WO2017069109A1

WO2017069109A1 - Polyarylene sulfide resin composition, molded product, and methods for producing said composition and product

Info

Publication number: WO2017069109A1
Application number: PCT/JP2016/080801
Authority: WO
Inventors: 早織奈良; 新也宜保; 井上　敏; 高志古沢
Original assignee: Dic株式会社
Priority date: 2015-10-20
Filing date: 2016-10-18
Publication date: 2017-04-27
Also published as: JPWO2017069109A1

Abstract

Provided are: a polyarylene sulfide resin composition capable of being molded under a low temperature condition and having excellent heat resistance; a molded product thereof; and methods for producing the composition and product. More specifically, provided are: a polyarylene sulfide resin composition characterized by containing a resin (A) which is a polyarylene sulfide resin having an arylene thioether as a repeating unit, and in which the bonding point between the thioether and the arylene group is at the para position, and a resin (B) which is a polyarylene sulfide resin having an arylene thioether as a repeating unit, and which has a structural site (p) and a structural site (m) where the bonding point between the thioether and the arylene group binds at the para position and the meta position, respectively; a molded product thereof; and methods for producing the composition and product.

Description

Polyarylene sulfide resin composition, molded article, and production method thereof

The present invention relates to a polyarylene sulfide resin composition that can be molded under low temperature conditions and has excellent heat resistance.

Polyarylene sulfide resins are used in various applications such as electrical / electronic equipment parts and automobile parts, taking advantage of their excellent heat resistance and chemical resistance. Various melt processing methods such as injection molding, extrusion molding, compression molding, blow molding and the like are used for molding thermoplastic resins such as polyarylene sulfide resins. It is widely used as a molding method suitable for mass production. In the injection molding method, the resin is heated to a temperature equal to or higher than the melting point to improve fluidity, and this is injected and filled into a mold heated to an appropriate temperature, cooled and solidified to obtain a molded product. In the case of conventional polyarylene sulfide resins, the appropriate mold temperature is relatively high, about 130 to 180 ° C, so the energy and time required to reheat the mold during the molding cycle greatly affect production efficiency. Therefore, it has been desired to develop a polyarylene sulfide resin that can be molded at a lower mold temperature.

As a method for improving the low temperature moldability of polyarylene sulfide resin, a method of copolymerizing paradichlorobenzene and metadichlorobenzene is known (see Patent Document 1). However, the resin obtained by this method is excellent in low-temperature moldability, but the heat resistance is remarkably lowered, and the low-temperature moldability and heat resistance cannot be achieved at the same time.

JP 2014-051655 A

Therefore, the problem to be solved by the present invention is to provide a polyarylene sulfide resin composition that can be molded under a low temperature condition and also excellent in heat resistance, a molded product thereof, and a method for producing them.

As a result of diligent efforts to solve the above problems, the present inventors have found that in the arylene sulfide structure of the polyarylene sulfide resin, the bonding point of the arylene group is in the para position and the bonding point of the arylene group is in the para position. The polyarylene sulfide resin composition obtained by melt-kneading two types of resin having both a site and a meta-position site is excellent in heat resistance while being moldable under low temperature conditions. The headline and the present invention were completed.

That is, the present invention is a polyarylene sulfide resin having an arylene thioether as a repeating unit, wherein the thioether and the arylene group have a para-bonding point (A),
A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thioether and the arylene group is bonded at the para position and a structural site (m) bonded at the meta position. And a polyarylene sulfide resin composition comprising a resin (B).

Further, the present invention is a polyarylene sulfide resin having an arylene thioether as a repeating unit, the resin (A) in which the bonding point of the thioether and the arylene group is para-position,
A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thioether and the arylene group is bonded at the para position and a structural site (m) bonded at the meta position. The present invention relates to a method for producing a polyarylene sulfide resin composition in which a resin (B) is melt-kneaded in a temperature range equal to or higher than the melting point of the resin (A).

Furthermore, the present invention relates to a molded article comprising the polyarylene sulfide resin composition.

Furthermore, the present invention provides a method for producing a molded article comprising a step of molding the polyarylene sulfide resin composition in a mold, wherein the mold temperature is in the range of 40 to 180 ° C. It relates to a manufacturing method.

According to the present invention, it is possible to provide a polyarylene sulfide resin composition excellent in heat resistance while being capable of being molded under low temperature conditions, a molded product thereof, and a method for producing them.

The polyarylene sulfide resin composition of the present invention is a polyarylene sulfide resin having an arylene thioether as a repeating unit, the resin (A) in which the bonding point between the thioether and the arylene group is para-position,
A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thioether and the arylene group is bonded at the para position and a structural site (m) bonded at the meta position. Resin (B).

More preferably, the polyarylene sulfide resin composition of the present invention has the following structural formula (X)

[Wherein R ¹ is any ^one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and k is an integer of 1 to 4. ]
A polyarylene sulfide resin having a structural part (x) represented by formula (II) as a repeating unit, wherein the thioether and the arylene group in the structural part (x) have a para-position at the bonding point, and the structure It contains a resin (B) having both a structural part (p) in which the bonding point of the thioether and the arylene group in the part (x) is in the para position and a structural part (m) in the meta position. To do.

The resin (A) is a polyarylene sulfide resin having an arylene thioether as a repeating unit, and the bonding point between the thioether and the arylene group is a para-position. The arylene thioether may have a substituent, and in this case, the substituent may be substituted with 1 to 4 hydrogen atoms bonded to the carbon atom of the arylene group. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group.

More preferably, the resin (A) has the structural moiety (x) represented by the structural formula (X) as a repeating unit, and the bonding point between the thioether and the arylene group in the structural moiety (x) is a parasite. It is rank. Specifically, it is a polyarylene sulfide resin having a structural site (p) represented by the following structural formula (X1) as a repeating unit.

