JP2022153336A - Polyphenylene sulfide resin composition and molded article comprising the same - Google Patents

Abstract

To obtain a polyphenylene sulfide resin composition combining excellent flame retardancy, flexibility and toughness, and a molded article comprising the same.SOLUTION: The polyphenylene sulfide resin composition contains (a) a polyphenylene sulfide resin, (b) an olefinic elastomer, (c) fibrillated polytetrafluoroethylene, and (d) a flame retardant. The content of the component (b) is 1 pt.wt. or more and 40 pts.wt. or less based on 100 pts.wt. of the component (a). The content of the component (c) is 0.01 pt.wt. or more and 10 pts.wt. or less based on 100 pts.wt. of the component (a).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition having excellent flame retardancy, flexibility and toughness, and a molded article made from the same.

Polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin is a super engineering plastic having well-balanced properties such as heat resistance, chemical resistance and flame retardancy. In addition, due to its cost advantage over other super engineering plastics, PPS resin is used in a wide range of applications such as automotive applications, housing equipment applications, electrical and electronic applications, etc. as a highly versatile resin material next to the five major engineering plastics.

Especially in recent years, in response to social issues represented by the SDGs, there has been a strong demand for energy saving through weight reduction in automobile applications and reduction of greenhouse gas emissions through electrification. , PPS resin can be used as a substitute for metal to achieve weight reduction and to exhibit high insulation and heat resistance for electrification, so the amount used in automobile applications tends to increase year by year.

On the other hand, in expanding the use of PPS resin, as an essential problem, compared with other resins, toughness represented by tensile elongation at break in a tensile test is low, and it has brittle properties.

Therefore, for applications requiring toughness, as described in Patent Document 1, a PPS resin composition containing an olefinic elastomer has been developed and put into practical use. In this composition, by blending an olefin-based elastomer, which is a softer material than the PPS resin, improvement in toughness as well as flexibility can be realized.

Patent Document 2 discloses a heat-shrinkable tube made of a PPS resin composition to which flexibility is imparted by adding a thermoplastic elastomer and a plasticizer to the PPS resin.

Further, Patent Documents 3 and 4 describe softening techniques in which a silicone elastomer is added to a PPS resin.

JP-A-61-21156 JP 2013-6919 A JP 2017-222867 A JP 2017-214586 A

However, the inventors of the present invention have evaluated the flame retardancy of a resin composition comprising a PPS resin and an olefin-based elastomer described in Patent Document 1. As a result, the flame retardance of the resin composition is lower than that of the PPS resin alone. It was found that the sex was significantly reduced. This is probably because the PPS resin alone has high flame retardancy, but the blending of the olefin-based elastomer, which is significantly inferior in flame retardancy, reduces the flame retardancy of the composition. While this composition has the advantage of having flexibility and toughness, it does not exhibit the excellent flame retardancy that PPS resins inherently possess, and thus has the problem of limited application development.

In the heat-shrinkable tube made of the PPS resin composition described in Patent Document 2, a plasticizer, which is a low-molecular-weight compound, is added in addition to the thermoplastic elastomer for the purpose of imparting flexibility. Since the flame retardancy is lowered by the addition, it is impossible to obtain the UL94 standard flame retardancy V-0.

Further, in the PPS resin composition described in Patent Document 3, as described in the examples of Patent Document 3, in addition to being inferior in flexibility, the tensile elongation at break is low, sufficient toughness is not obtained, and flame retardancy A PPS resin composition that combines flexibility, flexibility and toughness has not yet been realized.

In the PPS resin composition described in Patent Document 4, as described in the Examples of Patent Document 4, a composition that is excellent in flexibility and tensile elongation at break is shown, but in the composition described in the Examples, both properties In addition, it is impossible to have excellent flame retardancy at the same time.

Accordingly, an object of the present invention is to obtain a polyphenylene sulfide resin composition having both flexibility and toughness while maintaining the flame retardancy of the PPS resin.

As a result of investigations aimed at solving such problems, the present inventors have found that (a) polyphenylene sulfide resin, (b) olefin elastomer, (c) fibrillated polytetrafluoroethylene and (d) flame retardant are used as specific The present inventors have found that the polyphenylene sulfide resin composition contained in the composition has properties of both flame retardancy and toughness while having excellent flexibility. That is, the present invention has been made to solve at least part of the above problems, and can be implemented as the following modes.
(1) A polyphenylene sulfide resin composition comprising (a) a polyphenylene sulfide resin, (b) an olefinic elastomer, (c) fibrillated polytetrafluoroethylene, and (d) a flame retardant, wherein 100 parts by weight of component (a) The content of component (b) is 1 part by weight or more and 40 parts by weight or less per part, and the content of component (c) is 0.01 part by weight or more and 10 parts by weight or less per 100 parts by weight of component (a) A sulfide resin composition.
(2) The polyphenylene sulfide resin composition according to (1), which is a test piece obtained by injection molding the polyphenylene sulfide resin composition, in a bending test in accordance with ISO 178 (2010), 3.0 GPa or less A polyphenylene sulfide resin composition having a flexural modulus of 0 and a flame retardancy of V-0 in a test piece having a thickness of 1.6 mmt or less in measurement according to the UL94 standard.
(3) The polyphenylene sulfide resin composition according to any one of (1) to (2), which is flame retardant measured in a test piece having a thickness of 1.0 mmt or less in measurement according to the UL94 standard. is V-0.
(4) The polyphenylene sulfide resin composition according to any one of (1) to (3), which has a tensile elongation at break of 10% or more in a tensile test according to ISO 527-1,2 (2012). A polyphenylene sulfide resin composition.
(5) The polyphenylene sulfide resin composition according to any one of (1) to (4), wherein the component (c) is acrylic ester-modified polytetrafluoroethylene. thing.
(6) The polyphenylene sulfide resin composition according to any one of (1) to (5), wherein the component (a) forms a continuous phase in the morphology (phase structure) of the polyphenylene sulfide resin composition. and a polyphenylene sulfide resin composition having a phase separation structure in which the component (c) is dispersed with a number average dispersed particle size of 1.0 μm or less to form a dispersed phase.
(7) The polyphenylene sulfide resin composition according to any one of (1) to (6), wherein the component (d) is a phosphorus flame retardant, a halogen flame retardant, and an inorganic flame retardant. A polyphenylene sulfide resin composition as at least one selected flame retardant.
(8) The polyphenylene sulfide resin composition according to any one of (1) to (7), wherein the component (a) is measured using a capillograph at 300° C., orifice length L (mm)/ A polyphenylene sulfide resin composition having a non-Newtonian exponent N calculated by the following formula (1) when measuring shear rate and shear stress under the condition of orifice diameter D (mm) = 10 is 1.30 or more.

SR= ^K.SSN (1)
(Here, N is the non-Newtonian exponent, SR is the shear rate (1/sec), SS is the shear stress (dynes/cm ² ), and K is a constant.)
(9) The polyphenylene sulfide resin composition according to any one of (1) to (8), which is measured using a capillograph at 300° C., orifice length L (mm)/orifice diameter D (mm)= A polyphenylene sulfide resin composition having a melt viscosity of 400 Pa·s or more at a shear rate of 122 s ⁻¹ when measured under conditions of No. 10.
(10) The polyphenylene sulfide resin composition according to any one of (1) to (9), wherein (e) epoxy group, amino group, carboxy group, Polyphenylene sulfide resin containing 0.1 to 5 parts by weight of silicone oil having at least one functional group selected from carbinol group, methacryl group, mercapto group, phenol group, isocyanate group and oxazoline group. Composition.
(11) A molded article made of the polyphenylene sulfide resin composition according to any one of (1) to (10).
(12) A molded article made of the polyphenylene sulfide resin composition according to (11), which is for piping and has a hollow shape.

INDUSTRIAL APPLICABILITY According to the present invention, a polyphenylene sulfide resin composition having excellent flame retardancy, flexibility, toughness and moldability, and a molded product made of the same can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.

(1) (a) polyphenylene sulfide resin (a) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula,

From the viewpoint of heat resistance, a polymer containing 70 mol % or more, more preferably 90 mol % or more of a polymer containing a repeating unit represented by the above structural formula is preferred. In the (a) PPS resin, about less than 30 mol % of the repeating units may be composed of repeating units having the following structure.

A PPS copolymer partially having such a structure has a lower melting point than 280° C., which is the general melting point of PPS, and thus such a resin composition is advantageous in terms of moldability.

The weight-average molecular weight of the (a) PPS resin used in the present invention is not particularly limited, but the weight-average molecular weight is preferably 30,000 to 150,000, more preferably 40,000 to 130,000, and more preferably 45,000 to 110,000 in order to obtain better mechanical properties. is more preferred, and 50,000 to 90,000 is more preferred. When the weight average molecular weight is small, the mechanical properties of the PPS resin itself deteriorate, so it is preferably 30,000 or more. On the other hand, when the weight-average molecular weight exceeds 150,000, the melt viscosity is significantly increased, which tends to be unfavorable in molding.

In addition, the weight average molecular weight in the present invention is a value calculated in terms of polystyrene using gel permeation chromatography (GPC) manufactured by Senshu Kagaku.

The non-Newtonian exponent N of the (a) PPS resin used in the present invention is preferably 1.30 or more, more preferably 1.35 or more, and even more preferably 1.40 or more. When the non-Newtonian index is less than 1.30, the viscosity of the PPS resin is relatively low in a low-shear flow field. This is an unfavorable tendency due to the deterioration of flame retardancy due to reappearance). On the other hand, there is no particular upper limit for the non-Newtonian index. As a method for obtaining a PPS resin having a non-Newtonian index of 1.30 or more, a polyhalogenated aromatic compound having 3 or more halogen atoms in one molecule is used as a polymerization raw material, and a branched structure is introduced into the polymer. Alternatively, after the polymerization of the PPS resin is completed, thermal oxidation crosslinking is performed by heating in an oxygen atmosphere and heating with addition of a crosslinking agent such as a peroxide.

The non-Newtonian exponent in the present invention is measured using a capillograph at 300° C. under the conditions of orifice length L (mm)/orifice diameter D (mm)=10, and shear rate and shear stress are measured. It is calculated from the following formula (1).
SR= ^K.SSN (1)
(Here, N is the non-Newtonian exponent, SR is the shear rate (1/sec), SS is the shear stress (dynes/cm ² ), and K is a constant.)

