferably 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the block copolymer. In this range, the resin composition has good moldability, particularly releasability, and the mechanical strength of the molded product is improved, which is preferable.

In order to further improve the mechanical properties, the composition according to the present embodiment may contain a filler as an optional component, if necessary. Here, as long as the inorganic filler does not impair the effects of the present invention, known and commonly used materials may be used, and examples of such fillers include fillers of various shapes, such as granular and plate-shaped ones. For example, fibrous fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, and natural fibers may be used, and non-fibrous fillers such as glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, zeolite, milled fiber, and calcium sulfate may be used. In addition, these inorganic fillers may be surface-treated, and may be treated with epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, borane treatment, ceramic coating, etc., if necessary.

The content of the inorganic filler is not particularly limited, but from the viewpoint of obtaining better mechanical properties and dimensional stability, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, relative to 100 parts by mass of the block copolymer. Also, from the viewpoint of obtaining better flowability and processability of the resin composition and smoothness of the surface of the molded product, it is more preferably 350 parts by mass or less, even more preferably 300 parts by mass or less, and particularly preferably 250 parts by mass or less, relative to 100 parts by mass of the block copolymer.

In addition to the above components, the composition according to the present embodiment may contain a thermoplastic elastomer as an optional component in order to further improve the thermal shock resistance and impact resistance. Examples of the thermoplastic elastomer include polyolefin elastomers, fluorine elastomers, and silicone elastomers, among which polyolefin elastomers are preferred. The amount of these thermoplastic elastomers is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and more preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the block copolymer. Within this range, a molded product having excellent moldability and mechanical properties, particularly excellent impact resistance, can be obtained.

For example, the polyolefin-based elastomer may be a homopolymer of an α-olefin, a copolymer of two or more α-olefins, or a copolymer of one or more α-olefins and a vinyl polymerizable compound having a functional group, where the α-olefin may be an α-olefin having 2 or more to 8 or less carbon atoms, such as ethylene, propylene, or 1-butene. In addition, the functional group may be a carboxy group, an acid anhydride group (-C(=O)OC(=O)-), an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, an oxazoline group, or the like. Examples of the vinyl polymerizable compound having the functional group include one or more of vinyl acetate; α,β-unsaturated carboxylic acids such as (meth)acrylic acid; alkyl esters of α,β-unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, and butyl acrylate; metal salts of α,β-unsaturated carboxylic acids such as ionomers (metals include alkali metals such as sodium, alkaline earth metals such as calcium, and zinc); glycidyl esters of α,β-unsaturated carboxylic acids such as glycidyl methacrylate; α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and derivatives of the α,β-unsaturated dicarboxylic acids (monoesters, diesters, and acid anhydrides). The above-mentioned thermoplastic elastomers may be used alone or in combination of two or more.

In addition to the above components, the composition according to the present embodiment may further contain synthetic resins such as polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylate resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, epoxy resin, phenolic resin, urethane resin, and liquid crystal polymer (hereinafter simply referred to as synthetic resin) as optional components depending on the application. In particular, it is preferable to add a fluorine-based resin because it improves the sliding properties. In the present disclosure, the synthetic resin is not an essential component, but when it is added, the ratio of the synthetic resin is not particularly limited as long as it does not impair the effects of the present invention, and it differs depending on each purpose and cannot be generally defined, but the ratio of the synthetic resin to be added in the resin composition according to the present disclosure is, for example, in the range of 5 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the block copolymer. In other words, the ratio of the block copolymer to the total of the block copolymer and the synthetic resin is preferably in the range of (100/115) or more, and more preferably in the range of (100/105) or more, based on mass.

In addition, the composition according to the present embodiment may contain other known and commonly used additives, such as colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant assistants, rust inhibitors, and release agents (metal salts or esters of fatty acids having 18 to 30 carbon atoms, including stearic acid and montanic acid, polyolefin waxes such as polyethylene, etc.), as optional components, as necessary. These additives are not essential components, and may be used in an amount of, for example, preferably 0.01 parts by mass or more, and preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the block copolymer, as appropriate for the purpose and use so as not to impair the effects of the present invention.