[Wherein R ¹ is any ^one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and k is an integer of 1 to 4. ]

R ¹ in the formula (X1) in the resin (A) is any ^one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group. When k is an integer of 2 or more, a plurality of R ¹ present in the formula may be the same structural site, or may be different structural sites. Especially, since it becomes a polyarylene sulfide resin composition excellent in heat resistance and mechanical strength, R ¹ is preferably a hydrogen atom.

When the resin (A) has the structural moiety (p) represented by the structural formula (X1) as a repeating unit, any one of the following structural formulas (Y1) to (Y6) in addition to the structural moiety (p) It may have a structural site (y) represented by

[Wherein R ² is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and r is an integer of 1 to 4. ]

When the resin (A) has the structural site (y) in addition to the structural site (p), it becomes a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength. ) And the structural part (y), the proportion of the structural part (y) is preferably 30 mol% or less. Moreover, when the said resin (A) has the said structure site | part (y), either a random copolymer or a block copolymer may be sufficient as the coupling | bonding mode of each structure site | part.

Further, the resin (A) includes, in addition to the structural sites (p) and (y), a branched structural site represented by the following structural formula (Z) and a naphthyl sulfide represented by the following structural formula (V). It may have a structural part. When the resin (A) has these structural sites, it becomes a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength, so that the total of the structural site (p) and the structural site (y). However, it is preferably 3 mol% or less, particularly preferably 1 mol% or less.

[Wherein R ³ and R ⁴ are each independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group; An integer of 6 and t is an integer of 1 to 3. ]

The melting point (Tm) of the resin (A) is preferably in the range of 270 to 300 ° C. because it becomes a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength. In addition, the recrystallization temperature (Tc2) of the resin (A) is preferably in the range of 210 to 260 ° C. because it is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength.

The difference ΔT between the melting point (Tm) of the resin (A) and the recrystallization temperature (Tc2) is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength. The range is preferable, and the range of 35 to 55 ° C. is more preferable.

The melt viscosity (V6) measured at 300 ° C. of the resin (A) is preferably in the range of 2 to 1000 [Pa · s] because the balance between fluidity and mechanical strength is good. A range of 500 [Pa · s] is more preferable, and a range of 2 to 200 [Pa · s] is particularly preferable. In the present invention, the melt viscosity (V6) is 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10 (mm) using a polyarylene sulfide resin, a flow tester manufactured by Shimadzu Corporation, CFT-500D. / 1 (mm), and held for 6 minutes, then the melt viscosity is measured.

The non-Newtonian index of the resin (A) is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.90 to 2.00, and is preferably in the range of 0.90 to 1.50. More preferably, the range is 0.95 to 1.20. In the present invention, the non-Newtonian index (N value) is a shear rate (SR) under the conditions of 300 ° C., ratio of orifice length (L) to orifice diameter (D), L / D = 40 using a capillograph. And the shear stress (SS) were measured and calculated using the following formula. The closer the non-Newtonian index (N value) is to 1, the closer it is to a linear structure, and the higher the non-Newtonian index (N value), the more branched the structure is.

[SR is the shear rate (second ⁻¹ ), SS is the shear stress (dyne / cm ² ), and K is a constant. ]

The resin (A) can be produced by an ordinary method for producing a polyarylene sulfide resin, specifically, a dihalogenoaromatic compound, and if necessary, a polyhalogenoaromatic compound or other copolymer component. In the presence of sulfur and sodium carbonate (Method 1), a dihalogenoaromatic compound in a polar solvent, and a polyhalogenoaromatic compound and other copolymerization components, if necessary, as a sulfidizing agent, etc. And a method of polymerizing in the presence of (Method 2), a method of self-condensing p-chlorothiophenol and other copolymerization components as necessary (Method 3), and the like. Among these production methods, Method 2 is versatile and preferable. In addition, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added for the purpose of adjusting the degree of polymerization during the reaction.

In order to describe in more detail a more preferable form of the method 2, for example, hydrous sulfidation is performed on a mixture containing at least a heated organic polar solvent and an essential raw material dihalogenoaromatic compound as necessary, and a polyhalogenoaromatic compound as an optional raw material. The agent is sequentially added and reacted at a rate at which water can be removed from the reaction mixture, and the amount of water in the reaction system is controlled to be in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. However, a method for producing a polyarylene sulfide resin (see JP 07-228699 A), a dihalogeno aromatic compound as an essential raw material in the presence of a solid alkali metal sulfide in an aprotic polar organic solvent, If necessary, using polyhalogenoaromatic compound or other copolymerization component as an optional raw material, organic acid alkali metal salt amount A method of reacting while controlling the amount of water in the reaction system within a range of 0.01 to 0.9 mol with respect to 1 mol of sulfur source and within a range of 0.02 mol with respect to 1 mol of aprotic polar organic solvent. (See the pamphlet of WO 2010/058713).

Examples of the dihalogenoaromatic compound and polyhalogenoaromatic compound used as a raw material for the resin (A) include p-dihalobenzene and 4,4′-dihalodiphenyl as essential raw materials for introducing the structural moiety (p) into the resin. From the group consisting of sulfide, 2,5-dihalotoluene, 2,5-dihaloanisole, 2,5-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,5-dihaloaniline, 2,5-dihalobiphenyl, etc. One or more dihalogenoaromatic compounds selected may be mentioned, and optional raw materials used as necessary include p, p′-dihalodiphenyl ether, 4,4′-dihalobenzophenone, bis (4-halophenyl) methane, 4,4 '-Dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalobiphenyl, 1,4- Halonaphthalene, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5- One or more polyhalogeno aromatic compounds selected from the group consisting of tetrahalobenzene, 1,4,6-trihalonaphthalene and the like can be mentioned. These may be used alone or in combination of two or more.

