JP7136394B1 - Polyarylene sulfide resin composition, molded article and method for producing the same - Google Patents

Abstract

A PAS resin molded article that contains polyarylene sulfide resin (PAS resin), fibrous filler and non-fibrous filler, suppresses swelling due to fuel, and has excellent dimensional stability and mechanical properties even after immersion in fuel, and the molded article To provide a PAS resin composition capable of providing More specifically, it is a PAS resin composition for fuel system parts, comprising a PAS resin (A), a glass fiber (B), and a non-fibrous filler (C) as essential components, wherein the PAS resin (A) is a crosslinked PAS resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes, and the glass fiber (B) is is 50 to 150 parts by mass, and the fibrous filler (C) is in the range of 50 to 150 parts by mass. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to a polyarylene sulfide resin composition, a polyarylene sulfide resin molded article, and a method for producing them.

In recent years, engineering plastics with excellent productivity, moldability, and high heat resistance have been developed, and because they are lightweight, they are widely used as materials for electric, electronic equipment, automobiles, etc. as materials to replace metal materials. In particular, polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin, represented by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin, has excellent heat resistance, mechanical strength, chemical resistance, Due to its excellent moldability and dimensional stability, it is widely used in fields such as automobile parts and electrical and electronic equipment.

Automotive fuel system parts are exposed to fuel such as gasoline and their vapors in addition to high temperature environments. However, there was a problem that the physical strength was lowered.

In order to improve this, a resin composition obtained by blending a PPS resin having a non-Newton index of 1.15 or more, a fibrous filler and a non-fibrous filler in a specific range of ratio (see Patent Document 1), , a resin composition containing a PPS resin having a peak molecular weight in the molecular weight distribution of 34,200 to 100,000 and a thermoplastic elastomer comprising an acid-modified α-olefin copolymer and an epoxy resin is provided (Patent Document 2). reference).

Furthermore, there is known a resin composition comprising a PPS resin forming a continuous phase, a thermoplastic elastomer comprising a polyolefin resin and at least a part of a dynamically crosslinked saturated rubber-like polymer, and a compatibilizer. (See Patent Document 3).

JP 2008-266616 A Japanese Patent Application Laid-Open No. 2004-300272 JP-A-2006-45401

However, the fuel swelling resistance of the resin molded articles obtained by these methods is not sufficient, and further improvement has been desired.

Therefore, the problem to be solved by the present invention is to provide a polyarylene sulfide molded article that suppresses swelling due to fuel and has excellent dimensional stability and mechanical properties even after immersion in fuel, a PAS resin composition that can provide the molded article, and It is to provide those manufacturing methods.

The present inventors have made intensive studies to solve the above problems. The inventors have found that the molded article has excellent fuel swelling resistance and excellent dimensional stability and mechanical properties after being immersed in fuel, leading to the completion of the present invention.

That is, the PAS resin composition for fuel system parts of the present disclosure is
A PAS resin composition for fuel system parts, comprising a PAS resin (A), a glass fiber (B), and a non-fibrous filler (C) as essential components,
The PAS resin (A) is a crosslinked PAS resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes;
The glass fiber (B) is in the range of 50 to 150 parts by mass and the non-fibrous filler (C) is in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the PAS resin (A). . By providing the above configuration, it is excellent in fuel swelling resistance.

Further, in the PAS resin composition for fuel system parts of the present disclosure, the total amount of the glass fiber (B) and the non-fibrous filler (C) is 180 to 300 mass parts with respect to 100 mass parts of the PAS resin (A). It is preferably in the range of part. In this case, the fuel swelling resistance effect can be achieved at a higher level.

The molded article of the present disclosure is obtained by melt-molding the PAS resin composition for fuel system parts described above.

The method for producing the PAS resin composition for fuel system parts of the present disclosure comprises:
A fuel comprising a step of blending a PAS resin (A), a glass fiber (B), and a non-fibrous filler (C) as essential components, and melt-kneading them in a temperature range above the melting point of the PAS resin (A). A method for producing a PAS resin composition for system parts, comprising:
The PAS resin (A) is a crosslinked PAS resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes;
The glass fiber (B) is in the range of 50 to 150 parts by mass and the non-fibrous filler (C) is in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the PAS resin (A). .

Further, in the method for producing a PAS resin composition for fuel system parts of the present disclosure, the total amount of the glass fiber (B) and the non-fibrous filler (C) is 180 parts per 100 parts by mass of the PAS resin (A). It is preferably in the range of up to 300 parts by mass. In this case, fuel swelling resistance can be further improved.

The method for producing a molded article of the present disclosure includes a step of melt-molding the PAS resin composition obtained by the method of producing a PAS resin composition for fuel system parts of the present disclosure, and a step of annealing the resulting molded article. have. In this case, fuel swelling resistance, dimensional stability, and mechanical strength can be further improved.