The method for producing the composition according to this embodiment includes a step of blending the block copolymer obtained by the method for producing the block copolymer described above with the optional components described above, and melt-kneading the mixture. The melt-kneading can be performed in the same manner as in the method for producing the block copolymer described above. That is, the method includes a step of blending the block copolymer with other components that are the optional components described above, and melt-kneading the mixture in a temperature range equal to or higher than the melting point of the block copolymer.

Another embodiment of the present disclosure relates to a method for producing a block copolymer composition, which comprises blending the component (A), the component (B), and the other optional components described above, and melt-kneading the blend. For example, by blending a filler or additive among the optional components described above, it is possible to obtain a block copolymer composition that is excellent in mechanical properties and processability while reducing the number of steps.

For example, when a fibrous filler is added as an optional component as required, it is preferable from the viewpoint of dispersibility to feed the filler into the twin-screw kneading extruder from a side feeder of the twin-screw kneading extruder. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin feed section (top feeder) to the side feeder to the total length of the screws of the twin-screw kneading extruder is 0.1 or more, and more preferably 0.3 or more. Moreover, this ratio is preferably 0.9 or less, and more preferably 0.7 or less.

<Molded products and methods for manufacturing molded products>
The molded article according to the present embodiment is produced by melt-molding the block copolymer or the composition. The method for producing the molded article according to the present embodiment includes a step of melt-molding the block copolymer or the composition. The method will be described in detail below.

The block copolymer and block copolymer composition according to the present embodiment can be subjected to various molding processes such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, and transfer molding, but are particularly suitable for injection molding applications due to their excellent releasability. When molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a normal general method. For example, in an injection molding machine, the composition is melted in a temperature range in which the resin temperature is equal to or higher than the melting point of the block copolymer or the composition, preferably in a temperature range of said temperature +10°C or higher, more preferably in a temperature range of said temperature +10°C to said temperature +100°C, and even more preferably in a temperature range of said temperature +20°C to said temperature +50°C, and then the resin is injected into a mold from a resin outlet and molded. In this case, the mold temperature may also be set to a known temperature range, for example, room temperature (23°C) to 300°C, preferably 130 to 190°C.

<Applications>
The block copolymer according to the present embodiment can be used as a matrix resin for compositions and molded products, similar to ordinary resins. It can also be used as a compatibilizer, and in particular, by blending it with a PAS resin composition, it exhibits excellent compatibility with other resins. When used for this purpose, it is preferable to blend it in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of PAS resin. If blended in excess of this range, the mechanical properties may be poor, and if blended below this range, it cannot fully function as a compatibilizer.

The block copolymer, resin composition, and molded article of the present embodiment are also suitable for various parts such as automobile parts, electrical and electronic parts, and water-related parts. Specifically, for example, electrical and electronic parts such as protective and support members for box-shaped electrical and electronic part integrated modules, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related parts; VTR parts, television parts, irons, hair dryers, rice cooker parts, electronic lasers, and the like. Home and office electrical appliance parts such as range parts, audio parts, audio/visual equipment parts such as audio/laser discs, compact discs, DVD discs, and Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and water-related equipment parts such as water heaters, bath water volume and temperature sensors; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters, typewriters, and other machine related parts; optical equipment and precision machinery related parts such as microscopes, binoculars, cameras, and watches; alternator terminals, alternator connectors, brush holders, slip rings, etc. , IC regulators, potentiometer bases for light dimmers, relay blocks, inhibitor switches, various valves such as exhaust gas valves, various pipes for fuel, exhaust systems and intake systems, air intake nozzle snorkels, intake manifolds, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, temperature sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, hot air flow control valves for heating, brush holders for radiator motors, water heater ... Examples of automotive and vehicle-related parts include turbo pump impellers, turbine vanes, wiper motor-related parts, distributors, starter switches, ignition coils and their bobbins, motor insulators, motor rotors, motor cores, starter relays, transmission wire harnesses, windshield washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and other various other applications.

The following examples and comparative examples are used to explain the present invention, but the present invention is not limited to these examples. In the following, unless otherwise specified, "%" and "parts" are based on mass.