The method for producing the (a) PPS resin used in the present invention will be described below, but the method is not limited to the following method as long as the (a) PPS resin having the properties described above can be obtained.

First, the contents of the polyhalogenated aromatic compound, the sulfidating agent, the polymerization solvent, the molecular weight modifier, the polymerization aid and the polymerization stabilizer used in the production method will be described.

[Polyhalogenated Aromatic Compound]
A polyhalogenated aromatic compound is a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexa Polyhalogenated aromatics such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene group compounds, preferably p-dichlorobenzene is used. In addition, for the purpose of introducing a carboxyl group, carboxyl group-containing dihalogenated aromatics such as 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, and 3,5-dichlorobenzoic acid It is also one of preferred embodiments to use compounds and mixtures thereof as copolymerizable monomers. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, It is preferable to use p-dihalogenated aromatic compound as a main component.

The amount of the polyhalogenated aromatic compound used is 0.9 to 2.0 mol, preferably 0.95 to 1.0 mol, per mol of the sulfidating agent, from the viewpoint of obtaining the (a) PPS resin having a viscosity suitable for processing. A range of 5 mol, more preferably 1.005 to 1.2 mol can be exemplified.

[Sulfidation agent]
Sulfidating agents include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

Specific examples of alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, with sodium sulfide being preferred. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in anhydrous form.

Specific examples of alkali metal hydrosulfides include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in anhydrous form.

Alkali metal sulfides prepared in situ in the reaction system from alkali metal hydrosulfides and alkali metal hydroxides can also be used. Alternatively, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and transferred to a polymerization tank for use.

Alternatively, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used. Alternatively, an alkali metal sulfide can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and transferred to a polymerization tank for use.

The amount of the charged sulfidating agent means the remaining amount obtained by subtracting the loss from the actual charged amount when a part of the sulfiding agent is lost before the start of the polymerization reaction due to dehydration or the like.

An alkali metal hydroxide and/or an alkaline earth metal hydroxide can be used together with the sulfidating agent. Specific examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures of two or more thereof. Specific examples of metal hydroxides include calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Among them, sodium hydroxide is preferably used.

When an alkali metal hydrosulfide is used as the sulfidating agent, it is particularly preferable to use an alkali metal hydroxide at the same time. 0.20 mol, preferably 1.00 mol to 1.15 mol, more preferably 1.005 mol to 1.100 mol.

[Polymerization solvent]
It is preferable to use an organic polar solvent as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidine non-, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric acid triamide, dimethylsulfone, aprotic organic solvents represented by tetramethylene sulfoxide, and mixtures thereof; It is preferably used because of its high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

The organic polar solvent is used in an amount of 2.0 mol to 10 mol, preferably 2.25 mol to 6.0 mol, more preferably 2.5 mol to 5.5 mol, per 1 mol of the sulfidating agent. be

[Molecular weight modifier]
(a) A monohalogen compound (not necessarily an aromatic compound) is combined with the polyhalogenated aromatic compound in order to form a terminal of the PPS resin to be produced, or to adjust the polymerization reaction or molecular weight. Can be used together.

[Polymerization aid]
In order to obtain the (a) PPS resin with a relatively high degree of polymerization in a shorter time, it is also one of preferred embodiments to use a polymerization aid. The term "polymerization aid" as used herein means a substance that has the effect of increasing the viscosity of the resulting (a) PPS resin. Specific examples of such polymerization aids include organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earth metal salts. metal phosphates and the like. These may be used alone or in combination of two or more. Among them, organic carboxylates, water, and alkali metal chlorides are preferable, and more preferable organic carboxylates are alkali metal carboxylates, and alkali metal chlorides are lithium chloride.

The alkali metal carboxylate has the general formula R(COOM) _n (wherein R is an alkyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms). M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, n is an integer of 1 to 3). Alkali metal carboxylates can also be used as hydrates, anhydrous or aqueous solutions. Specific examples of alkali metal carboxylates include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. can be mentioned.

The alkali metal carboxylate is prepared by adding an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates in approximately equal chemical equivalents to react them. may be formed by Among the above alkali metal carboxylates, lithium salts are highly soluble in the reaction system and have a large auxiliary effect, but are expensive, and potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Therefore, sodium acetate, which is inexpensive and has moderate solubility in the polymerization system, is most preferably used.

When these alkali metal carboxylates are used as polymerization aids, the amount used is usually in the range of 0.01 mol to 2 mol per 1 mol of the charged alkali metal sulfide. A range of 0.1 mol to 0.6 mol is preferred, and a range of 0.2 mol to 0.5 mol is more preferred.

When water is used as a polymerization aid, the amount added is usually in the range of 0.3 mol to 15 mol per 1 mol of the charged alkali metal sulfide. A range of ˜10 mol is preferred, and a range of 1 mol to 5 mol is more preferred.

Of course, it is possible to use two or more kinds of these polymerization aids in combination. For example, if an alkali metal carboxylate and water are used in combination, it is possible to increase the molecular weight with a smaller amount of each.

The timing of addition of these polymerization auxiliaries is not particularly specified, and they may be added at any time during the pre-process described later, at the start of polymerization, or during polymerization, or may be added in multiple portions. When an alkali metal carboxylate is used as a polymerization aid, it is more preferable to add it at the start of the preceding step or at the same time as the start of polymerization from the viewpoint of ease of addition. Further, when water is used as a polymerization aid, it is effective to add it during the polymerization reaction after charging the polyhalogenated aromatic compound.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One indication of side reactions is the formation of thiophenol, and the addition of a polymerization stabilizer can suppress the formation of thiophenol. Specific examples of polymerization stabilizers include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferred. The alkali metal carboxylates mentioned above also act as polymerization stabilizers. In addition, when an alkali metal hydrosulfide is used as the sulfidation agent, it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also serve as polymerization stabilizers.

These polymerization stabilizers may be used alone or in combination of two or more. The amount of the polymerization stabilizer is usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, per 1 mol of the charged alkali metal sulfide. It is preferred to use in If this ratio is too small, the stabilizing effect will be insufficient.

The timing of addition of the polymerization stabilizer is not particularly specified. It is more preferable from the point that it is easy to add at the time of starting the process or at the time of starting the polymerization.

Next, a preferred method for producing the (a) PPS resin used in the present invention will be specifically described in order of the pre-process, the polymerization reaction process, the recovery process, and the post-treatment process, but it is of course limited to this method. not something.

[pre-process]
(a) In the method for producing the PPS resin, the sulfidation agent is usually used in the form of a hydrate. It is preferable to warm and remove excess water out of the system.

Further, as described above, a sulfidating agent prepared from an alkali metal hydrosulfide and an alkali metal hydroxide either in situ in the reaction system or in a tank separate from the polymerization tank can also be used. can be done. Although this method is not particularly limited, it is desirable to add an alkali metal hydrosulfide and an alkali metal hydroxide to an organic polar solvent in an inert gas atmosphere at a temperature range of room temperature to 150°C, preferably room temperature to 100°C. In addition, there is a method in which the temperature is raised to at least 150° C. or higher, preferably 180 to 260° C., under normal pressure or reduced pressure to distill off water. A polymerization aid may be added at this stage. In addition, toluene or the like may be added to carry out the reaction in order to accelerate the distillation of water.

In the polymerization reaction, the amount of water in the polymerization system is preferably 0.3 mol to 10.0 mol per 1 mol of the charged sulfidating agent. Here, the amount of water in the polymerization system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water fed into the polymerization system. Moreover, the water to be charged may be in any form such as water, an aqueous solution, or water of crystallization.

[Polymerization reaction step]
(a) PPS resin is produced by reacting a sulfidating agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200°C or higher and lower than 290°C.

When starting the polymerization reaction step, the organic polar solvent, the sulfidation agent and the polyhalogenated aromatic compound are mixed at a temperature range of normal temperature to 240°C, preferably 100°C to 230°C, preferably in an inert gas atmosphere. do. A polymerization aid may be added at this stage. These raw materials may be added in any order, or may be added at the same time.

Such a mixture is usually heated to a temperature in the range of 200°C to less than 290°C. There is no particular limitation on the heating rate, but a rate of 0.01 to 5°C/min is usually selected, and a range of 0.1 to 3°C/min is more preferable.

In general, the temperature is finally raised to a temperature of 250 to less than 290° C., and the reaction is normally carried out at that temperature for 0.25 to 50 hours, preferably 0.5 to 20 hours.

A method in which the temperature is raised to 270° C. to less than 290° C. after reacting at 200° C. to 260° C. for a certain period of time before reaching the final temperature is effective in obtaining a higher degree of polymerization. In this case, the reaction time at 200° C. to 260° C. is usually selected in the range of 0.25 hours to 20 hours, preferably in the range of 0.25 hours to 10 hours.

In order to obtain a polymer with a higher degree of polymerization, it may be effective to carry out polymerization in multiple stages. When the polymerization is carried out in multiple stages, it is effective that the conversion rate of the polyhalogenated aromatic compound in the system at 245° C. reaches 40 mol % or more, preferably 60 mol %.

The conversion rate of the polyhalogenated aromatic compound (hereinafter abbreviated as PHA) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When the polyhalogenated aromatic compound is added in excess molar ratio to the alkali metal sulfide Conversion rate = [PHA charge amount (mol) - PHA residual amount (mol)] / [PHA charge amount (mol) -PHA excess (mol)].
(B) In cases other than the above (A) Conversion rate = [PHA charged amount (mol) - PHA residual amount (mol)]/[PHA charged amount (mol)].

[Recovery process]
(a) In the method for producing a PPS resin, solid matter is recovered from a polymerization reaction product containing a polymer, a solvent, and the like after completion of polymerization. As for the recovery method, it is essential to adopt a method of recovering the particulate polymer by slow cooling after completion of the polymerization reaction. The slow cooling rate at this time is not particularly limited, but it is usually about 0.1° C./min to 3° C./min. It is not necessary to cool slowly at the same rate in all steps of the slow cooling process, and a method of slow cooling at a rate of 0.1 to 1° C./min until the polymer particles crystallize and precipitate, and then at a rate of 1° C./min or more may be used. may be adopted.