According to the present disclosure, a molded article containing a PAS resin, a fibrous filler, and a non-fibrous filler, having excellent dimensional stability and mechanical properties, and excellent fuel swelling resistance, and the molded article It is possible to provide a PAS resin composition that can provide and a method for producing them.

The PAS resin composition of the present disclosure is a PAS resin composition for fuel system parts, which is obtained by blending PAS resin (A), glass fiber (B), and non-fibrous filler (C) as essential components. hand,
The PAS resin (A) is a crosslinked PAS resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes;
The glass fiber (B) is 50 to 150 parts by mass and the non-fibrous filler (C) is 50 to 150 parts by mass with respect to 100 parts by mass of the PAS resin (A). This will be explained below.

<PAS resin (A)>
The PAS resin composition of the present disclosure contains a crosslinked PAS resin as an essential component.

The PAS resin has a resin structure in which a repeating unit is a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, 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と、必要に応じてさらに下記一般式（２）

(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). and, if necessary, the following general formula (2)

で表される３官能性の構造部位と、を繰り返し単位とする樹脂である。式（２）で表される３官能性の構造部位は、他の構造部位との合計モル数に対して０．００１～３モル％の範囲が好ましく、特に０．０１～１モル％の範囲であることが好ましい。

It is a resin having a trifunctional structural site represented by and a repeating unit. The trifunctional structural site represented by formula (2) is preferably in the range of 0.001 to 3 mol%, particularly in the range of 0.01 to 1 mol%, relative to the total number of moles with other structural sites. is preferably

Here, the structural moiety represented by the general formula (1), particularly R ¹ and R ² in the formula, is preferably a hydrogen atom from the viewpoint of the mechanical strength of the PAS resin. Examples include those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4).

これらの中でも、特に繰り返し単位中の芳香族環に対する硫黄原子の結合は前記一般式（３）で表されるパラ位で結合した構造であることが前記ＰＡＳ樹脂の耐熱性や結晶性の面で好ましい。

Among these, the structure in which the sulfur atom is bonded to the aromatic ring in the repeating unit at the para position represented by the general formula (3) is particularly desirable in terms of heat resistance and crystallinity of the PAS resin. preferable.

In addition, the PAS resin includes not only the structural sites represented by the general formulas (1) and (2), but also the following structural formulas (5) to (8).

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（５）～（８）で表される構造部位は１０モル％以下であることが、ＰＡＳ樹脂の耐熱性、機械的強度の点から好ましい。前記ＰＡＳ樹脂中に、上記一般式（５）～（８）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。

30 mol % or less of the total of the structural moieties represented by the general formulas (1) and (2) may be contained. In particular, in the present disclosure, it is preferable that the structural sites represented by the general formulas (5) to (8) are 10 mol % or less from the viewpoint of heat resistance and mechanical strength of the PAS resin. When the PAS resin contains the structural sites represented by the general formulas (5) to (8), the binding mode thereof may be either a random copolymer or a block copolymer.

In addition, the PAS resin may have a naphthyl sulfide bond or the like in its molecular structure. The following are preferable.

As for the method for cross-linking the PAS resin, a low-molecular-weight linear polymer obtained by condensation polymerization of a monomer mainly composed of a bifunctional halogen aromatic compound represented by the general formula (1) is treated with oxygen or an oxidizing agent. A method of increasing the melt viscosity by heating at a high temperature in the presence of a compound having 3 or more halogen functional groups as represented by the above general formula (2) can also be used when polycondensing. A method of partially forming a branched or crosslinked structure by using a small amount of a monomer such as a polyhaloaromatic compound can also be used.

The physical properties of the PAS resin are not particularly limited as long as they do not impair the effects of the present invention, but are as follows.

(melt viscosity)
The melt viscosity of the PAS resin used in the present disclosure is not particularly limited, but the melt viscosity (V6) measured at 300 ° C. is preferably in the range of 2 Pa s or more because the balance between fluidity and mechanical strength is good. and is preferably in the range of 1000 Pa·s or less, more preferably in the range of 500 Pa·s or less, and still more preferably in the range of 200 Pa·s or less. However, the melt viscosity (V6) was measured using a PAS resin flow tester, CFT-500D manufactured by Shimadzu Corporation, at 300° C., load: 1.96×10 ⁶ Pa, L/D=10 (mm)/ It is defined as the measured value of the melt viscosity measured after holding at 1 (mm) for 6 minutes.