The halogen atom contained in each compound is preferably a chlorine atom or a bromine atom.

The post-treatment method of the reaction mixture containing the resin (A) obtained by each of the production methods is not particularly limited. For example, an acid or a base may be added to the reaction mixture after completion of the polymerization reaction as necessary. In addition, after distilling off the solvent under reduced pressure or atmospheric pressure, the solid after distilling off the solvent is one or more with water, the solvent used during the polymerization reaction, other organic solvents such as acetone, methyl ethyl ketone, alcohol compounds, etc. A method of washing twice, further neutralizing, washing with water, filtering and drying (Method 1), and the reaction mixture after completion of the polymerization reaction is added to water, acetone, methyl ethyl ketone, alcohol compound, ether compound, halogenated hydrocarbon, aromatic hydrocarbon , Precipitating solvents such as aliphatic hydrocarbons (solvents that are soluble in the solvent used during the polymerization reaction and that are poor solvents for at least polyarylene sulfide) A method for precipitating solid products such as polyarylene sulfide and inorganic salts, filtering them, washing and drying (Method 2), and for the reaction mixture after completion of the polymerization reaction, was used during the polymerization reaction After adding a solvent (or an organic solvent having an equivalent solubility with respect to a low molecular weight polymer), stirring and filtering to remove the low molecular weight polymer, once with a solvent such as water, acetone, methyl ethyl ketone, alcohol compound or the like. A method of washing several times, further neutralizing, washing with water, filtering and drying (Method 3), a method of adding water and, if necessary, an acid to the reaction mixture after completion of the polymerization reaction, and filtering and washing the washed product (Method 4) After completion of the polymerization reaction, a method of filtering the reaction mixture, washing with a reaction solvent one or more times as necessary, further washing with water, filtering and drying (Method 5) and the like can be mentioned.

In the post-treatment methods exemplified in the above methods 1 to 5, the polyarylene sulfide resin may be dried in a vacuum, or in an inert gas atmosphere such as air or nitrogen. .

The resin (A) thus obtained has a molecular end that is a carboxyl group or an alkali metal carboxylate.

The resin (B) is a polyarylene sulfide resin having an arylene thioether as a repeating unit, and a structural site (p) in which the bonding point of the thioether and the arylene group is bonded at the para position, and a structural site ( m). The arylene thioether may have a substituent, and in this case, the substituent may be substituted with 1 to 4 hydrogen atoms bonded to the carbon atom of the arylene group. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group.

More preferably, the resin (B) has the structural site (x) represented by the structural formula (X) as a repeating unit, and the bonding point between the thioether and the arylene group in the structural site (x) is a parasite. It has both a structural site (p) that is a position and a structural site (m) that is a meta position. Specifically, a polyarylene sulfide resin having as a repeating unit both a structural moiety (p) represented by the following structural formula (X1) and a structural moiety (m) represented by the following structural formula (X2). is there.

The molar ratio [(p) / (m)] of the structural part (p) and the structural part (m) of the resin (B) can be molded under low temperature conditions, but also has good heat resistance. In order to obtain an excellent polyarylene sulfide resin composition, it is preferably in the range of 99/1 to 60/40, more preferably in the range of 95/5 to 75/25.

R ¹ in the formulas (X1) and (X2) in the resin (B) is any ^one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group. It is. When k is an integer of 2 or more, a plurality of R ¹ present in the formula may be the same structural site, or may be different structural sites. Especially, since it becomes a polyarylene sulfide resin composition excellent in heat resistance and mechanical strength, R ¹ is preferably a hydrogen atom.

The resin (B) has a structural site (y) represented by any of the following structural formulas (Y1) to (Y6) in addition to the structural site (p) and the structural formula (m). Also good.

When the resin (B) has the structural part (y), since it becomes a polyarylene sulfide resin composition having excellent heat resistance while being moldable under low temperature conditions, the structural part (p), It is preferable that the ratio of the structural site (y) to the total of (m) and (y) is 30 mol% or less. Moreover, when the said resin (B) has the said structure site | part (y), either a random copolymer or a block copolymer may be sufficient as the coupling | bonding mode of each structure site | part.

The resin (B) is represented by the structural site (p), (m), (y), a branched structural site represented by the following structural formula (Z), or the following structural formula (V). It may have a naphthyl sulfide structure site. When the resin (B) has these structural sites, the polyarylene sulfide resin composition is excellent in heat resistance while being moldable under low temperature conditions. Therefore, the structural sites (p), (m ) And (y), preferably 3 mol% or less, particularly preferably 1 mol% or less.

The melting point (Tm) of the resin (B) is preferably 200 ° C. or higher because it becomes a polyarylene sulfide resin composition that can be molded under low temperature conditions and is also excellent in heat resistance. A range of 280 ° C. is more preferable. Further, the recrystallization temperature (Tc2) of the resin (B) is 200 ° C. or lower because it becomes a polyarylene sulfide resin composition having excellent heat resistance while being moldable under low temperature conditions. The temperature is preferably in the range of 130 to 160 ° C.

Further, the difference ΔT between the melting point (Tm) of the resin (B) and the recrystallization temperature (Tc2) is 20 ° C. or higher because it becomes a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength. The temperature is preferably in the range of 50 to 100 ° C.

The melt viscosity (V6) measured at 300 ° C. of the resin (B) is preferably in the range of 2 to 1000 [Pa · s] because the balance between fluidity and mechanical strength is good. A range of 500 [Pa · s] is more preferable, and a range of 2 to 200 [Pa · s] is particularly preferable.

The non-Newtonian index of the resin (B) is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.90 to 2.00, and is preferably in the range of 0.90 to 1.50. More preferably, the range is 0.95 to 1.20.