[Post-treatment process]
(a) The PPS resin may be subjected to acid treatment, hot water treatment, washing with an organic solvent, alkali metal or alkaline earth metal treatment after being produced through the above polymerization and recovery steps.

When acid treatment is performed, it is as follows. (a) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not decompose the (a) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid are more preferably used, but those such as nitric acid that decompose and deteriorate the (a) PPS resin are not preferable.

The method of acid treatment includes a method of immersing the (a) PPS resin in an acid or an aqueous solution of an acid. For example, when using acetic acid, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous solution of pH 4 heated to 80 to 200° C. and stirring for 30 minutes. The pH after the treatment may be 4 or higher, eg, about pH 4-8. The acid-treated (a) PPS resin is preferably washed several times with water or hot water in order to remove residual acids or salts. The water used for washing is preferably distilled water or deionized water in the sense that the preferable chemical modification effect of the (a) PPS resin by acid treatment is not impaired.

The case of performing hot water treatment is as follows. (a) When the PPS resin is treated with hot water, the temperature of the hot water is preferably 100° C. or higher, more preferably 120° C. or higher, still more preferably 150° C. or higher, and particularly preferably 170° C. or higher. If the temperature is less than 100°C, the desired chemical modification effect of (a) the PPS resin is small, which is not preferable.

The water to be used is preferably distilled water or deionized water in order to exhibit the desired chemical modification effect of the (a) PPS resin by washing with hot water. There are no particular restrictions on the operation of the hot water treatment, and a predetermined amount of (a) PPS resin is added to a predetermined amount of water, heated and stirred in a pressure vessel, or continuously subjected to hot water treatment. will be As for the ratio of (a) PPS resin and water, it is preferable that the amount of water is large, but usually a bath ratio of 200 g or less of (a) PPS resin per 1 liter of water is selected.

In addition, since decomposition of terminal groups is undesirable, the atmosphere for the treatment is desirably an inert atmosphere in order to avoid this. Furthermore, the (a) PPS resin that has undergone this hot water treatment operation is preferably washed several times with warm water to remove residual components.

When washing with an organic solvent, it is as follows. (a) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not decompose the (a) PPS resin. Examples include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphorasamide, and piperazinones, sulfoxide/sulfone solvents such as dimethylsulfoxide, dimethylsulfone, and sulfolane, ketones such as acetone, methylethylketone, diethylketone, and acetophenone Ether solvents such as dimethyl ether, dipropyl ether, dioxane and tetrahydrofuran, chloroform, methylene chloride, trichlorethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, chlorobenzene Alcohol/phenol solvents such as halogen-based solvents, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and aromatic hydrocarbons such as benzene, toluene, and xylene Solvents and the like are included. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferred. These organic solvents are used singly or in combination of two or more.

As a method for washing with an organic solvent, there is a method such as immersing (a) the PPS resin in an organic solvent, and if necessary, it is possible to appropriately stir or heat the resin. The washing temperature for washing the (a) PPS resin with an organic solvent is not particularly limited, and any temperature in the range of normal temperature to about 300° C. can be selected. There is a tendency that the higher the washing temperature, the higher the washing efficiency. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Also, the cleaning time is not particularly limited. Although it depends on the cleaning conditions, in the case of batch cleaning, a sufficient effect can be obtained by cleaning for 5 minutes or more. It is also possible to wash continuously.

Examples of the method of treating with an alkali metal or alkaline earth metal include a method of adding an alkali metal salt or an alkaline earth metal salt before, during, or after the pre-process, a method of adding an alkali metal salt or an alkaline earth metal salt before, during, or after the pre-process, before, during, or during the polymerization process. Examples include a method of adding an alkali metal salt or alkaline earth metal salt to the polymerization reactor afterward, or a method of adding an alkali metal salt or alkaline earth metal salt at the beginning, middle or end of the washing process. Among them, the easiest method includes a method of adding an alkali metal salt or an alkaline earth metal salt after removing residual oligomers and residual salts by washing with an organic solvent or washing with hot or hot water. Alkali metals and alkaline earth metals are preferably introduced into the PPS in the form of alkali metal ions and alkaline earth metal ions such as acetates, hydroxides and carbonates. Further, it is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water or the like. When the alkali metal or alkaline earth metal is introduced, the concentration of the alkali metal ion or alkaline earth metal ion is preferably 0.001 mmol or more, more preferably 0.01 mmol or more, relative to 1 g of PPS. The temperature is preferably 50°C or higher, more preferably 75°C or higher, and particularly preferably 90°C or higher. Although there is no particular upper limit temperature, 280° C. or less is usually preferable from the viewpoint of operability. The bath ratio (the weight of the washing liquid to the weight of the dry PPS) is preferably 0.5 or more, more preferably 3 or more, and even more preferably 5 or more.

In the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition excellent in retention stability, residual oligomers and residual salts are removed by repeating organic solvent washing and hot water washing at about 80° C. or the above hot water washing several times. After that, acid treatment or treatment with an alkali metal salt or alkaline earth metal salt is preferred, and a method of treatment with an alkali metal salt or alkaline earth metal salt is more preferred.

In addition, the (a) PPS resin can be used after being polymerized by thermal oxidation cross-linking treatment by heating in an oxygen atmosphere and heating with addition of a cross-linking agent such as a peroxide after completion of polymerization.

When dry heat treatment is performed for the purpose of increasing the molecular weight by thermal oxidation crosslinking, the temperature is preferably 160 to 260°C, more preferably 170 to 250°C. Also, the oxygen concentration is desirably 5% by volume or more, more preferably 8% by volume or more. Although there is no particular upper limit for the oxygen concentration, the upper limit is about 50% by volume. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, even more preferably 2 to 25 hours. The heat treatment device may be a normal hot air dryer, or a heating device with a rotating or stirring blade. It is more preferred to use a device.

It is also possible to perform dry heat treatment for the purpose of suppressing thermal oxidation cross-linking and removing volatile matter. The temperature is preferably 130-250°C, more preferably 160-250°C. In this case, the oxygen concentration is desirably less than 5% by volume, more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, even more preferably 1 to 10 hours. The heat treatment device may be a normal hot air dryer, or a heating device with a rotating or stirring blade. It is more preferred to use a device.

In the present invention, a plurality of (a) PPS resins having different melt viscosities may be mixed and used.

In the (a) PPS resin of the present invention, functional groups such as carboxyl groups and amino groups are introduced into the ends and side chains of the PPS resin from the viewpoint of improving the reactivity with (b) the olefin elastomer and other additives. good too. The amount of functional groups is preferably 25 to 400 μmol/g, more preferably 25 to 250 μmol/g, still more preferably 30 to 150 μmol/g, even more preferably 30 to 80 μmol/g. When the amount of functional groups is 25 μmol/g or more, reactivity with (b) the olefin elastomer and other additives is obtained, which is preferable. On the other hand, when the amount of functional groups in the PPS resin is 400 μmol/g or less, it is possible to suppress deterioration in processability, flame retardancy, and chemical resistance due to an increase in the amount of volatile components, which is preferable.

(a) Methods for introducing functional groups such as carboxyl groups and amino groups into the PPS resin include a method of copolymerizing a polyhalogenated aromatic compound containing a carboxyl group and an amino group and a sulfidating agent, and a method of or an amino group-containing compound, such as maleic anhydride or sorbic acid, and reacted with (a) the PPS resin while being melt-kneaded. The type of functional group is preferably a carboxyl group or an amino group.

(2) (b) Olefin-Based Elastomer The addition of (b) an olefin-based elastomer to the PPS resin composition of the embodiment of the present invention is essential for achieving both excellent flexibility and toughness of the resin composition. In addition, olefinic elastomers are selected from the viewpoint of cost advantage over other flexible materials.

Examples of (b) olefin elastomers include ethylene-butene copolymers, ethylene-propylene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, and ethylene-acrylic acid. Methyl copolymer, ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-styrene copolymer, ethylene-acrylic acid Methyl-glycidyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, among others, from the viewpoint of compatibility and dispersibility in PPS resin from, ethylene-butene copolymer, ethylene-propylene copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer , ethylene-vinyl acetate-glycidyl methacrylate copolymer.

The (b) olefin-based elastomer used in the present invention may preferably contain a reactive functional group from the viewpoint of forming intermolecular bonds with the PPS resin.

(b) The reactive functional groups possessed by the olefin elastomer are not particularly limited, and specific examples include vinyl groups, epoxy groups, carboxyl groups, acid anhydride groups, ester groups, aldehyde groups, carbonyldioxy groups, Haloformyl group, alkoxycarbonyl group, amino group, hydroxyl group, styryl group, methacryl group, acryl group, ureido group, mercapto group, sulfide group, isocyanate group, hydrolyzable silyl group, oxazoline group and the like can be exemplified. Epoxy groups, carboxyl groups, amino groups, acid anhydride groups, amino groups, hydroxyl groups, isocyanate groups, and oxazoline groups are preferred, and two or more of these reactive functional groups may be contained.

(b) A method of introducing a reactive functional group into an olefinic elastomer includes a method of blending a compound or resin that is compatible with the olefinic elastomer and containing the functional group, and a method of polymerizing the olefinic elastomer. A method of copolymerizing a polymerizable monomer containing a functional group or a functional group convertible to the functional group to the main chain, side chain or terminal thereof, and a method of polymerizing an olefin elastomer containing the functional group. or a method using an initiator containing a functional group convertible to the functional group, or a method using an olefin elastomer and a polymerizable monomer containing the functional group or a functional group convertible to the functional group as a radical generator. and a method of modifying an olefinic elastomer by a technique such as oxidation or thermal decomposition. Among them, when polymerizing an olefin-based elastomer, a method of copolymerizing a polymerizable monomer containing the above-mentioned functional group or a functional group convertible to the above-mentioned functional group on the main chain, side chain or terminal, A method of reacting an elastomer with a polymerizable monomer containing the above functional group or a functional group convertible to the above functional group in the presence of a radical generator is preferred from the viewpoint of quality, cost and introduction amount control.