(isothermal crystallization time)
The isothermal crystallization time of the PAS resin used in the present disclosure is preferably in the range of 0.7 minutes or more, more preferably 0.9 minutes or more, because moldability, mechanical strength, and fuel swelling resistance are improved. and preferably in the range of 3.7 minutes or less, more preferably in the range of 3.0 minutes or less, and even more preferably in the range of 2.2 minutes or less. Within this range, the PAS resin exhibits excellent crystallization properties, and exhibits good moldability, mechanical strength, and fuel swelling resistance. However, the isothermal crystallization time was measured using a differential scanning calorimeter. After melting the PAS resin at 350°C for 3 minutes, it was rapidly cooled to 240°C at a rate of 150°C/min. The measured value is the time required to reach the top of the exothermic peak during quenching. The differential scanning calorimeter includes, for example, a DSC device Pyris Diamond manufactured by Perkin Elmer.

(non-Newton exponent)
Although the non-Newtonian index of the PAS resin used in the present disclosure is not particularly limited, it is preferably in the range of 1.26 or more and 2.50 or less. However, in the present disclosure, the non-Newtonian exponent (N value) is the shear rate (SR ) and shear stress (SS) are measured and calculated using the following formula. The closer the non-Newtonian index (N value) to 1, the more linear the structure, and the higher the non-Newtonian index (N value), the more branched the structure.

［ただし、ＳＲは剪断速度（秒^－１）、ＳＳは剪断応力（ダイン／ｃｍ^２）、そしてＫは定数を示す。］

[Where SR is shear rate (sec ⁻¹ ), SS is shear stress (dynes/cm ² ), and K is a constant. ]

(sodium content)
The PAS resin used in the present disclosure preferably has a sodium atom content of 1800 ppm or less, more preferably 1600 ppm or less, derived from the sulfidation agent used as the starting material. On the other hand, the lower limit of the sodium concentration is preferably reduced to below the detection limit, but excessive reduction may reduce productivity, so it is preferably in the range of 40 ppm or more, and further in the range of 50 ppm or more. is more preferable, and a range of 70 ppm or more is particularly preferable. The sodium atom content contained in the PAS resin was determined by baking the resin at 500° C. and then baking the resin at 530° C. for 6 hours. (manufactured by Shimadzu Corporation) to refer to the concentration of sodium atoms (mass standard).

(Production method)
The method for producing the PAS resin is not particularly limited, but for example (production method 1), a dihalogeno aromatic compound is added in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymer components are added to polymerize. (Manufacturing method 2) A method of polymerizing a dihalogeno aromatic compound in the presence of a sulfidating agent or the like in a polar solvent, and if necessary, adding a polyhalogeno aromatic compound or other copolymerization components, (Manufacturing method 3) A method of self-condensing p-chlorothiophenol by adding other copolymerization components if necessary, (Manufacturing method 4) A diiodo aromatic compound and elemental sulfur are combined with a functional group such as a carboxy group or an amino group. A method of performing melt polymerization under reduced pressure in the presence of an optional polymerization inhibitor, and the like. Among these methods, the method of (manufacturing method 2) is versatile and preferable. During the reaction, an alkali metal salt of carboxylic acid or sulfonic acid, or an alkali hydroxide may be added in order to adjust the degree of polymerization. Among the above-described methods (manufacturing method 2), a hydrous sulfidation agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at such a rate that water can be removed from the reaction mixture, and dihalogeno is produced in the organic polar solvent. adding an aromatic compound and a sulfidating agent to a polyhalogenoaromatic compound, if necessary, and reacting them, and adjusting the amount of water in the reaction system to 0.02 to 0.5 mol per 1 mol of the organic polar solvent; A method for producing a PAS resin by controlling the range of (see JP-A-07-228699), and a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, if necessary For example, a polyhalogeno aromatic compound or other copolymer components are added, and an alkali metal hydrosulfide and an organic acid alkali metal salt are added in an amount of 0.01 to 0.9 mol per 1 mol of the sulfur source. And those obtained by a method of reacting while controlling the water content in the reaction system in the range of 0.02 mol or less per 1 mol of the aprotic polar organic solvent (see WO2010/058713 pamphlet) are particularly preferable. Specific examples of dihalogenoaromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4′-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p '-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and each of the above compounds and compounds having an alkyl group having 1 to 18 carbon atoms in the aromatic ring of, and polyhalogenoaromatic compounds such as 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 and the like. Further, the halogen atoms contained in each of the above compounds are desirably chlorine atoms and bromine atoms.