The resin (B) can be produced by the same method as the resin (A) described above.

Examples of the dihalogenoaromatic compound and polyhalogenoaromatic compound used as the raw material for the resin (B) include p-dihalobenzene and 4,4′-dihalodiphenyl as essential raw materials for introducing the structural moiety (p) into the resin. From the group consisting of sulfide, 2,5-dihalotoluene, 2,5-dihaloanisole, 2,5-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,5-dihaloaniline, 2,5-dihalobiphenyl, etc. One or more dihalogenoaromatic compounds selected, and m-dihalobenzene, 2,4-dihalotoluene, 3,5-dihalotoluene, 2,4-dihaloanisole as essential raw materials for introducing the structural moiety (m), 3,5-dihaloanisole, 2,4-dihalobenzoic acid, 3,5-dihalobenzoic acid, 2,4-dihalonitrobenzene, 3 And one or more dihalogenoaromatic compounds selected from the group consisting of 5-dihalonitrobenzene, 2,4-dihaloaniline, 3,5-dihaloaniline, 2,4-dihalobiphenyl, 3,5-dihalobiphenyl, etc. As an optional raw material used as necessary, p, p′-dihalodiphenyl ether, 4,4′-dihalobenzophenone, bis (4-halophenyl) methane, 4,4′-dihalodiphenyl sulfoxide, 4,4′- Dihalodiphenyl sulfone, 4,4′-dihalobiphenyl, 1,4-dihalonaphthalene, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1 , 2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, etc. Poriharogeno aromatic least one compound which can be cited. These may be used alone or in combination of two or more.

In the raw material of the resin (B), the mass ratio of the component for introducing the structural site (p) and the component for introducing the structural site (m) is the same as that of the resin (B) described above. According to the molar ratio [(p) / (m)] between the structural site (p) and the structural site (m).

The resin (B) thus obtained has a molecular end that is a carboxyl group or an alkali metal carboxylate.

The polyarylene sulfide resin composition of the present invention is a melt-kneaded product obtained by melt-kneading the resin (A) and the resin (B). The blending mass ratio [(A) / (B)] of the resin (A) and the resin (B) at this time is a polyarylene sulfide resin that can be molded under low temperature conditions and has excellent heat resistance. The range is preferably from 95/5 to 40/60, more preferably from 90/10 to 70/30, because it is a composition.

Since the polyarylene sulfide resin composition of the present invention is excellent in heat resistance and mechanical strength, the melting point (Tm) is 270 ° C. or more and the recrystallization temperature (Tc 2) is 210 ° C. or less. preferable. Further, it is particularly preferable that the melting point (Tm) is in the range of 270 ° C. to 290 ° C. and the recrystallization temperature (Tc 2) is in the range of 180 to 210 ° C. Further, the difference ΔT between the melting point (Tm) and the recrystallization temperature (Tc2) is preferably 70 ° C. or more, particularly preferably in the range of 70 to 90 ° C.

The melt viscosity (V6) measured at 300 ° C. of the polyarylene sulfide resin composition of the present invention is in the range of 2 to 1000 [Pa · s] because the balance between fluidity and mechanical strength is good. The range is preferably 2 to 500 [Pa · s], more preferably 2 to 200 [Pa · s].

The non-Newtonian index of the polyarylene sulfide resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.90 to 2.00, preferably 0.90 to 1.50. Is more preferable, and a range of 0.95 to 1.20 is particularly preferable.

In addition to the resin (A) and the resin (B), the polyarylene sulfide resin composition of the present invention includes a filler, a silane coupling agent, other resins, a colorant, a heat stabilizer, an ultraviolet stabilizer, and a foaming agent. In addition, components such as a rust inhibitor, a flame retardant, and a lubricant may be contained.

The filler may be in any shape such as fibrous, granular, plate-like, specifically, glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, Fibrous fillers such as fibers such as calcium sulfate and calcium silicate, natural fibers such as wollastonite, glass beads, glass flakes, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica And non-fibrous fillers such as mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, and glass beads. These may be used alone or in combination of two or more.

Examples of the silane coupling agent include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compound: γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ- Isocyanato group-containing alkoxysilane compounds such as isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane; γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-amino Chill) aminopropyltrimethoxysilane, amino group-containing alkoxysilane compounds such as .gamma.-aminopropyltrimethoxysilane; .gamma.-hydroxypropyl trimethoxysilane, hydroxyl group-containing alkoxysilane compounds such as .gamma.-hydroxypropyl triethoxysilane and the like. These may be used alone or in combination of two or more.

Examples of the other resins include polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyether sulfone resins, polyether ether ketone resins, polyether ketone resins, poly Arylene resin, polyolefin resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenol resin, urethane resin, liquid crystal polymer, silicone resin, or other synthetic resin, or fluorine rubber And other elastomers.

The method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited. For example, the resin (A), the resin (B) as a raw material, and the other components described above as necessary are mixed with powder, beret, fine powder. In various forms, such as a piece, put into a ribbon blender, Henschel mixer, V blender, etc., dry blend, then feed into a known melt kneader such as a Banbury mixer mixing roll, a single or twin screw extruder, and a knee. A temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin composition (more specifically, the higher one of the resin (A) and the resin (B) in the polyarylene sulfide resin composition), preferably The temperature range of melting point + 10 ° C. or more, more preferably the temperature range of melting point + 10 ° C. to melting point + 100 ° C., more preferably And a method of melt-kneading at a temperature range of a point + 20 ~ mp + 50 ° C.. Among them, a typical method is melt-kneading using a single-screw or twin-screw extruder having a sufficient kneading force.

The polyarylene sulfide resin composition of the present invention can be used for various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, and transfer molding. Especially, it can use suitably for an injection molding application taking advantage of the effect of this invention which can be fabricated under low temperature conditions.