The polymerizable monomer containing the functional group is not particularly limited, but for example acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, hymic acid, acid anhydrides thereof, acrylic acid glycidyl, glycidyl methacrylate, glycidyl ethylacrylate, glycidyl itaconate, vinyl acetate, vinyl propionate, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like.

(b) The amount of functional groups contained in the olefin-based elastomer is preferably 0.01% by weight or more based on the weight of the olefin-based elastomer, from the viewpoint of sufficient progress of the reaction with the (a) PPS resin. 0.1% by weight or more is preferable, and 1% by weight or more is more preferable. As the reactivity with the PPS resin is improved, the compatibility is improved, and fine dispersion of the olefinic elastomer in the PPS resin is expected, which is accompanied by an improvement in impact properties, toughness, and the like. The upper limit of the amount of functional groups is not particularly limited as long as the inherent properties of the olefinic elastomer are not impaired, and in consideration of deterioration of fluidity, etc., it is preferably 40% by weight or less, more preferably 30% by weight or less. It can be exemplified as a range.

The amount of the (b) olefin-based elastomer in the embodiment of the present invention must be 1 part by weight or more and 40 parts by weight or less relative to 100 parts by weight of the (a) PPS resin, and is 3 parts by weight or more and 35 parts by weight. The amount is preferably 5 parts by weight or more and 30 parts by weight or less, and more preferably 7 parts by weight or more and 25 parts by weight or less. If the olefinic elastomer exceeds 40 parts by weight with respect to 100 parts by weight of the PPS resin, the olefinic elastomer tends to coarsen in the PPS resin, resulting in a decrease in toughness. On the other hand, if the amount of the olefinic elastomer is less than 1 part by weight with respect to 100 parts by weight of the PPS resin, the flexibility and toughness of the resin composition are unfavorably lowered.

It is also preferable to use two or more types of olefinic elastomers in combination from the viewpoint of improving dispersibility.

(3) (c) fibrillated polytetrafluoroethylene The addition of (c) fibrillated polytetrafluoroethylene to the PPS resin composition of the embodiment of the present invention provides a resin composition with excellent flexibility and toughness at the same time. It is essential to have flame retardancy. The addition of fibrillated polytetrafluoroethylene improves the flame retardance of the composition and exhibits the effect of preventing dripping during the flame retardance test.

Examples of the (c) fibrillated polytetrafluoroethylene include fibrillated polytetrafluoroethylene alone or a polytetrafluoroethylene-based mixture comprising fibrillated polytetrafluoroethylene and an organic polymer.

Fibrillated polytetrafluoroethylene is polytetrafluoroethylene in which polytetrafluoroethylene molecules are bonded together by an external action such as a shearing force to form a fibrous structure. Also, fibrillated polytetrafluoroethylene has a very high molecular weight, and its number average molecular weight ranges from 1.5 million to several tens of millions. The polymerization method for fibrillated polytetrafluoroethylene may be either emulsion polymerization or suspension polymerization. Fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, perfluoroalkylvinyl ether, etc., and fluorine-containing such as perfluoroalkyl (meth)acrylate are used as copolymer components within the range that does not impair fibrillation characteristics. Alkyl (meth)acrylates can be used. The content of the copolymer component is preferably 10% by weight or less with respect to tetrafluoroethylene.

From the viewpoint of fibrillating polytetrafluoroethylene, sintering polytetrafluoroethylene to make it a low-crystalline substance, decomposing polytetrafluoroethylene obtained by emulsion polymerization to reduce its molecular weight, and fibrillating It is not preferable to form a structure with polytetrafluoroethylene of low molecular weight as the core and shell of low-molecular-weight polytetrafluoroethylene.

The polytetrafluoroethylene-based mixture is prepared by (1) a method of mixing an aqueous dispersion of fibrillated polytetrafluoroethylene and an aqueous dispersion or solution of an organic polymer to coprecipitate to obtain a coaggregated mixture; 2) a method of mixing an aqueous dispersion of fibrillated polytetrafluoroethylene and dried organic polymer particles; (3) uniformly mixing an aqueous dispersion of fibrillated polytetrafluoroethylene and a solution of organic polymer particles; (4) polymerizing monomers to form an organic polymer in an aqueous dispersion of fibrillated polytetrafluoroethylene; and (5) polytetrafluoroethylene. After uniformly mixing an aqueous dispersion of fluoroethylene and an organic polymer dispersion, a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained. Modified polytetrafluoroethylene can be used.

Components of the organic polymer include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4 - Aromatic vinyl monomers such as dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, methacryl Butyl acid, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, etc. Acrylic acid ester monomers; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α,β-unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide maleimide monomers such as; epoxy group-containing monomers such as glycidyl methacrylate; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; α-olefin monomers such as isobutylene; diene monomers such as butadiene, isoprene and dimethylbutadiene; , Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate Acrylic acid ester-modified polytetrafluoroethylene using acrylic acid ester monomers such as polytetrafluoroethylene is preferable from the viewpoint of improving dispersibility in resin, flame retardancy accompanying increase in melt viscosity, and moldability. These monomers can be used alone or in combination of two or more.

A preferred example of the (c) fibrillated polytetrafluoroethylene used in the present invention is branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is branched polytetrafluoroethylene, a sufficient anti-dripping effect can be obtained even if the amount of polytetrafluoroethylene added is reduced.

The amount of (c) fibrillated polytetrafluoroethylene in the embodiment of the present invention is essentially 0.01 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the (a) PPS resin. It is preferably 0.05 to 7 parts by weight, more preferably 0.1 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight. If the amount of fibrillated polytetrafluoroethylene exceeds 10 parts by weight with respect to 100 parts by weight of the PPS resin, the melt viscosity and melt tension of the PPS resin composition are significantly increased, which is undesirable. On the other hand, if the amount of fibrillated polytetrafluoroethylene is less than 0.01 parts by weight with respect to 100 parts by weight of the PPS resin, the flame retardancy and anti-dripping effect of the resin composition are not exhibited, which is not preferable.

It is also preferable to use two or more types of fibrillated polytetrafluoroethylene in combination from the viewpoint of improving dispersibility.

(4) (d) Flame Retardant Addition of (d) a flame retardant to the PPS resin composition of the embodiment of the present invention is essential for achieving both excellent flexibility and toughness and flame retardancy of the resin composition. is.

The (d) flame retardant is preferably a phosphorus-based flame retardant, a halogen-based flame retardant, or an inorganic flame retardant.

The phosphorus-based flame retardant used in the present invention is a flame retardant containing a phosphorus component, and includes an aromatic phosphate ester compound, a phosphazene compound, a phosphaphenanthrene compound, a metal phosphinate, a phosphonic acid polymer, ammonium polyphosphate, and polyphosphorus. acid melamine, phosphate ester amide and red phosphorus. Among these, aromatic phosphate ester compounds, phosphazene compounds, phosphaphenanthrene compounds, and metal phosphinates are preferred, and aromatic phosphate ester compounds, phosphazene compounds, and phosphaphenanthrene compounds are more preferred. You may contain 2 or more types of these.

Examples of the aromatic phosphate compounds include resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, bisphenol A diphenyl phosphate, and biphenyl diphenyl phosphate. Commercially available products include PX-202, CR-741, PX-200, PX-201 manufactured by Daihachi Chemical Industry Co., Ltd., FP-500, FP-600, FP-700 and PFR manufactured by Adeka Co., Ltd. etc. can be mentioned.

Examples of the phosphazene compound include a phosphonitrile linear polymer and/or a cyclic polymer, and in particular, those containing linear phenoxyphosphazene as a main component are preferably used. The phosphazene compound can be obtained, for example, by reacting phosphorus pentachloride or phosphorus trichloride as a phosphorus source and ammonium chloride or ammonia gas as a nitrogen source by a known method (the cyclic product may be purified), and the resulting substance is converted into an alcohol , phenols and amines. Also, commercially available products such as “Ravitoru” (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. and SPB-100 manufactured by Otsuka Chemical Co., Ltd. are preferably used.

The phosphaphenanthrene compound is a phosphorus flame retardant having at least one phosphaphenanthrene skeleton in the molecule, and commercially available products include HCA, HCA-HQ, BCA and SANKO-220 manufactured by Sanko Co. and M-Ester.

The metal phosphinates are phosphinates and/or diphosphinates and/or polymers thereof, and the salts include salts of calcium, aluminum, zinc, and the like. Commercially available metal phosphinic acid salts include “Exolit” (registered trademark) OP1230 and OP1240 manufactured by Clariant Japan.

The phosphonic acid polymer is a polymer compound having a phosphorus atom in the main chain, and examples thereof include copolymers of bisphenol A-diphenyl methylphosphonate. HM1100 etc. are mentioned.

The phosphate ester amide is an aromatic amide flame retardant containing a phosphorus atom and a nitrogen atom. Since it is a powdery substance with a high melting point at room temperature, it is excellent in handleability during compounding, and can further improve the heat distortion temperature of molded articles. As a commercially available phosphate ester amide, SP-703 manufactured by Shikoku Kasei Co., Ltd. is preferably used.

Examples of the ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and carbamyl ammonium polyphosphate. It may be coated with a thermosetting resin such as a thermosetting phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, and urea resin.

Examples of the melamine polyphosphate include melamine polyphosphate such as melamine pyrophosphate, melamine pyrophosphate and phosphates with melamine, melam and melem. "MPP-A" manufactured by Sanwa Chemical Co., Ltd., PMP-100 and PMP-200 manufactured by Nissan Chemical Co., Ltd., etc. are preferably used.

The red phosphorus includes not only untreated red phosphorus, but also red phosphorus treated with one or more compound coatings selected from the group consisting of thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. It can be preferably used. Examples of the thermosetting resin for the thermosetting resin coating include phenol-formalin resin, urea-formalin resin, melamine-formalin resin, and alkyd resin. Examples of the metal hydroxide of the metal hydroxide coating include aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. The metal of the metal plating film is not particularly limited as long as it is a resin that can be coated with red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof. Furthermore, two or more of these films may be combined, or two or more may be laminated.