The post-treatment method of the reaction mixture containing the PAS resin obtained by the polymerization step is not particularly limited. is added, the solvent is distilled off under reduced pressure or normal pressure, and the solid matter after the solvent is distilled off is treated with water, a reaction solvent (or an organic solvent having an equivalent solubility for the low-molecular-weight polymer), acetone, methyl ethyl ketone. , a method of washing with a solvent such as alcohols once or twice or more, followed by neutralization, washing with water, filtration and drying; , ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons (solvents that are soluble in the polymerization solvent used and are poor solvents for at least PAS) as precipitants. A method of precipitating solid products such as PAS and inorganic salts, and filtering, washing, and drying them, or (Post-treatment 3) After completion of the polymerization reaction, the reaction mixture is added with a reaction solvent (or low-molecular-weight An organic solvent having the same solubility as the polymer) is added and stirred, filtered to remove the low molecular weight polymer, and then washed once or twice with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc. (Post-treatment 4) After completion of the polymerization reaction, add water to the reaction mixture, wash with water, filter, and if necessary, add an acid or base at the time of washing with water. (Post-treatment 5) After completion of the polymerization reaction, the reaction mixture is filtered, and if necessary, washed with a reaction solvent once or twice or more, and further washed with water, filtered and dried. , etc. In any post-treatment method, the reactivity, crystallization rate, sodium content, etc. of the PAS resin can be controlled by adding an acid or base during the water washing step to adjust the pH. The pH after the step can be controlled to be in the range of 6.5-11.5, more preferably in the range of 6.5-8.5.

In the post-treatment methods exemplified in (Post-treatment 1) to (Post-treatment 5) above, the PAS resin may be dried in a vacuum, or in the air or in an inert gas atmosphere such as nitrogen. You can do it with

The method for cross-linking the linear-structured PAS resin thus obtained is not particularly limited as long as it is a known method. A method of performing heat treatment in a toxic atmosphere can be mentioned. The heating conditions are preferably in the range of 180° C. or higher to 20° C. lower than the melting point of the PAS resin, from the viewpoint of the time required for the heat treatment and the thermal stability of the PAS resin when it is melted after the heat treatment. . However, the melting point here refers to the one measured according to JIS K 7121 using a differential scanning calorimeter (for example, DSC device Pyris Diamond manufactured by Perkin Elmer).

When the heat treatment is performed in an oxidizing atmosphere such as air or oxygen-enriched air, the oxygen concentration is preferably 5% by volume or more, more preferably 10% by mass or more, from the viewpoint of a high oxidation rate and a short processing time. and from the viewpoint of suppressing the increase in radical generation amount and suppressing the thickening during heat treatment, and from the viewpoint of good hue, preferably 30% by volume or less, more preferably 25% by volume or less. It can be within the range.

<Glass fiber (B)>
The PAS resin composition of the present disclosure contains glass fiber (B) as an essential component.

As the raw material of the glass fiber (B) used in the present disclosure, those known to those skilled in the art can be used, and the fiber diameter, fiber length, aspect ratio, etc. can be appropriately adjusted according to the use of the molded product. .

The glass fiber (B) used in the present disclosure may be processed with a surface treatment agent or a sizing agent. This is preferable because the adhesive strength with the PAS resin can be improved. Examples of the surface treatment agent or sizing agent include silane compounds, titanate compounds, acrylic resins, urethane resins, polyether resins and epoxy resins having functional groups such as amino groups, epoxy groups, isocyanate groups and vinyl groups. At least one polymer selected from the group may be mentioned, and it is particularly preferable to contain a urethane resin from the viewpoint of suppressing excessive fibrillation during processing. When the surface treatment agent or sizing agent contains a urethane resin, the content is not particularly limited, but from the viewpoint of fuel swelling resistance, it is preferably in the range of 35% by mass or less, and in the range of 20% by mass or less. is more preferable.

From the viewpoint of obtaining better mechanical strength, the blending amount of the glass fiber (B) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and 70 parts by mass with respect to 100 parts by mass of the PAS resin (A). A range of at least 1 part is more preferable. On the other hand, it is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 85 parts by mass or less, from the viewpoint of fluidity and workability of the resin composition.

<Non-fibrous filler (C)>
The PAS resin composition of the present disclosure contains a non-fibrous filler (C) as an essential component.

The non-fibrous filler (C) used in the present disclosure is an essential ingredient for improving fuel swelling resistance and high dimensional accuracy. As the non-fibrous filler (C), known and commonly used materials can be used, and examples thereof include fillers of various shapes such as plate-like ones and powder-like ones. Specifically, glass flakes, milled fibers, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, zeolite, boehmite, silica, quartz powder, glass beads, glass powder, silicon silicates such as calcium phosphate, aluminum silicate and diatomaceous earth; metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate Salt, silicon carbide, silicon nitride, boron nitride, various metal powders, and the like. In the present disclosure, these can be used singly or in combination of two or more. Among them, calcium carbonate can be preferably used.

The range of the average particle size (D ₅₀ ) of the non-fibrous filler (C) used in the present disclosure is not particularly limited, but from the viewpoint of excellent mechanical strength and fluidity, it is preferably in the range of 20 μm or less. , 15 μm or less, more preferably 8 μm or less, and particularly preferably 2 μm or less. The average particle size is an average particle size (D ₅₀ ) obtained based on the particle size distribution measured according to a conventional method using a laser diffraction/scattering particle size distribution analyzer (Microtrac MT3300EXII).