The various conditions for molding the polyarylene sulfide resin composition of the present invention by injection molding are not particularly limited, and can be usually molded by a general method. Prior to molding, the appearance and mechanical properties of the molded product are improved by preliminary drying at a temperature of 100 to 150 ° C. The cylinder temperature may be a temperature equal to or higher than the melting point of the polyarylene sulfide resin composition, but is preferably 300 ° C. or higher in order to obtain sufficient fluidity. The mold temperature is usually set in the range of 130 to 180 ° C. However, since the polyarylene sulfide resin composition of the present invention has excellent low-temperature moldability, even under relatively low temperature conditions of 130 ° C. or less. A molded product excellent in appearance and mechanical properties can be obtained. The mold temperature is more preferably 120 ° C. or less, and preferably in the range of 40 to 120 ° C. Therefore, the polyarylene sulfide resin composition of the present invention can be molded by molding in a mold having a mold temperature in the range of 40 to 180 ° C, more preferably in the range of 40 to 120 ° C.

The molded product obtained by using the polyarylene sulfide resin composition of the present invention can be used for various applications by taking advantage of its excellent heat resistance, for example, a protective / support member for a box-shaped electrical / electronic component integrated module, 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 boards, electronics Representative of circuit, LSI, IC, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, terminal block, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts, etc. Electricity / electricity Parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / video equipment parts such as audio / laser discs / compact discs / DVD discs / Blu-ray discs, lighting parts, refrigerator parts , Air conditioner parts, typewriter parts, word processor parts, home appliances such as water heaters, bath water volume, water sensor parts such as temperature sensors, office computer parts, office computer parts, telephone equipment parts, facsimile Machine-related parts represented by related parts, copier-related parts, cleaning jigs, motor parts, writers, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternators Terminal, alternator connector, IC regulator , Potentiometer base for light diamond, relay block, inhibitor switch, various valves such as exhaust gas valve, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, Carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow Control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor Starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical equipment It can also be applied to parts / insulators, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, parts for automobiles and vehicles such as ignition device cases, and other various uses.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
In Examples, the melt viscosity (V6) at 300 ° C. of the polyarylene sulfide resin and the polyarylene sulfide resin composition was 300 ° C. under a load of 1.96 × using a flow tester “CFT-500D” manufactured by Shimadzu Corporation. It measured after hold | maintaining for 6 minutes on the conditions of 10 < ⁶ > Pa, L / D = 10 (mm) / 1 (mm).
In addition, the melting point (Tm) or (Tm2), recrystallization temperature (Tc2), glass transition temperature (Tg), and melt crystallization temperature (Tmc) of the polyarylene sulfide resin and the polyarylene sulfide resin composition are resin or resin. The composition was melted at 350 ° C. and then rapidly cooled to prepare an amorphous film. Approximately 4 mg was weighed from this film and measured using a differential scanning calorimeter (“DSC8500” manufactured by Perkin Elmer).

Production Example 1 Production of polyarylene sulfide resin (A-1) In a 150 liter autoclave equipped with a pressure gauge, a thermometer, a condenser blade connected to a condenser, and a bottom valve, a 14.148 kg of a 47.55 mass% sodium hydrogen sulfide aqueous solution, 9.541 kg of 48.8 mass% sodium hydroxide aqueous solution and 38.0 kg of N-methyl-2-pyrrolidone were charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 12.150 kg of water (the amount of water remaining was 1.13 moles per mole of sodium hydrogen sulfide). Thereafter, the autoclave was sealed and cooled to 180 ° C., and 17.464 kg of paradichlorobenzene and 16.0 kg of N-methyl-2-pyrrolidone were charged. The liquid temperature was set to 150 ° C., and nitrogen gas was used to increase the gauge pressure to 0.1 MPa, and the temperature increase was started. When the temperature reached 260 ° C., watering was started on the top of the autoclave, and the reaction was carried out at 260 ° C. for 2 hours while adjusting the liquid temperature so as not to decrease. The maximum pressure during the reaction was 0.87 MPa. The temperature was lowered and sprinkling cooling at the top of the autoclave was stopped. When the temperature reached 100 ° C., the bottom valve was opened, and the reaction slurry was transferred to a 150 liter flat filter and filtered under pressure at 120 ° C. The obtained cake was washed and filtered with 50 kg of hot water at 70 ° C., and washing and filtering with 25 kg of hot water were repeated four times. The polyarylene sulfide resin (A-1) was obtained by drying at 120 ° C. for 15 hours using a hot air circulating dryer. The resulting polyarylene sulfide resin (A-1) has a melting point (Tm) of 280 ° C., a recrystallization temperature (Tc2) of 231 ° C., a difference ΔT between them of 49 ° C. and a melt viscosity (V6) at 300 ° C. It was 52 Pa · s.