Specific examples of halogen flame retardants preferably used in the present invention include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis(2,4,6-tri Bromophenoxy)ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl[3,5-dibromo-4-(2,3-dibromopropoxy)]benzene, polydibromophenylene oxide, tetrabromobisphenol-S , tris(2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenol-A, tetrabromobisphenol-A derivatives, tetrabromobisphenol-A-epoxy oligomers or polymers, tetrabromobisphenol-A-carbonate oligomers or polymers, brominated epoxy resins such as brominated phenolic novolac epoxy, tetrabromobisphenol-A-bis(2-hydroxydiethyl ether) , tetrabromobisphenol-A-bis(2,3-dibromopropyl ether), tetrabromobisphenol-A-bis(allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris(tribromoneopentyl)phosphate, octabromotrimethylphenylindane, dibromoneopentyl glycol, pentabromobenzyl polyacrylate, dibromocresyl glycidyl ether, and N,N'-ethylene-bis-tetrabromophthalimide, brominated polyphenylene ether, and the like. Among these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, brominated epoxy resin, brominated polystyrene, pentabromobenzyl polyacrylate, brominated polyphenylene ether and the like are preferably used.

Specific examples of inorganic flame retardants preferably used in the present invention include aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide.

The amount of the flame retardant (d) in the embodiment of the present invention is preferably 1 part by weight or more and 150 parts by weight or less, and 5 parts by weight or more and 100 parts by weight or less per 100 parts by weight of the olefin elastomer (b). is preferred, 10 to 75 parts by weight is more preferred, and 20 to 50 parts by weight is more preferred. When the flame retardant is 150 parts by weight or less with respect to 100 parts by weight of the olefinic elastomer, it is preferable because the flexibility and toughness of the PPS resin composition can be maintained. On the other hand, when the flame retardant is 1 part by weight or more with respect to 100 parts by weight of the olefinic elastomer, the effect of improving the flame retardancy of the resin composition can be exhibited, which is preferable. The (d) flame retardant in the embodiment of the present invention may contain two or more of the phosphorus-based flame retardant, the halogen-based flame retardant, and the inorganic flame retardant.

Regarding the dispersion state of the flame retardant (d) in the resin composition in the embodiment of the present invention, a state in which it is uniformly dispersed in the resin composition or a state in which it is unevenly distributed in the olefin elastomer is selected from the viewpoint of improving flame retardancy. preferable.

(5) (e) reactive functional group-containing silicone oil to the PPS resin composition of the embodiment of the present invention (e) epoxy group, amino group, carboxy group, carbinol group, methacryl group, mercapto group, phenol group, isocyanate and an oxazoline group. It is preferable because it also has flame retardancy. As a specific example, at least one of the side chains or terminals of the polydimethylsiloxane has at least one group selected from an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, a phenol group, an isocyanate group, and an oxazoline group. Mention may be made of modified polysiloxane oils with one functional group, or mixtures thereof.

The amount of (e) reactive functional group-containing silicone oil in the embodiment of the present invention is preferably 0.1 parts by weight or more and 5 parts by weight or less, and 0.2 parts by weight or more and 4 parts by weight based on 100 parts by weight of the PPS resin. part is more preferable, and 0.3 to 3 parts by weight is more preferable. By setting the reactive functional group-containing silicone oil to 5 parts by weight or less with respect to 100 parts by weight of the PPS resin, the compatibility of the reactive functional group-containing silicone oil with the PPS resin composition affects bleed out and coarse dispersion. It is preferable because it can suppress the accompanying decrease in toughness. On the other hand, when the reactive functional group-containing silicone oil is 0.1 parts by weight or more with respect to 100 parts by weight of the PPS resin, the effect of improving the toughness and flame retardancy of the resin composition is exhibited, which is preferable.

The term "silicone oil" as used herein refers to a compound having a degree of polymerization of organopolysiloxane of about 10 or more and 70 or less.

(6) (f) Other additives Furthermore, the PPS resin composition of the embodiment of the present invention contains (a) a PPS resin, (b) an olefinic elastomer, and (c) as long as the effects of the present invention are not impaired. A resin other than fibrillated polytetrafluoroethylene may be added and blended. Specific examples include polyamide, polyamide elastomer, polybutylene terephthalate, polyethylene terephthalate, polyester elastomer, polyetherimide, polyetherimide-siloxane copolymer, polyketone, liquid crystal polymer, polyetherketone, polyetheretherketone, fibrillation fluororesin (ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetra Examples include, but are not limited to, fluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), styrene-based elastomers, and silicone-containing polymer compounds. The amount of such resin added is preferably less than 20 parts by weight, preferably less than 15 parts by weight, and more preferably less than 10 parts by weight with respect to 100 parts by weight of the PPS resin. In addition, as a lower limit, it is preferable that these resins are not included, that is, 0 parts by weight.

The blending of other resins forms a phase separation structure with the PPS resin, which is thought to lead to a decrease in toughness due to a decrease in adhesion.

The following compounds can be added to the PPS resin composition of the embodiment of the present invention for the purpose of modification. Polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, plasticizers such as organic phosphorus compounds, crystal nucleating agents such as organic phosphorus compounds, polyether ether ketones, montanic acid waxes, lithium stearate, aluminum stearate Metal soaps such as ethylenediamine/stearic acid/sebacic acid polycondensates, release agents such as silicone compounds, and other usual additives such as water, lubricants, UV inhibitors, anti-coloring agents, coloring agents, foaming agents, etc. can be blended. If any of the above compounds exceeds 10 parts by weight based on the total composition, the original properties of the PPS resin composition of the present invention are impaired, so it is preferable to add 5 parts by weight or less, more preferably 1 part by weight or less.

In addition, in the present invention, a compatibilizing agent can be used in combination for the purpose of enhancing the compatibility between the resins. Specifically, organic silane compounds and epoxy resins can be exemplified.

Specific examples of the organosilane compound are preferably organosilane compounds having at least one functional group selected from an isocyanate group, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a ureido group, and an alkoxy group. Specific examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, methoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, dimethoxymethyl-3-piperazinopropylsilane, 3 -piperazinopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanato Preferable examples include propylethyldimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptomethyldimethoxysilane, and γ-ureidopropyltrimethoxysilane. can.

Among the above organosilane compounds, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane are preferred from the viewpoint of reactivity and handling. .

These alkoxy organic silane compounds can be used alone or in the form of a mixture of two or more.

The blending amount of these organic silane compounds used in the present invention is preferably 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the PPS resin. A more preferable embodiment can be exemplified by 3 to 3 parts by weight. It is preferable that the content of the organic silane compound is 10 parts by weight or less because the flame retardancy of the PPS resin composition to be obtained can be maintained. When the amount of the organic silane compound is 0.01 parts by weight or more, the reaction between the PPS and the organic silane compound is sufficient, and excellent toughness can be exhibited, which is preferable.

Specific examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated epoxy resins, bifunctional epoxy resins with special skeletons having a biphenyl skeleton or naphthalene skeleton, cresol novolak type or trisphenolmethane type epoxy resins, di Glycidyl ether type epoxy resins typified by polyfunctional epoxy resins such as cyclopentadiene type, etc., glycidyl amine type epoxy resins typified by aromatic amine type and aminophenol type typified by hydrophthalic acid type and dimer acid type. A glycidyl ester type epoxy resin can be mentioned. The amount of the epoxy resin to be added is preferably 0.1 to 5 parts by weight, particularly preferably 0.2 to 3 parts by weight, per 100 parts by weight of the total PPS resin composition.

In the present invention, a flame retardant aid can be used in combination for the purpose of enhancing flame retardancy. Specific examples include antimony compounds and nitrogen-containing compounds.

The antimony compound preferably used in the present invention is one that can synergistically improve flame retardancy when used in combination with an organic bromine compound, and includes antimony trioxide, antimony pentoxide, sodium antimonate and antimony phosphate Antimony compounds such as are exemplified, and antimony compounds subjected to surface treatment or the like can also be used. Antimony trioxide is particularly preferred from the viewpoint of flame retardancy.

Nitrogen-containing compounds preferably used in the present invention include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea, and the like. Nitrogen-containing phosphorus-based flame retardants such as ammonium polyphosphate as exemplified in the above phosphorus-based flame retardants are not included in the nitrogen-containing compounds referred to herein, and are treated as (d) flame retardants. Examples of aliphatic amines include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like. Examples of aromatic amines include aniline and phenylenediamine. Examples of nitrogen-containing heterocyclic compounds include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and triazine compounds. Dicyandiamide etc. can be mentioned as a cyanide compound. Examples of aliphatic amides include N,N-dimethylacetamide. Examples of aromatic amides include N,N-diphenylacetamide.

The triazine compounds exemplified above are nitrogen-containing heterocyclic compounds having a triazine skeleton, and include triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, ameline, and amelide. , thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine, and the like.

As melamine cyanurate or melamine isocyanurate, adducts of cyanuric acid or isocyanuric acid and triazine compounds are preferred, usually adducts having a composition of 1:1 (molar ratio), optionally 1:2 (molar ratio). things can be mentioned. The compound is produced by a known method. For example, a mixture of melamine and cyanuric acid or isocyanuric acid is prepared as an aqueous slurry, mixed well to form a salt of the two in the form of fine particles, and then the slurry is filtered. , generally obtained in powder form after drying. Moreover, the above salt does not need to be completely pure, and may contain some unreacted melamine, cyanuric acid, or isocyanuric acid. Also, the average particle diameter before blending with the resin is preferably 100 to 0.01 μm, more preferably 80 to 1 μm, from the viewpoint of flame retardancy, mechanical strength and surface properties of molded articles.

The amount of the flame retardant auxiliary is selected to be less than 30 parts by weight, preferably less than 25 parts by weight, more preferably less than 20 parts by weight, based on 100 parts by weight of the olefin elastomer (b). Preferably, the range of 15 parts by weight or less is more preferable. Although there is no particular lower limit, 1 part by weight or more is preferable. The addition of a flame retardant auxiliary is effective in improving the properties of the flame retardant, but on the other hand, if the amount exceeds 30 parts by weight per 100 parts by weight of the olefinic elastomer, the toughness and flexibility will be reduced. , unfavorable.