The amount of the non-fibrous filler (C) blended in the PAS resin composition of the present disclosure is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably 50 parts by mass with respect to 100 parts by mass of the PAS resin (A). parts or more, more preferably 60 parts by mass or more, more preferably 70 parts by mass or more, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 85 parts by mass or less. Within this range, the resin composition has good fuel swelling resistance and good moldability, especially mold releasability, and the molded product exhibits high dimensional accuracy, which is preferable.

In the PAS resin composition of the present disclosure, the total amount of the glass fiber (B) and the non-fibrous filler (C) is preferably in the range of 180 parts by mass or more with respect to 100 parts by mass of the PAS resin (A). , 200 parts by weight or more. Also, it is preferably in the range of 300 parts by mass or less, more preferably in the range of 250 parts by mass or less. This range is preferable because the resin composition has good fuel swelling resistance and workability, and is excellent in mechanical strength.

The PAS resin composition of the present disclosure can optionally contain a silane coupling agent as an optional component. The silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but is preferably a silane coupling agent 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. mentioned. Examples of such silane coupling agents include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. Alkoxysilane compound containing, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane , γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and other isocyanato group-containing alkoxysilane compounds, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)amino Examples include amino group-containing alkoxysilane compounds such as propyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. In the present disclosure, the silane coupling agent is not an essential component, but when blended, the amount is not particularly limited as long as the effect of the present invention is not impaired. , preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less. This range is preferable because the resin composition has good moldability, particularly releasability, and the mechanical strength of the molded product is improved.

The PAS resin composition of the present disclosure may optionally contain a thermoplastic elastomer as an optional component. Examples of thermoplastic elastomers include polyolefin elastomers, fluorine elastomers, and silicone elastomers, among which polyolefin elastomers are preferred. When these elastomers are added, the blending amount is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.01 parts by mass or more, more preferably The range is from 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. This range is preferable because the resulting PAS resin composition has improved impact resistance.

For example, the polyolefin elastomer is an α-olefin homopolymer, a copolymer of two or more α-olefins, or a copolymer of one or two or more α-olefins and a vinyl polymerizable compound having a functional group. coalescence is mentioned. At this time, examples of the α-olefin include α-olefins having from 2 to 8 carbon atoms such as ethylene, propylene and 1-butene. Examples of the functional group include 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, and the like. . Examples of the vinyl polymerizable compound having the functional group include vinyl acetate; α,β-unsaturated carboxylic acids such as (meth)acrylic acid; α,β- Alkyl esters of unsaturated carboxylic acids; Metal salts of α,β-unsaturated carboxylic acids such as ionomers (metals include alkali metals such as sodium, alkaline earth metals such as calcium, zinc, etc.); glycidyl esters of β-unsaturated carboxylic acids; α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; derivatives of the above α,β-unsaturated dicarboxylic acids (monoesters, diesters, acid anhydrides ), etc., or two or more. The above thermoplastic elastomers may be used alone or in combination of two or more.

Furthermore, in addition to the above components, the PAS resin composition of the present disclosure may contain polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, Polyether sulfone resin, polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoride ethylene resin, polystyrene resin, ABS resin, phenolic resin, urethane Synthetic resins such as resins and liquid crystal polymers (hereinafter simply referred to as synthetic resins) can be blended as optional components. In the present disclosure, the synthetic resin is not an essential component, but when blended, the blending ratio is not particularly limited as long as it does not impair the effects of the present invention. Although it cannot be specified, the ratio of the synthetic resin to be blended in the resin composition according to the present disclosure is, for example, a range of 5 parts by mass or more to 100 parts by mass of the PAS resin (A), and a range of 15 parts by mass or less. The degree of In other words, the ratio of the PAS resin to the total of the PAS resin (A) 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. Range.

In addition, the PAS resin composition of the present disclosure also contains a coloring agent, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, an auxiliary flame retardant, and an antirust agent. , And release agents (metal salts and esters of fatty acids with 18 to 30 carbon atoms including stearic acid and montanic acid, polyolefin waxes such as polyethylene, etc.), etc. May be blended. These additives are not essential components, for example, with respect to 100 parts by mass of the PAS resin (A), preferably in the range of 0.01 parts by mass or more, and preferably 1000 parts by mass or less, more preferably 100 parts by mass It may be used in an amount of not more than 10 parts by mass, more preferably not more than 10 parts by mass, and adjusted appropriately according to the purpose and application so as not to impair the effects of the present invention.