Production Example 2 Production of polyarylene sulfide resin (A-2) In a 150 liter autoclave equipped with a pressure gauge, a thermometer, a condenser blade connected to a condenser, and a bottom valve, a 14.148 kg of a 47.55 mass% sodium hydrogen sulfide aqueous solution, 9.474 kg of 48.7 mass% sodium hydroxide aqueous solution and 38.0 kg of N-methyl-2-pyrrolidone were charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 12.150 kg of water (the amount of water remaining was 1.13 moles per mole of sodium hydrogen sulfide). Thereafter, the autoclave was sealed and cooled to 180 ° C., and 17.129 kg of paradichlorobenzene and 16.0 kg of N-methyl-2-pyrrolidone were charged. The liquid temperature was set to 150 ° C., and nitrogen gas was used to increase the gauge pressure to 0.1 MPa, and the temperature increase was started. After stirring at a liquid temperature of 220 ° C. for 4 hours, when the temperature was further raised to 260 ° C., watering was started on the top of the autoclave, and the reaction was carried out at 260 ° C. for 3 hours while adjusting the liquid temperature so as not to decrease. The maximum pressure during the reaction was 0.86 MPa. The temperature was lowered and sprinkling cooling at the top of the autoclave was stopped. When the temperature reached 100 ° C., the bottom valve was opened, and the reaction slurry was transferred to a 150 liter flat filter and filtered under pressure at 120 ° C. Using a 150 liter vacuum dryer equipped with a stirring blade, the mixture was stirred at 150 ° C. under reduced pressure for 2 hours to distill off N-methyl-2-pyrrolidone. The obtained cake was washed and filtered with 50 kg of warm water at 70 ° C., and further washed and filtered with 25 kg of warm water 7 times. It dried at 120 degreeC for 15 hours using the hot air circulation dryer, and obtained the polyarylene sulfide resin intermediate body whose melt viscosity (V6) in 300 degreeC is 122 Pa.s. This was heat-treated at 250 ° C. for 4 hours using a hot air circulating dryer to obtain the desired polyarylene sulfide resin (A-2). The resulting polyphenylene sulfide resin (A-2) has a melting point (Tm) of 279 ° C., a recrystallization temperature (Tc 2) of 238 ° C., a difference ΔT between them of 41 ° C. and a melt viscosity (V6) at 300 ° C. of 612 Pa.・ It was s.

Production Example 3 Production of Polyarylene Sulfide Resin (A-3) 33.222 kg of paradichlorobenzene and N-methyl-2-pyrrolidone were added to a 150 liter autoclave with a stirring blade connected with a pressure gauge, thermometer, condenser, decanter and rectifying tower. 2.280 kg, 27.300 kg of 47.23 mass% sodium hydrogen sulfide aqueous solution and 18.533 g of 49.21 mass% sodium hydroxide aqueous solution were charged, and the temperature was raised to 173 ° C. over 5 hours with stirring in a nitrogen atmosphere. After distilling 27.300 kg of water, the autoclave was sealed. Paradichlorobenzene distilled by azeotropic distillation during dehydration was separated with a decanter and returned to the autoclave as needed. After completion of the dehydration, the finely divided anhydrous sodium sulfide composition was dispersed in paradichlorobenzene in the autoclave. Since the N-methyl-2-pyrrolidone content in this composition was 0.069 kg, 97 mol% of the charged N-methyl-2-pyrrolidone was an NMP ring-opened product (4- (methylamino) It was shown to be hydrolyzed to the sodium salt of butyric acid (hereinafter abbreviated as “SMAB”). The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave. When the total amount of sodium hydrogen sulfide and sodium hydroxide charged is changed to anhydrous sodium sulfide, the theoretical dehydration amount is 27.921 g. Therefore, of the remaining water amount of 621 g in the autoclave, 401 g is N-methyl-2-pyrrolidone and water. It was consumed in the hydrolysis reaction with sodium oxide and was not present in the autoclave as water, and the remaining 220 g remained in the autoclave in the form of water or crystal water. The amount of water in the autoclave was 0.053 mol per mol of sulfur atoms present in the autoclave.
After completion of the dehydration step, the internal temperature was cooled to 160 ° C., a mixed solution of 25.0 g of 1,3,5-trichlorobenzene and 47.492 kg of N-methyl-2-pyrrolidone was charged, and the temperature was raised to 185 ° C. The amount of water in the autoclave was 0.025 mol per mol of N-methyl-2-pyrrolidone charged in Step 2. When the gauge pressure reached 0.00 MPa, the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, the cooling and the valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled vapor of paradichlorobenzene and water was condensed by a condenser and separated by a decanter, and paradichlorobenzene was returned to the autoclave. The amount of distilled water was 179 g, the water content in the autoclave was 41 g, 0.005 mol per mol of N-methyl-2-pyrrolidone charged after dehydration, and 0.010 mol per mol of sulfur atoms present in the autoclave. there were. The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave, as in dehydration. Next, the temperature was raised from an internal temperature of 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 3 hours, then heated to 250 ° C. and stirred for 1 hour. The gauge pressure at an internal temperature of 200 ° C. was 0.03 MPa, and the final gauge pressure was 0.30 MPa. After cooling, 6.5 kg of the obtained slurry was poured into 30 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake was again stirred with 30 liters of warm water for 1 hour, washed and filtered. This operation was repeated four times, followed by filtration and drying overnight at 120 ° C. using a hot air dryer to obtain a white powdery polyarylene sulfide resin (A-3). The resulting polyarylene sulfide resin (A-3) has a melting point (Tm) of 284 ° C., a recrystallization temperature (Tc2) of 245 ° C., a difference ΔT between them of 39 ° C., and a melt viscosity (V6) at 300 ° C. 505 Pa · s.