Although not an essential component, the PPS resin composition of the embodiment of the present invention may contain an inorganic filler as long as the effect of the present invention is not impaired. Specific examples of such inorganic fillers include glass fibers, carbon fibers, carbon nanotubes, carbon nanohorns, potassium titanate whiskers, zinc oxide whiskers, calcium carbonate whiskers, wollastonite whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, and silicon carbide fibers. , ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, etc., or fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina Silicates such as silicate, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass Non-fibrous fillers such as beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black, silica, and graphite are used. Silica is particularly preferred from the viewpoint of anti-corrosion and lubricant effects. These inorganic fillers may be hollow, and two or more of them may be used in combination. Further, these inorganic fillers may be pretreated with a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound, and an epoxy compound before use. Among them, calcium carbonate, silica, and carbon black are preferable from the viewpoint of anti-corrosion and lubricant.

The amount of the inorganic filler to be blended is selected from a range of less than 10 parts by weight, preferably less than 5 parts by weight, and more preferably less than 3 parts by weight, based on the total 100 parts by weight of the PPS resin composition. A range of 1 part by weight or less is more preferable. Although there is no particular lower limit, 0.0001 parts by weight or more is preferable. Although the addition of inorganic fillers is effective in improving the strength of the material, addition of more than 10 parts by weight is not preferable because it results in a decrease in toughness and softening.

(7) Method for producing a resin composition Examples of the method for producing the PPS resin composition of the embodiment of the present invention include production in a molten state and production in a solution state. Production in situ is preferably used. For production in a molten state, melt-kneading by an extruder, melt-kneading by a kneader, or the like can be used, but from the viewpoint of productivity, melt-kneading by an extruder, which enables continuous production, is preferably used. For melt-kneading by an extruder, at least one extruder such as a single-screw extruder, a twin-screw extruder, a multi-screw extruder such as a four-screw extruder, or a twin-screw single-screw composite extruder can be used. From the viewpoint of improving reactivity and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and melt-kneading by a twin-screw extruder is most preferable.

A more specific method of melt-kneading is not necessarily limited to this, but L/D (L: screw length, D: screw diameter) is 10 or more, preferably 20 or more, and kneading It is preferable to use a twin-screw extruder having two or more, preferably three or more, sections. Although the upper limit of L/D is not particularly limited, 60 or less is preferable from the viewpoint of economy. Also, the upper limit of the number of kneading parts is not particularly limited, but from the viewpoint of productivity, it is preferably 10 or less. The ratio of the kneading portion to the total length of the screw is preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more. If the ratio of the kneading portion to the total length of the screw is less than 15%, the kneading force is poor, so the number average dispersed particle size of (c) the fibrillated polytetrafluoroethylene becomes coarse, and desired physical properties are difficult to develop. On the other hand, the upper limit of the ratio of the kneading portion to the total length of the screw is preferably 70% or less from the viewpoint of preventing deterioration of the resin due to excessive shear heat generation during kneading.

A preferred method is kneading at a screw speed of 150 to 1000 rpm, preferably 300 to 1000 rpm, more preferably 350 to 800 rpm. When the screw rotation speed exceeds 150 rotations/minute, the kneading force is sufficient, so the number-average dispersed particle size of (c) the fibrillated polytetrafluoroethylene becomes finer, leading to the development of the desired toughness. If the screw rotation speed exceeds 1000 rpm, the resin and additives deteriorate due to excessive heat generated by shear during kneading, resulting in a decrease in toughness, a decrease in mold fouling resistance, and burrs due to a decrease in melt viscosity. It is not preferable because it leads to deterioration of molding processability such as.

The preferred range of cylinder temperature (°C) is (a) a temperature range of +5 to 100°C with respect to 250 to 280°C, which is the melting point of the PPS resin, specifically a range of 280 to 400°C, A range of 280 to 360°C is more preferred, and a range of 280 to 330°C is even more preferred.

The order of mixing raw materials during melt-kneading is not particularly limited, but a method of melt-kneading by the above method after blending all the raw materials, a method of melt-kneading by the above method after blending some of the raw materials, A method of blending this and the remaining raw materials and melt-kneading them, or a method of blending a part of the raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading with a twin-screw extruder. may be used. Among them, the method of preliminarily melt-kneading (b) the olefin-based elastomer and (d) the flame retardant and then mixing the remaining raw materials is preferable because it improves the flame retardancy, which is a problem.

(8) PPS Resin Composition The PPS resin composition of the present invention has a flexural modulus (according to ISO 178, bending speed 2 mm/min, 23° C.), which is one of the physical property values indicating the flexibility of the material. It is preferably 0 GPa or less. 2.8 GPa or less is more preferable, and 2.5 GPa or less is even more preferable. For pipe members having a hollow shape, flexibility is required from the viewpoint of bending workability during pipe member production and actual use, and prevention of breakage when joint members are press-fitted into pipe members. The elastic modulus is required to be 3.0 GPa or less. The bending elastic modulus is preferably as low as possible from the viewpoint of flexibility, and although there is no particular lower limit, 0.1 GPa or more that can substantially retain the shape can be exemplified. The method for obtaining a PPS resin composition having such properties is not particularly limited, but for example, (a) the content of the olefinic elastomer (b) relative to 100 parts by weight of the PPS resin is 1 part by weight or more and 40 parts by weight or less. Forming a resin composition and forming a structure in which the component (b) is finely dispersed in the PPS resin can be mentioned.

The PPS resin composition of the present invention preferably has a flame retardance of V-0 measured in a test piece having a thickness of 1.6 mm or less in the measurement according to the UL94 standard, which is an index of flame retardancy of materials. It is preferable that the test piece having a thickness of 1.0 mm or less is V-0, and it is more preferable that the test piece having a thickness of 0.5 mm or less is V-0. In general, the flame retardant property tends to exhibit excellent properties as the thickness of the test piece increases. have Possessing such flame-retardant properties means that it is possible to achieve thin-walled molded products and accompanying weight-reduction of molded products while maintaining excellent flame-retardant properties. Since it contributes not only to the contribution but also to the energy saving effect associated with weight reduction, it can be suitably used for automotive members such as electric vehicles. The method for obtaining a PPS resin composition having such properties is not particularly limited, but for example, (a) the content of (c) fibrillated polytetrafluoroethylene relative to 100 parts by weight of the PPS resin is 0.01 parts by weight or more. 10 parts by weight or less and (d) a resin composition containing a flame retardant, component (c) forming a finely dispersed structure with a number average dispersion diameter of 1.0 μm or less in the PPS resin, and (d) flame retardant For example, the blending amount of the fuel agent (b) is 1 part by weight or more and 150 parts by weight or less per 100 parts by weight of the olefin elastomer.

The PPS resin composition of the present invention has a tensile elongation at break (dumbbell test piece (ISO527-2-1A), tensile speed of 50 mm/min, 23°C, ISO527-1,2 ) is preferably 10% or more, more preferably 12.5% or more, even more preferably 15% or more, and particularly preferably 20% or more. From the viewpoint of suppressing breakage of hollow piping members and various molded products during actual use, it is desirable that the tensile elongation at break of the resin composition is 10% or more. The tensile elongation at break is preferably higher from the viewpoint of suppressing member breakage during actual use, and although there is no particular upper limit, it can be substantially 500% or less. The method for obtaining a PPS resin composition having such properties is not particularly limited, but for example, (a) the content of the olefinic elastomer (b) relative to 100 parts by weight of the PPS resin is 1 part by weight or more and 40 parts by weight or less. Forming a resin composition, forming a finely dispersed structure of the component (b) in the PPS resin, and having a reactive functional group in the component (b) can be mentioned.

The PPS resin composition of the present invention exhibits excellent flame retardancy even when the flexibility and toughness of the PPS resin are improved by blending an olefinic elastomer. In order to express such characteristics, in the phase structure of the PPS resin composition, the PPS resin forms a continuous phase, and (c) the fibrillated polytetrafluoroethylene is dispersed with a number average dispersed particle size of 1.0 μm or less. It is preferred to form a phase. The lower limit is preferably about 1 nm, which is the minimum diameter of substantially non-compatible dispersed particles, although the finer the dispersed diameter, the better. On the other hand, when the number average dispersed particle size exceeds 1.0 μm, it means that the fibrillated polytetrafluoroethylene is poorly dispersed in the resin composition and relatively large aggregates are formed. In the case of this dispersed state, it is considered unfavorable because it becomes the starting point of the breaking point in the tensile test and bending test. As means for controlling the number average dispersed particle size of fibrillated polytetrafluoroethylene in the PPS resin composition to 1.0 μm or less, at least (a) PPS resin, (b) olefinic elastomer, and (c) fibrillation In melt kneading of polytetrafluoroethylene with a twin-screw extruder, it is preferable to satisfy the conditions of L / D of 20 or more, two or more kneading parts, and a screw rotation speed of 200 to 500 rpm. I can give an example. The number-average dispersed particle size referred to here is obtained by molding an ISO527-1-1A test piece at a molding temperature of +20 to 40°C melting peak temperature of the PPS resin, and a thin piece of 0.1 μm or less from the center at room temperature. is cut in the cross-sectional direction perpendicular to the flow direction of the resin during molding of the dumbbell piece, and observed at a magnification of 1000 to 5000 times with a field emission scanning electron microscope SU8220 manufactured by Hitachi High Technologies. For 100 fibrillated polytetrafluoroethylene, first, the maximum diameter and minimum diameter of each are measured, the average value is taken as the dispersed particle diameter, and then the average value thereof is obtained.

Further, setting the melt viscosity of the PPS resin composition to 400 Pa·s or more is also preferable as a means for exhibiting excellent toughness, flame retardancy and moldability. A melt viscosity of 400 Pa·s or more is preferable because it suppresses breakage and deformation of the molten resin at the time of take-up in the extrusion molding of hollow or plate-shaped molded products, and exhibits excellent moldability. In order to increase the melt viscosity of the PPS resin composition to 400 Pa·s or more, it is preferable to use (b) an olefin-based elastomer or to use (a) a PPS resin having a high melt viscosity. From the viewpoint of obtaining excellent toughness, flame retardancy, and moldability, the melt viscosity of the PPS resin composition is more preferably 500 Pa·s or higher, and even more preferably 600 Pa·s or higher. On the other hand, if the viscosity is extremely high, a load will be applied to the torque of the molding apparatus and the like, so the upper limit of the melt viscosity of the PPS resin composition is preferably 3000 Pa·s or less. The melt viscosity of the PPS resin composition in the present invention is measured using a capillograph at 300°C under the conditions of orifice length L (mm)/orifice diameter D (mm) = 10 and a shear rate of 122 s. ^-1 .