In the method for producing the PAS resin composition of the present disclosure, the PAS resin (A), the glass fiber (B), and the non-fibrous filler (C) are blended as essential components, and the melting point of the PAS resin (A) or higher is wherein the PAS resin (A) is a crosslinked PAS resin and the isothermal crystallization time is 0.7 50 to 150 parts by mass of the glass fiber (B) and 50 to 150 parts by mass of the non-fibrous filler (C) with respect to 100 parts by mass of the PAS resin (A). It is characterized by being in the range of part. Details will be described below.

The method for producing the PAS resin composition of the present disclosure has a step of blending the essential components and melt-kneading them in a temperature range equal to or higher than the melting point of the PAS resin (A). More specifically, the PAS resin composition of the present disclosure contains each essential component and, if necessary, other optional components. The method for producing the resin composition used in the present disclosure is not particularly limited, but a method of blending essential components and optionally optional components and melt-kneading, more specifically, a tumbler or Henschel as necessary A method of homogeneously dry-mixing with a mixer or the like, then introducing into a twin-screw extruder and melt-kneading may be mentioned.

Melt-kneading is performed in a temperature range in which the resin temperature is the melting point of the PAS resin (A) or higher, preferably in a temperature range in which the melting point is +10°C or higher, more preferably the melting point is +10°C or higher, and further preferably the melting point is +20°C or higher. , preferably the melting point + 100°C or less, more preferably the melting point + 50°C or less.

As the melt-kneader, a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. It is preferable to melt-knead while appropriately adjusting the range of and melt-kneading under conditions where the ratio (discharge rate / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). is more preferred. Moreover, addition and mixing of each component to the melt-kneader may be performed simultaneously, or may be performed separately. For example, when adding the glass fiber (B), which is an essential component among the above components, it is preferable from the viewpoint of dispersibility to feed into the extruder from the side feeder of the twin-screw kneading extruder. Regarding the position of the side feeder, the ratio of the distance from the extruder resin input part (top feeder) to the side feeder with respect to the total screw length of the twin-screw kneading extruder is preferably 0.1 or more, and 0 .3 or more is more preferable. Also, the ratio is preferably 0.9 or less, more preferably 0.7 or less.

The PAS resin composition according to the present disclosure obtained by melt-kneading in this manner is a molten mixture containing the essential components, optional components added as necessary, and components derived from them. Therefore, the PAS resin composition of the present disclosure has a morphology in which the PAS resin (A) forms a continuous phase and other essential components and optional components are dispersed. After the melt-kneading, the PAS resin composition according to the present disclosure is processed into pellets, chips, granules, powder, and the like by a known method, for example, extruding the resin composition in a molten state into strands. Therefore, it is preferable to pre-dry in the temperature range of 100 to 150° C. as necessary.

The molded article of the present disclosure is obtained by melt-molding the PAS resin composition. Further, the method for producing a molded article of the present disclosure has a step of melt-molding the PAS resin composition. Therefore, the molded article of the present disclosure has a morphology in which the PAS resin (A) forms a continuous phase and other essential components and optional components are dispersed. When the PAS resin composition has such a morphology, a molded article having excellent fuel swelling resistance and mechanical strength can be obtained.

The PAS resin composition of the present disclosure can be subjected to various molding such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, transfer molding. Also suitable for injection molding applications. When molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a general method. For example, in an injection molding machine, the resin temperature is in the range of the melting point of the PAS resin (A) or higher, preferably the melting point +10°C or higher, more preferably the melting point +10°C to the melting point +100°C, more preferably After passing through the step of melting the PAS resin composition in the temperature range of +20°C to +50°C, the composition may be molded by injecting it into a mold through the resin discharge port. At that time, the mold temperature may also be set within a known temperature range, for example, room temperature (23°C) to 300°C, preferably 130 to 190°C.

A method for manufacturing a PAS resin molded product of the present disclosure includes a step of annealing the molded product. Optimum conditions for the annealing treatment are selected according to the use, shape, etc. of the molded product, and the annealing temperature is preferably in the range of 100° C. or higher, more preferably in the range of 120° C. or higher. On the other hand, it is preferably in the range of 260° C. or lower, more preferably in the range of 240° C. or lower. Although the annealing time is not particularly limited, it is preferably in the range of 0.5 hours or longer, and more preferably in the range of 1 hour or longer. On the other hand, it is preferably in the range of 10 hours or less, more preferably in the range of 8 hours or less. This range is preferable because the distortion of the resulting molded product is reduced and the crystallinity of the resin is improved. Annealing may be performed in the air, but is preferably performed in an inert gas such as nitrogen gas.

The PAS resin molded product of the present disclosure has a weight change rate per unit amount when immersed in FAMB (mixed solution of 30 vol% isooctane + 50 vol% toluene + 5 vol% ethanol + 15 vol% diisobutylene) at 80 ° C. for 1500 hours. , 1.3% or less. Within this range, excellent dimensional stability and mechanical strength can be maintained even after immersion in fuel.