Production Example 4 Production of Polyarylene Sulfide Resin (B-1) A 150-liter autoclave was charged with 19.222 kg of flaky sodium sulfide (60.9 mass%) and 45.0 kg of N-methyl-2-pyrrolidone. While stirring under a nitrogen stream, the temperature was raised to 204 ° C. to distill 4.438 kg of water (the amount of water remaining was 1.14 mol per mol of sodium sulfide). Thereafter, the autoclave was sealed and cooled to 180 ° C., paradichlorobenzene 21.721 kg, metadichlorobenzene 3.833 kg (molar ratio of both [(p) / (m)] = 85/15) and N-methyl-2- 18.0 kg of pyrrolidone was charged. The temperature was increased by pressurizing to 1 kg / cm ² G using nitrogen gas at a liquid temperature of 150 ° C. While stirring at a liquid temperature of 220 ° C. for 3 hours, an 80 ° C. refrigerant was passed through a coil wound around the outside of the upper part of the autoclave to cool it. Thereafter, the temperature was raised, and the mixture was stirred at a liquid temperature of 260 ° C. for 3 hours. Then, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping. The maximum pressure during the reaction was 8.91 kg / cm ² G. The obtained slurry was washed twice with warm water and filtered to obtain a filter cake containing about 50% by mass of water. Next, 60 kg of water and 100 g of acetic acid were added to the filter cake to re-slurry, stirred at 50 ° C. for 30 minutes, and then filtered again. At this time, the pH of the slurry was 4.6. The operation of adding 60 kg of water to the obtained filter cake and stirring for 30 minutes and then filtering again was repeated 5 times. The obtained filter cake was dried in a hot air circulating dryer at 120 ° C. for 4.5 hours to obtain a white powdered polyarylene sulfide resin (B-1). The resulting polyarylene sulfide resin (B-1) has a melting point (Tm) of 230 ° C., a recrystallization temperature (Tc 2) of 155 ° C., a difference ΔT between them of 75 ° C., and a melt viscosity (V6) at 300 ° C. It was 45 Pa · s.

Production Example 5 Production of polyarylene sulfide resin (B-2) Except that paradichlorobenzene was changed to 22.999 kg and metadichlorobenzene was changed to 2.555 kg (molar ratio of both [(p) / (m)] = 90 / 10) A polyarylene sulfide resin (B-2) was obtained in the same manner as in Production Example 4. The resulting polyarylene sulfide resin (B-2) has a melting point (Tm) of 249 ° C., a recrystallization temperature (Tc2) of 160 ° C., a difference ΔT between them of 89 ° C., and a melt viscosity (V6) at 300 ° C. 22 Pa · s.

Production Example 6 Production of polyarylene sulfide resin (B-3) Except that paradichlorobenzene was changed to 24.276 kg and metadichlorobenzene was changed to 1.277 kg (molar ratio of both [(p) / (m)] = 95 / 5) A polyarylene sulfide resin (B-3) was obtained in the same manner as in Production Example 4. The resulting polyarylene sulfide resin (B-3) has a melting point (Tm) of 265 ° C., a recrystallization temperature (Tc2) of 179 ° C., a difference ΔT between them of 86 ° C. and a melt viscosity (V6) at 300 ° C. 10 Pa · s.

Production Example 7 Production of polyarylene sulfide resin (B-4) Except that paradichlorobenzene was changed to 20.442 kg and metadichlorobenzene was changed to 5.111 kg (molar ratio of both [(p) / (m)] = 80 / 20) A polyarylene sulfide resin (B-4) was obtained in the same manner as in Production Example 4. The resulting polyarylene sulfide resin (B-4) has a melting point (Tm) of 212 ° C., a recrystallization temperature (Tc2) of 147 ° C., a difference ΔT between them of 65 ° C., and a melt viscosity (V6) at 300 ° C. It was 21 Pa · s.

Production Example 8 Production of polyarylene sulfide resin (B-5) Except that paradichlorobenzene was changed to 17.887 kg and metadichlorobenzene was changed to 7.666 kg (molar ratio of both [(p) / (m)] = 70 / 30) A polyarylene sulfide resin (B-5) was obtained in the same manner as in Production Example 4. The resulting polyarylene sulfide resin (B-5) had a melt viscosity (V6) at 300 ° C. of 31 Pa · s.

Example 1
After mixing 60 parts by mass of polyarylene sulfide resin (A-1) and 40 parts by mass of polyarylene sulfide resin (B-1) in a powder state, a small twin-screw extruder (“Compounder 15” manufactured by DSM Explorer) Kneading is performed at a kneading temperature of 320 ° C., a rotation speed of 250 rpm, and a residence time of 1 minute, and the melt is extruded in a strand form from a head attached to the small twin-screw extruder and cut into a length of 2 mm. The pellet of the polyarylene sulfide resin composition (1) was obtained.
The melting point (Tm) and recrystallization temperature (Tc2) of the polyarylene sulfide resin composition (1) were measured, and the difference ΔT between them was calculated. The results are shown in Table 1.
The higher the melting point (Tm), the lower the recrystallization temperature (Tc2), and the larger the ΔT, the better the low-temperature moldability and the better the heat resistance.

Examples 2 to 7 and Comparative Examples 1 and 2
Polyarylene sulfide resin compositions (2) to (6) and (1 ′) and (2 ′) were produced in the same manner as in Example 1 using the respective polyarylene sulfide resins at the blending ratios shown in Table 1. The melting point (Tm) and the recrystallization temperature (Tc2) were measured, and the difference ΔT between them was calculated. The results are shown in Table 1.

Examples 8 and 9, Comparative Example 3
Ingredients other than “FT-562” (glass fiber) in the proportions shown in Table 2 below were uniformly mixed with a tumbler to obtain a blended material. Next, using a small twin-screw extruder with a side feeder (“Compounder 15” manufactured by DSM Explore), the compounding material was introduced from the resin charging portion, and “FT-562” (glass fiber) was charged from the side feeder. Melt kneading is performed at a kneading temperature of 320 ° C., a rotation speed of 200 rpm, and a discharge rate of 30 kg / h. The melt is extruded into a strand shape from a head attached to the small twin screw extruder, cut into a length of 2 mm, and polyarylene A pellet of a sulfide resin composition was obtained.

Details of each component in Table 2 are as follows.
· "OSF-6040": manufactured by Dow Corning "XIAMETER (R) OFS-6040 Silane" epoxy-functional alkoxysilane, "CaCO _3": Maruo manufactured calcium "MSK-PO"
"PE-190": "Licowax (registered trademark) PE190 Powder" manufactured by Clariant, high density polyethylene wax "AZO": Zinc oxide manufactured by Shodo Chemical Co., Ltd. "CS-100K": Zeolite manufactured by Katsuta Corporation “FT-562”: “FT-562” manufactured by OWENSCORNING, fiber diameter / 10 (μm), fiber length / 3 (mm), thermal conductivity 1 (W / m · K)

Heat resistance test About the pellet obtained previously, melting | fusing point (Tm2) was measured.