(9) Use of PPS resin composition The polyphenylene sulfide resin composition of the present invention can be molded by various molding techniques such as injection molding, extrusion molding, compression molding, blow molding, and injection compression molding. Useful for injection molding applications. In particular, since the polyphenylene sulfide resin composition of the present invention achieves both excellent flexibility and toughness, it is suitable for piping members having a hollow shape. It is suitable for piping members such as tubes and piping members for plumbing applications in housing equipment. It is also suitable for piping members for urban air mobility applications, which require both advanced properties and lightness. Furthermore, by combining the flame retardancy which is a feature of the polyphenylene sulfide resin composition of the present invention, higher safety can be realized in these uses.

Applications of molded products obtained by injection molding include generators, electric motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, and other poles. Electric equipment parts such as rods, electric parts cabinets, sensors, LED lamps, connectors, sockets, resistors, relay cases, small 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, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc.; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio equipment, laser discs (registered trademark) and compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriters Household/office electrical product parts represented by parts, word processor parts, etc. Representatives are office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, writers, typewriters, etc. Machinery related parts: Microscopes, binoculars, cameras, clocks and other optical equipment and precision machinery related parts; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dimmers, exhaust gas valves Fuel-related, exhaust system, intake system various pipes and ducts, turbo duct, air intake nozzle snorkel, intake manifold, fuel pump, 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, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating warm air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper Motor-related parts, distributors, starter switches, starter relays, wire harnesses for transmissions, window Washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter , crash pads, insulation locks, ignition device cases and other automotive and vehicle related parts, mobile phones, smartphones, notebook computers, tablet computers, video cameras, hybrid vehicles, gaskets for secondary batteries, etc. can be exemplified.

Molded products obtained by extrusion molding include round bars, square bars, sheets, films, tubes, pipes, etc. More specific uses include electric insulation for water heater motors, air conditioner motors, drive motors, etc. Materials, film capacitors, speaker diaphragms, magnetic tapes for recording, printed circuit board materials, printed circuit board peripheral parts, seamless belts, semiconductor packages, semiconductor transport trays, process/release films, protective films, film sensors for automobiles, wire cables insulating tape in lithium-ion batteries, insulating washers in lithium-ion batteries, hot and cooling water, chemical tubing, automotive fuel tubing, urban air mobility hot water, cooling water, chemicals, fuel tubing, hot water piping , chemical pipes for chemical plants, pipes for ultrapure water and ultrapure solvents, automobile pipes, pipes for CFCs and supercritical carbon dioxide refrigerants, workpiece holding rings for polishing equipment, and the like. In addition, wire harnesses and controls such as hybrid vehicles, electric vehicles, fuel cell vehicles, railroads, coated moldings for motor coil windings for power generation equipment, heat-resistant electric wires and cables for home appliances, flat cables used for wiring in automobiles, etc. Wires, signal transformers for communication, transmission, high frequency, audio, measurement, etc., and coated moldings of windings of vehicle-mounted transformers can be exemplified.

Applications of molded products obtained by blow molding include automobile fuel tanks, oil tanks, resonators, intercoolers, intake manifolds, turbo ducts, intake and exhaust ducts, radiator pipes, radiator headers, expansion tanks, and oil. A circulation pipe etc. can be illustrated.

These various molded products can of course be subjected to secondary processing such as hot plate welding, laser welding, induction heating welding, high frequency welding, spin welding, vibration welding, ultrasonic welding and injection welding.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

In Examples and Comparative Examples, (a) PPS resin, (b) olefinic elastomer, (c) fibrillated polytetrafluoroethylene, (d) flame retardant, (e) reactive functional group-containing silicone oil, (f) The following were used as other additives.

[(a) PPS resin (a-1, a-2, a-3, a-4, a-5)]
[Reference Example 1 PPS resin (a-1)]
In an autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2923.88 g (70.17 mol) of 96% sodium hydroxide, 11434 N-methyl-2-pyrrolidone (NMP) .50 g (115.50 mol), 1894.20 g (23.10 mol) of sodium acetate, and 10,500 g of ion-exchanged water were charged, and gradually heated to 230°C over about 3 hours while passing nitrogen at normal pressure. After distilling off .1 g and 280 g of NMP, the reactor was cooled to 160°C. The amount of water remaining in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.017 mol per 1 mol of alkali metal sulfide charged.

Then 10458.90 g (71.15 mol) of p-dichlorobenzene and 9078.30 g (91.70 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas and stirred at 240 rpm while stirring at 0.6°C/min. After the temperature was raised to 240°C at a rate of 240°C for 40 minutes, the temperature was raised to 275°C at a rate of 0.8°C/min. Thereafter, while cooling to 250°C at a rate of 1.3°C/min, 2394 g (133 mol) of deionized water was pressurized into the autoclave. After that, it was cooled to 200° C. at a rate of 1.0° C./min, and then rapidly cooled to near room temperature.

The contents were taken out and diluted with 26,300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the obtained particles were washed with 31,900 g of NMP and filtered. This was washed several times with 56,000 g of ion-exchanged water and filtered, and then washed with 70,000 g of a 0.05% by weight aqueous acetic acid solution and filtered. After washing with 70,000 g of ion-exchanged water and filtering, the resulting water-containing PPS particles were dried with hot air at 80°C and then dried at 120°C under reduced pressure. The obtained PPS resin (a-1) had a non-Newtonian index of 1.25, a weight average molecular weight of 54000, a melting point of 280° C., a carboxyl group content of 42 μmol/g and a melt viscosity of 170 Pa·s.

[Reference Example 2 PPS resin (a-2)]
8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone were placed in an autoclave with stirrer and bottom plug valve. (NMP) 11.45 kg (115.50 mol) and ion-exchanged water 10.5 kg were charged, and gradually heated to 245°C over about 3 hours while passing nitrogen at normal pressure to obtain 14.78 kg of water and 0.28 kg of NMP. was distilled off, the reaction vessel was cooled to 200°C. The amount of water remaining in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per 1 mol of the charged alkali metal sulfide.

After cooling to 200° C., 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm to 0.000. The temperature was raised from 200°C to 270°C at a rate of 6°C/min. After reacting at 270°C for 100 minutes, the bottom plug valve of the autoclave was opened, and the contents were flushed into a container with a stirrer over 15 minutes while being pressurized with nitrogen, and stirred at 250°C for a while to remove most of the NMP. .

The resulting solid matter and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70° C. for 30 minutes, and suction-filtered through a glass filter. Then, 76 liters of deionized water heated to 70° C. was poured into a glass filter and suction filtered to obtain a cake.

The resulting cake and 90 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, and acetic acid was added to adjust the pH to 7. After purging the inside of the autoclave with nitrogen, the temperature was raised to 192° C. and held for 30 minutes. The autoclave was then cooled and the contents were discharged.

After the content was suction-filtered through a glass filter, 76 liters of ion-exchanged water at 70° C. was poured thereinto and suction-filtration was performed to obtain a cake. Dry PPS was obtained by drying the resulting cake at 120° C. under a nitrogen stream. A heat treatment was performed at 200° C. in an oxygen stream to obtain a crosslinked PPS resin (a-2). The obtained PPS resin (a-2) had a non-Newtonian index of 1.45, a weight average molecular weight of 56000, a melting point of 280° C., a carboxyl group content of 25 μmol/g and a melt viscosity of 155 Pa·s.

[Reference Example 3 PPS resin (a-3)]
A PPS resin (a-3) was obtained under the same conditions as in Reference Example 1, except that 10420 g (70.89 mol) of p-dichlorobenzene was added. The obtained PPS resin (a-3) had a non-Newtonian index of 1.35, a weight average molecular weight of 73000, a melting point of 280° C., a carboxyl group content of 35 μmol/g and a melt viscosity of 398 Pa·s.

[Reference Example 4 PPS resin (a-4)]
In an autoclave equipped with a stirrer, 8.26 kg (70.0 mol) of 47.5% sodium hydrosulfide, 2.94 kg (70.6 mol) of 96% sodium hydroxide, 11 N-methyl-2-pyrrolidone (NMP) .45 kg (115.5 mol), 1.61 kg (19.6 mol) of sodium acetate, and 5.50 kg of ion-exchanged water were charged and gradually heated to 240°C while nitrogen was passed through at normal pressure, and 9.82 kg of water and NMP0 When 0.28 kg was distilled out, heating was finished and cooling was started. At this point, the amount of water remaining in the system per 1 mol of alkali metal hydrosulfide charged was 1.01 mol including the water consumed for hydrolysis of NMP. Moreover, since the amount of hydrogen sulfide scattered was 1.4 mol, the amount of sulfidation agent in the system after the dehydration step was 68.6 mol. Note that 1.4 mol of sodium hydroxide is newly generated in the system along with the scattering of hydrogen sulfide.

Next, p-dichlorobenzene (p-DCB) 10.33 kg (70.2 mol), 1,2,4-trichlorobenzene (TCB) 0.044 kg (0.24 mol), NMP 9.37 kg (94.5 mol) was added, the reaction vessel was sealed under nitrogen gas, the temperature was raised from 200° C. to 270° C. with stirring, and the polymerization reaction was carried out at 270° C. for 180 minutes. After completion of the reaction, the mixture was cooled to 200°C at a rate of 1.0°C/min, and then rapidly cooled to near room temperature. The slurry was diluted with NMP and stirred at 85° C. for 30 minutes, and filtered through an 80-mesh wire mesh to obtain a solid. The obtained solid matter was similarly washed with NMP and separated by filtration. The obtained solid matter was diluted with ion-exchanged water, stirred at 70° C. for 30 minutes, filtered through an 80-mesh wire mesh to collect the solid matter, and the operation was repeated four times. After that, it was washed in an aqueous solution containing 0.5% by weight of calcium acetate with respect to 1 g of the PPS resin, and filtered through an 80-mesh wire mesh to recover the solid matter. After further washing with ion-exchanged water and filtering, the obtained water-containing PPS particles were dried with hot air at 80°C and dried at 120°C under reduced pressure. The obtained PPS resin (a-4) had a non-Newtonian index of 2.05, a weight average molecular weight of 90000, a melting point of 275° C. and a melt viscosity of 2761 Pa·s.