<Examples 1 to 3 and Comparative Example 1>
Each material was blended according to the composition and blending amounts shown in Table 1. These blended materials were then fed into a vented twin-screw extruder "TEX-30α (product name)" manufactured by Japan Steel Works, Ltd., and melt-kneaded at a resin component discharge rate of 30 kg/hr, a screw rotation speed of 200 rpm, and a set resin temperature of 320°C to obtain pellets of the resin composition. The materials were mixed uniformly in advance and fed from the top feeder to obtain pellets of the resin composition. The resulting pellets of the resin composition were used to carry out the following tests.

<Reference Examples 1 to 3>
The following tests were carried out using the materials shown in Table 1 alone.

＜Evaluation＞

(1) DSC Measurement The pellets or materials of each Example, Comparative Example, and Reference Example were pressed at 340°C, and then quenched to prepare a film showing amorphousness. The obtained film was used as a test piece and measured under the following conditions using a differential scanning calorimeter (Perkin Elmer's "DSC8500"). The temperature was raised from 30°C to 330°C at a heating rate of 20°C/min, held for 3 minutes, cooled from 330°C to 30°C at a heating rate of 20°C/min, and then raised again from 30°C to 330°C at a heating rate of 20°C/min. During the first heating, the glass transition point (Tg, °C) and melting point (Tm, °C) were measured, and during cooling, the crystallization temperature (Tmc, °C) was measured. The results are shown in Table 1.

(2) Evaluation of Phase State The surface of each film prepared in (1) was observed at 2000 times magnification using a scanning electron microscope (SEM) ("JSM-6360A" manufactured by JEOL Ltd.) to evaluate the phase state.

The ingredients in Table 1 were mixed in the following ratios:

Cyclic PAS: mixture of 6 to 17 mers Chain PAS: weight average molecular weight 15,000
PA6T: "A6000" manufactured by Solvay Specialty Polymers Japan, 310°C

(Production Example 1) Production of cyclic PAS 19.413 kg (150 mol) of flake sodium sulfide (60.3 wt% Na2S) and 45.0 kg (454 mol) of N-methyl-2-pyrrolidone (NMP) were charged into a 150 L autoclave equipped with an agitator blade and a bottom valve connected to a pressure gauge, a thermometer, and a condenser. The temperature was raised to 209°C while stirring under a nitrogen stream, and 4.644 kg of water was distilled off (the remaining water content was 1.13 mol per mol of sodium sulfide). The autoclave was then sealed and cooled to 180°C, and 21.631 kg (147 mol) of p-dichlorobenzene and 18.0 kg (182 mol) of NMP were charged. At a liquid temperature of 150°C, the pressure was increased to 0.1 MPa using nitrogen gas at a gauge pressure, and the temperature was raised. The liquid temperature was raised to 240°C over 135 minutes and maintained for 30 minutes. The liquid temperature was then raised to 250°C over 40 minutes and maintained for 73 minutes to complete the reaction. The autoclave was then cooled. At 100°C, the bottom valve of the autoclave was opened, and the reaction slurry was transferred to a 150L plate filter and pressure filtered at 120°C. 48.0 kg of NMP was added, and the cake was washed and filtered again under pressure. The weight of the recovered NMP filtrate was 80.0 kg.
Water was added to the obtained NMP filtrate to form a water slurry, and solid-liquid separation and water washing were repeated twice, and then the mixture was dried for 4 hours in a hot air dryer at 120° C. to obtain a powder. Chloroform was added to the obtained powder, and the mixture was stirred for 1 hour at 65° C. After cooling to room temperature, the mixture was filtered, and the residue after filtration was washed with chloroform at 25° C. The solid content after removing the filtrate was dried for 4 hours in a hot air dryer at 120° C. to obtain a cyclic PAS.