The PAS resin molded article of the present disclosure is characterized by being excellent in fuel swelling resistance. Fossil fuels such as heavy oil, saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, isododecane, unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene, cyclohexane , cyclic saturated hydrocarbons such as cycloheptane, cyclooctane, cyclodecane and decalin; cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene and cyclododecene; It may be one or a plurality of hydrocarbons represented by aromatic hydrocarbons such as benzene, toluene, and xylene.) and fuel system parts that are in contact with or immersed in the vapor. Fuel system parts include, for example, pipes, containers, joints, etc. More specifically, in-vehicle fuel system parts such as fuel tanks, fuel tubes, fuel sensors, fuel pumps, vane pumps, auto ratio flow meters, etc. It can be used preferably. In addition, the molded article of the present disclosure is not only for fuel system parts for vehicles, but also printing parts such as containers, nozzles, brushes, cartridges, pumps, etc. It can also be suitably used for cleaning equipment parts, sliding parts that come into contact with lubricating oil, and cleaning equipment parts that use hydrocarbons as solvents. In addition to this, it can also be made into the following normal resin moldings. For example, protection and support members for box-shaped electrical and electronic component integrated modules Multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, Oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, Electric/electronic parts such as parabolic antennas, computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio/laser discs/compact discs/DVD discs/Blu-ray discs Household and office electrical equipment such as audio/visual equipment parts such as discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and plumbing equipment parts such as water heaters, bath water volume, temperature sensors, etc. Product parts; machine-related parts such as office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, writers, typewriters, etc.: microscopes, binoculars, cameras, watches Optical equipment, precision machinery related parts such as; alternator terminal, alternator connector, brush holder, slip ring, IC regulator, potentiometer base for light dimmer, relay block, inhibitor switch, various valves such as exhaust gas valve, fuel related・Exhaust system / intake system various pipes, air intake nozzle snorkel, intake manifold, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crank Shaft position sensors, temperature sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, hot air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, dust distributors, Starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter Relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, connectors for fuses, horn terminals, insulating plates for electrical components, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons , solenoid bobbins, engine oil filters, and ignition device cases.

The present invention will be described below using Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, unless otherwise specified, "%" and "parts" are based on mass.

<Examples 1 and 2 and Comparative Examples 1 to 3>
Each material was blended according to the compositional components and blending amounts shown in Table 1. After that, these compounding materials are put into a vented twin-screw extruder “TEX-30α (product name)” manufactured by The Japan Steel Works, Ltd., and the resin component discharge amount is 30 kg / hr, the screw rotation speed is 200 rpm, and the set resin temperature is 320 ° C. The pellets of the resin composition were obtained by melt-kneading. The glass fiber was fed from the side feeder (S/T ratio 0.5), and the other materials were premixed uniformly in a tumbler and fed from the top feeder. After drying the obtained pellets of the resin composition in a gear oven at 140° C. for 2 hours, they were injection molded to prepare various test pieces, and the following tests were performed.

<Evaluation>

(1) Weight change rate evaluation during fuel swelling The obtained pellets were supplied to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) set at a cylinder temperature of 320 ° C, and the mold temperature was adjusted to 140 ° C. ISO Injection molding was performed using a D2 sheet piece molding die to obtain an ISO D2 sheet for each example and comparative example. A test piece and a fuel (CM15 or FAMB) were enclosed, heated to 80° C., and exposed for 1500 hours while filling the autoclave with fuel vapor. After slowly cooling to room temperature, the weight change rate (%) relative to the initial weight of the test piece was measured. Note that CM15 is a mixed solution of 15 vol% methanol + 85 vol% Fuel C, FAMB is a mixed solution of 30 vol% isooctane + 50 vol% toluene + 5 vol% ethanol + 15 vol% diisobutylene, and Fuel C is 50 vol% isooctane + It is a mixed solution of 50 vol % toluene.

(2) Evaluation of dimensional change rate after fuel swelling The test piece and fuel (CM15 or FAMB) prepared in the same manner as in (1) are sealed in an autoclave, heated to 80 ° C., and the autoclave is filled with fuel vapor. It was left exposed for 1500 hours. After slowly cooling to room temperature, the dimension of the test piece in the direction perpendicular to the resin flow direction was measured, and the dimensional change rate relative to the test piece not exposed to fuel vapor was calculated.

(3) Evaluation of tensile strength change rate after fuel swelling The obtained pellets were supplied to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) set to a cylinder temperature of 320 ° C., and the mold temperature was adjusted to 140 ° C. Injection molding was performed using an ISO Type-A dumbbell piece molding mold to obtain an ISO Type-A dumbbell piece for each example and comparative example. In addition, the resin was injected from a single gate so as to produce a test piece that did not include a weld portion. The prepared test piece and fuel (CM15 or FAMB) were sealed in an autoclave, heated to 80° C., and exposed for 3000 hours while filling the autoclave with fuel vapor. After slow cooling to room temperature, the tensile strength (MPa) was measured by the measurement method based on ISO 527-1 and 2, and the strength change rate (%) was calculated for the test piece not exposed to fuel vapor.