Fluidity test Using the 1.6 mm thick spiral flow mold, the spiral flow length when molded at a cylinder temperature of 320 ° C., a mold temperature of 150 ° C., an injection pressure of 90 MPa, and 6 seconds is used. It was measured. 40 cm or more was evaluated as ◎, and less than 40 cm was evaluated as x.

Burr generation test The pellet obtained above was melted at 320 ° C. with an injection molding machine (“SE75DU” manufactured by Sumitomo Heavy Industries, Ltd.), and a mold for molding Type-A dumbbell specimen (surface roughness of the mold surface). Was formed into a Type-A dumbbell test piece at a cylinder temperature of 320 ° C. and a mold temperature of 60 ° C., and was generated in a degassing gap (clearance of 20 μm) opposite to the gate in the mold. The burr length (μm) was measured and evaluated. The results are shown in Table 2.

Evaluation of Surface Whitening First, the pellets obtained in Comparative Example 3 were melted at 320 ° C. with an injection molding machine (“SE75DU” manufactured by Sumitomo Heavy Industries, Ltd.), and a mold for molding a Type-A dumbbell specimen ( Using a mold surface roughness Rz value of 30 μm, a Type-A dumbbell test piece (surface roughness Rz value 80 μm) was molded at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. to obtain a standard product. Next, the pellets obtained in Examples 8 and 9 and Comparative Examples 3 and 4 were molded into Type-A dumbbell test pieces at the cylinder temperature of 320 ° C. and the mold temperature of 60 ° C. using the same mold. It was. Next, 5 testers compared the degree of surface whitening between the standard product and the test product and scored according to the following criteria.
There is no difference in the degree of whitening between the standard product and the test product ... 0 points The test product is whitened compared to the standard product ... 1 point The average value of the total score of five people was calculated and evaluated according to the following criteria. The results are shown in Table 2.
The average value of total points is 0 points.
Average value of total points is more than 0 to less than 1 point ... “○”
Average value of total points is more than 1 to 2 points ... "△"
The average value of the total points is more than 2 points.

Measurement of surface roughness The pellet obtained above was melted at 320 ° C. with an injection molding machine (“SE75DU” manufactured by Sumitomo Heavy Industries, Ltd.), and a mold for molding a Type-A dumbbell specimen (surface of the mold surface) A Type-A dumbbell test piece was molded at a cylinder temperature of 320 ° C. and a mold temperature of 60 ° C. using a roughness Rz value of 30 μm. The surface roughness (Rz value) of the obtained test piece was measured using a scanning probe microscope (“SPM-9600” manufactured by Keyence Corporation).

Claims

A polyarylene sulfide resin having an arylene thioether as a repeating unit, wherein the bonding point of the thioether and the arylene group is in the para position;
A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thioether and the arylene group is bonded at the para position and a structural site (m) bonded at the meta position. A polyarylene sulfide resin composition comprising a resin (B).
The resins (A) and (B) are each represented by the following structural formula (X)

[Wherein R 1 is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a carboxy group, a nitro group, an amino group, and a phenyl group, and k is an integer of 1 to 4. ]
A polyarylene sulfide resin having as a repeating unit the structural moiety (x) represented by formula (A), wherein the bonding point between the thioether and the arylene group in the structural moiety (x) is in the para position;
A resin (B) having both a structural moiety (p) in which the bonding point of the thioether and the arylene group in the structural moiety (x) is in the para position and a structural moiety (m) in the meta position. 2. The polyarylene sulfide resin composition according to 1.
The polyarylene sulfide resin composition according to claim 1 or 2, wherein a blending mass ratio [(A) / (B)] of the resin (A) and the resin (B) is in a range of 95/5 to 40/60. object.
The molar ratio [(p) / (m)] of the structural part (p) and the structural part (m) of the resin (B) is in the range of 99/1 to 60/40. 4. The polyarylene sulfide resin composition according to any one of 3 above.
The polyarylene sulfide resin according to any one of claims 1 to 4, wherein both the resin (A) and the resin (B) are polyarylene sulfide resins having a carboxyl group or an alkali metal carboxylate at the molecular end. Composition.
The polyarylene sulfide resin composition according to any one of Claims 1 to 5, wherein the melting point (Tm) is 270 ° C or higher and the recrystallization temperature (Tc2) is 210 ° C or lower.
The polyarylene sulfide resin composition according to claim 6, wherein the difference ΔT between the melting point (Tm) and the recrystallization temperature (Tc2) is 70 ° C or higher.
A polyarylene sulfide resin having an arylene thioether as a repeating unit, wherein the bonding point of the thioether and the arylene group is in the para position;
A polyarylene sulfide resin having an arylene thioether as a repeating unit, which has both a structural site (p) where the bonding point of the thioether and the arylene group is bonded at the para position and a structural site (m) bonded at the meta position. The manufacturing method of the polyarylene sulfide resin composition which melt-kneads resin (B) in the temperature range more than melting | fusing point of the said resin (A).
A molded article comprising the polyarylene sulfide resin composition according to any one of claims 1 to 7.
A method for producing a molded article comprising a step of molding the polyarylene sulfide resin composition according to any one of claims 1 to 7 in a mold, wherein the mold temperature is in the range of 40 to 180 ° C. A method for producing a molded product characterized by the above.
The method for producing a molded article according to claim 10, wherein the mold temperature is in the range of 40 to 120 ° C.