(Production Example 2) Production of linear PAS 14.148 kg of 45% sodium hydrosulfide (47.55 wt% NaSH), 9.541 kg of 48% caustic soda (48.8 wt% NaOH), and 38.0 kg of NMP were charged into a 150 L autoclave equipped with a stirring blade and a bottom valve connected to a pressure gauge, a thermometer, and a condenser. The temperature was raised to 209°C while stirring under a nitrogen stream, and 12.150 kg of water was distilled off (the remaining water content was 1.13 moles per mole of NaSH). The autoclave was then sealed and cooled to 180°C, and 17.874 kg of paradichlorobenzene and 16.0 kg of NMP were charged. At a liquid temperature of 150°C, the pressure was increased to 0.1 MPa at a gauge pressure using nitrogen gas, and the temperature was increased. When the temperature was raised to 260°C, the autoclave was cooled by spraying water on the top, and the reaction was carried out at 260°C for 2 hours. During cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. Next, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. The maximum pressure during the reaction was 0.87 MPa. After the reaction, the mixture was cooled, the bottom valve was opened at 100°C, and the reaction slurry was transferred to a 150L flat plate filter and pressure filtered at 120°C. 50 kg of 70°C hot water was added to the obtained cake, stirred, filtered, and 25 kg of hot water was further added and filtered. Next, 25 kg of hot water was added, stirred for 1 hour, filtered, and then 25 kg of hot water was added and filtered. This operation was repeated twice. The obtained cake was dried at 120°C for 15 hours using a hot air circulation dryer to obtain a chain PAS.

Table 1 shows that the compositions of the examples have a single glass transition point, melting point, and crystallization temperature. In addition, the thermal properties were at different temperatures for the raw materials, cyclic PAS and polyamide, suggesting that the compositions of the examples form a copolymer. The composition using linear PAS in Comparative Example 1 had two glass transition points, melting points, and crystallization temperatures each derived from the raw materials used, suggesting that it does not form a copolymer but is simply an alloy.

Claims (15)

A block copolymer comprising a polyarylene sulfide block made from a cyclic polyarylene sulfide (A) and another block made from a thermoplastic resin (B) other than polyarylene sulfide,
A block copolymer, wherein the thermoplastic resin (B) other than the polyarylene sulfide does not have a cyclic structure. The block copolymer according to claim 1, wherein the thermoplastic resin (B) other than the polyarylene sulfide is at least one selected from the group consisting of polyamide-based resins, polyester-based resins, and polyether-based resins. The block copolymer according to claim 1 or 2, wherein the cyclic polyarylene sulfide (A) is a 4-40-mer. A block copolymer in which the mass ratio of a polyarylene sulfide block made from the cyclic polyarylene sulfide (A) to another block made from a thermoplastic resin other than the polyarylene sulfide (B) is in the range of 1/0.1 to 1/1000. A method for producing a block copolymer, comprising a step of blending a cyclic polyarylene sulfide (A) and a thermoplastic resin other than a polyarylene sulfide resin (B) as essential components, and melt-kneading the blended components at a temperature equal to or higher than the melting point of the cyclic polyarylene sulfide (A) and the flow temperature of the thermoplastic resin other than a polyarylene sulfide (B),
A method for producing a block copolymer, characterized in that the blending amount of the thermoplastic resin (B) other than the polyarylene sulfide is 0.1 to 1000 parts by mass per 1 part by mass of the cyclic polyarylene sulfide (A). The method for producing a block copolymer according to claim 5, wherein the thermoplastic resin (B) other than the polyarylene sulfide does not have a cyclic structure. The method for producing a block copolymer according to claim 5 or 6, wherein the thermoplastic resin (B) other than polyarylene sulfide is at least one selected from the group consisting of polyamide-based resins, polyester-based resins, and polystyrene-based resins. The method for producing a block copolymer according to claim 5 or 6, wherein the cyclic polyarylene sulfide (A) is a 4-40-mer. A block copolymer composition comprising the block copolymer according to claim 1 or 2 and other materials. A method for producing a block copolymer composition, comprising a step of blending and melt-kneading a block copolymer obtained by the method for producing a block copolymer according to claim 5 or 6 with other materials. A method for producing a block copolymer composition, comprising a step of blending and melt-kneading a cyclic polyarylene sulfide (A), a thermoplastic resin other than polyarylene sulfide (B), and other materials. A molded article obtained by melt molding the block copolymer according to claim 1 or 2. A molded article obtained by melt molding the block copolymer composition according to claim 9. A method for producing a molded product, comprising a step of melt molding the block copolymer obtained by the method for producing a block copolymer according to claim 5 or 6. A method for producing a molded article, comprising a step of melt molding a block copolymer composition obtained by the method for producing a block copolymer composition according to claim 10 or 11.

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