(4) Evaluation of Charpy impact strength change rate after fuel swelling It was used as a test piece. A test piece and a fuel (CM15 or FAMB) were sealed in an autoclave, heated to 80° C., and exposed for 3000 hours while filling the autoclave with fuel vapor. After slowly cooling to room temperature, a Charpy impact test was performed using a measurement method conforming to ISO179-1/1eA, the impact strength (kJ/mm ² ) was measured, and the strength change rate ( %) was calculated.

(5) Measurement of Tensile Strength Each dumbbell piece prepared in the same manner as in (3) was used to measure tensile strength (MPa) in accordance with ISO527-1 and 2.

(6) Measurement of flexural strength Using a dumbbell piece prepared in the same manner as in (3), flexural strength (MPa) was measured according to the measurement method of ISO 178 "Plastics - Determination of flexural properties".

PAS resin crosslinked PPS resin A-1: melt viscosity (V6) 42 Pa s, sodium content 1200 ppm, isothermal crystallization time 1.1 minutes a-2: melt viscosity (V6) 44 Pa s, sodium content 1400 ppm , Isothermal crystallization time 4.0 minutes Linear polyphenylene sulfide resin a-3: Melt viscosity (V6) 42 Pa s, sodium content 310 ppm, isothermal crystallization time 5.0 minutes

・Glass fiber B-1: surface-treated glass fiber, sizing agent: chopped strand containing 8% urethane resin, 11% polyether resin, 81% other components, fiber diameter 10 μm, fiber length 3 mm

・Non-fibrous filler C-1: calcium carbonate, particle size (D ₅₀ ) 1.7 μm
C-2: Talc, particle size (D ₅₀ ) 14 μm

From Table 1, when using the PPS resin compositions of Examples 1 and 2, compared to when using the PPS resin compositions of Comparative Examples 1 to 3, when using CM15 or FAMB, the weight change rate is low, the swelling when immersed in fuel is reduced, and it has become clear that the fuel swelling resistance is excellent. It was found that the decrease in modulus can be kept low, and the dimensional stability and mechanical properties after immersion in fuel are excellent.

Claims (8)

A polyarylene for fuel system parts that is in contact with or immersed in fuel and its vapor, comprising a polyarylene sulfide resin (A), a glass fiber (B), and a non-fibrous filler (C) as essential components. A sulfide resin composition,
The polyarylene sulfide resin (A) is a crosslinked polyarylene sulfide resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes;
The glass fiber (B) is in the range of 50 to 150 parts by mass and the non-fibrous filler (C) is in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). A polyarylene sulfide resin composition for fuel system parts that are in contact with or immersed in fuel and its vapor . The fuel and the A polyarylene sulfide resin composition for fuel system parts which is in contact with or immersed in the vapor . 3. The polyarylene sulfide resin composition for fuel system parts which is in contact with or immersed in fuel and its vapor according to claim 1 or 2, which is a melt-kneaded product. A molded article obtained by melt-molding the polyarylene sulfide resin composition for fuel system parts which is to be in contact with or immersed in the fuel and its vapor according to any one of claims 1 to 3. A method of using a molded article obtained by melt-molding the polyarylene sulfide resin composition according to any one of claims 1 to 3 as a fuel system part that is in contact with or immersed in fuel and its vapor . A polyarylene sulfide resin (A), a glass fiber (B), and a non-fibrous filler (C) are blended as essential components, and melt-kneaded in a temperature range above the melting point of the polyarylene sulfide resin (A). A method for producing a polyarylene sulfide resin composition for fuel system parts that is in contact with or immersed in a fuel and its vapor, comprising:
The polyarylene sulfide resin (A) is a crosslinked polyarylene sulfide resin, and the isothermal crystallization time is in the range of 0.7 to 3.7 minutes;
The glass fiber (B) is in the range of 50 to 150 parts by mass and the non-fibrous filler (C) is in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). A method for producing a polyarylene sulfide resin composition for fuel system parts that is in contact with or immersed in a fuel and its vapor . The fuel according to claim 6, wherein the total amount of the glass fiber (B) and the non-fibrous filler (C) is in the range of 180 to 300 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). and a method for producing a polyarylene sulfide resin composition for fuel system parts that are in contact with or immersed in the vapor . A method for producing a molded article by melt-molding the polyarylene sulfide resin composition for fuel system parts that is in contact with or immersed in the fuel and its vapor according to any one of claims 1 to 3,
A method for producing a molded product, comprising a step of annealing the obtained molded product.