[Reference Example 5 PPS resin (a-5)]
In an autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2962.50 g (71.10 mol) of 96% sodium hydroxide, 11434 N-methyl-2-pyrrolidone (NMP) 50 g (115.50 mol) of sodium acetate, 516.60 g (6.30 mol) of sodium acetate, and 10,500 g of ion-exchanged water were charged, and gradually heated to 230°C over about 3 hours while passing nitrogen at normal pressure. After distilling off .1 g and 280 g of NMP, the reactor was cooled to 160°C. The amount of water remaining in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.017 mol per 1 mol of alkali metal sulfide charged. Then 10363.50 g (70.50 mol) of p-dichlorobenzene and 9078.30 g (91.70 mol) of NMP are added, the reaction vessel is sealed under nitrogen gas and stirred at 240 rpm at 0.6° C./min. The temperature was raised to 270°C at a rate of , and held at 270°C for 140 minutes. After that, while cooling to 250°C at a rate of 1.3°C/min, 2520 g (140 mol) of deionized water was pressurized into the autoclave. After that, it was cooled to 200° C. at a rate of 1.0° C./min, and then rapidly cooled to near room temperature. The contents were taken out and diluted with 26,300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the obtained particles were washed with 31,900 g of NMP and filtered. This was washed several times with 56,000 g of ion-exchanged water and filtered, and then washed with 70,000 g of a 0.05% by weight aqueous acetic acid solution and filtered. After washing with 70,000 g of ion-exchanged water and filtering, the resulting water-containing PPS particles were dried with hot air at 80°C and then dried at 120°C under reduced pressure. The obtained PPS resin (a-5) had a non-Newtonian index of 1.10, a weight average molecular weight of 42000, a melting point of 280° C., a carboxyl group content of 45 μmol/g and a melt viscosity of 74 Pa·s.

[(b) Olefin-based elastomer (b-1)]
b-1: Ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd. olefin resin, Bond Fast ETX-6, melting point 105° C., MFR: 3 g/10 min (190° C., 21.2 N load)), reactive functional group Amount: 6% by weight

[(c) fibrillated polytetrafluoroethylene (c-1, c-2)]
c-1: Acrylic acid ester-modified fibrillated polytetrafluoroethylene (Metabrene A3800 manufactured by Mitsubishi Chemical Corporation)
c-2: fibrillated polytetrafluoroethylene (Polyflon MPA FA500H manufactured by Daikin Industries, Ltd.)

[(d) flame retardant (d-1, d-2, d-3)]
d-1: brominated polyphenylene ether (Pyrogard SR460B manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
d-2: brominated epoxy resin (SR-T3040 manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)
d-3: Metal phosphinate (OP1230 manufactured by Clariant Japan)

[(e) reactive functional group-containing silicone oil (e-1)]
e-1: Epoxy group-containing silicone oil (X-22-163B manufactured by Shin-Etsu Silicone Co., Ltd.)

[(f) other additives (f-1, f-2, f-3)]
f-1: 3-isocyanatopropyltriethoxysilane (KBE-9007N manufactured by Shin-Etsu Silicone Co., Ltd.)
f-2: Polyetherimide-polydimethylsiloxane copolymer (Siltem 1500 manufactured by SABIC)
f-3: Epoxy-terminated polydimethylsiloxane f-4: Polytetrafluoroethylene that is not fibrillated polytetrafluoroethylene (Lubron L-5 manufactured by Daikin Industries)

In the following examples, material properties were evaluated by the following methods.

[Bending test]
After drying the PPS resin composition pellets of the present invention at 130 ° C. for 3 hours using a hot air dryer, the injection molding machine manufactured by Sumitomo Heavy Industries Ltd. (SE-75DUZ) was set to a cylinder temperature of 310 ° C. and a mold temperature of 145 ° C. ), and using a type A1 test piece-shaped mold specified in ISO 20753 (2008), the average speed of the molten resin passing through the cross-sectional area of the central parallel part is 400 ± 50 mm / s. Injection molding was performed to obtain a test piece. A central parallel portion of this test piece was cut out to obtain a type B2 test piece. After conditioning this test piece for 16 hours under the conditions of 23 ° C. and 50% relative humidity, the flexural modulus is measured under the conditions of a span of 64 mm and a test speed of 2 mm / min in accordance with ISO 178 (2010) method. did

[Flame retardant test]
After drying the PPS resin composition pellets of the present invention at 130 ° C. for 3 hours using a hot air dryer, the cylinder temperature was set to 320 ° C. and the mold temperature was set to 150 ° C. in a Sumitomo Heavy Industries injection molding machine (SE-75DUZ). to obtain a test piece for flame retardancy evaluation. The flame retardancy of the test piece was evaluated according to the evaluation criteria specified in the UL94 vertical test. Flame retardancy is ranked in the order of V-0>V-1>V-2. If the V-2 criteria were not met, it was indicated as out. The thickness of the test piece used was 1.6 mm, 1.0 mm, and 0.5 mm.

[Tensile test]
The type A1 test piece obtained in the same manner as the bending test was conditioned at 23 ° C. and 50% relative humidity for 16 hours, and then according to ISO 527-1, 2 (2012) method, 114 mm between chucks, Test speed: Tensile elongation at break (and strain) was measured under the condition of 50 mm/min.

[Number average dispersed particle diameter of component (C)]
Cut a thin piece of 0.1 μm or less from the center of the central parallel part of the type A1 test piece obtained in the same manner as the bending test at room temperature in the cross-sectional direction perpendicular to the flow direction of the resin during molding of the dumbbell piece. Then, it was observed with a field emission scanning electron microscope SU8220 manufactured by Hitachi High-Technologies Corporation under magnification of 1000 to 5000 times. For arbitrary 100 fibrillated polytetrafluoroethylene, first, the maximum diameter and minimum diameter of each are measured, and the average value is taken as the dispersed particle diameter. and

[Non-Newtonian exponent]
The non-Newtonian index of PPS resin was determined by the following method. Shear stress and shear rate were measured at 300° C. using Toyo Seiki Capilograph 1B (10 mm long, 1 mm diameter capillary), and the non-Newtonian index was calculated by the following equation (1).
SR= ^K.SSN (1)
(Here, N is the non-Newtonian exponent, SR is the shear rate (1/sec), SS is the shear stress (dynes/cm ² ), and K is a constant.)

[Melt viscosity]
The melt viscosity of the PPS resin composition was obtained by the following method. Shear rate measured at 300°C under the conditions of orifice length L (mm)/orifice diameter D (mm) = 10 using Toyo Seiki Capilograph 1B (10 mm length, 1 mm diameter capillary) The value at 122s ^-1 was taken.

[Examples 1-2, 4-9, Comparative Examples 1-4]
PPS resin, olefin-based elastomer, fibrillated polytetrafluoroethylene, flame retardant, silicone oil, and other additives were dry-blended according to the formulation shown in Tables 1 and 2, and then TEX30α type manufactured by Japan Steel Works, Ltd. It was put into a twin-screw extruder (L/D=30, 3 kneading parts) and melt-kneaded. The kneading conditions were a temperature of 300° C. and a rotation speed of 300 rpm. This kneading method is referred to as method A (Table 1). After pelletizing with a strand cutter, the pellets dried at 130° C. for 3 hours were subjected to injection molding. Tables 1 and 2 show the evaluation results of the number average dispersed particle size, flexural modulus and flame retardancy of the fibrillated polytetrafluoroethylene.

[Example 3]
Melt-kneading was performed under the same conditions as in Example 1, except that the kneading part was set at one location, and the resin composition pellets were obtained, and various characteristics were evaluated. The melt-kneading method under these conditions is referred to as method B. The results were as shown in Table 1.

The results of the above examples and comparative examples will be compared and explained.

In Examples 1 to 13, a PPS resin composition containing (a) a PPS resin, (b) an olefin-based elastomer, (c) fibrillated polytetrafluoroethylene, and (d) a flame retardant in a characteristic composition, It exhibits both excellent flexibility and flame retardancy, as well as excellent toughness represented by tensile elongation at break. Comparing Example 2 and Example 3, which are different kneading methods, Example 3 is superior in the dispersibility of the fibrillated polytetrafluoroethylene, and is also superior in thin-wall flame retardancy and tensile elongation at break. In Example 13, Examples 1, 2, 10, and 11 have higher melt viscosity of the resin composition than Example 13 using the low-viscosity PPS resin (a-5), flame retardancy and tensile strength. Excellent breaking elongation.

Compared to Examples 2, 3, 5 to 8, Comparative Example 1 has the same composition of PPS resin and olefinic elastomer, but does not use fibrillated polytetrafluoroethylene and flame retardant, so it is flame retardant. The properties are significantly inferior, and a PPS resin composition having both flexibility, flame retardancy and toughness cannot be obtained.

In Comparative Example 2, the addition of fibrillated polytetrafluoroethylene slightly improved the flame retardancy compared to Comparative Example 1, but V-0 (0.5, 1, 1.6 mmt) characteristics were not exhibited. is not reached.

On the other hand, in Comparative Example 3, compared to Comparative Example 1, the addition of the aromatic phosphate compound slightly improved the flame retardancy, but the same V-0 (0.5, 1, 1.6 mmt) is not achieved.

Comparative Example 4, which has the same composition as Example 1 (Sample No. 4) described in Publicly Known Document 4, exhibits flexibility and high tensile elongation at break, but has low flame retardancy and does not have the flexibility desired by the present invention. However, it is impossible to obtain a PPS resin composition having all of the properties, flame retardancy and toughness.

Compared to Example 2, Comparative Example 5 has the same composition of the PPS resin, the olefin elastomer and the flame retardant, but uses non-fibrillated polytetrafluoroethylene. It is low, and a PPS resin composition having all of the flexibility, flame retardancy, and toughness that the present invention aims at cannot be obtained.

Claims (12)

A polyphenylene sulfide resin composition comprising (a) a polyphenylene sulfide resin, (b) an olefinic elastomer, (c) fibrillated polytetrafluoroethylene, and (d) a flame retardant, with respect to 100 parts by weight of component (a) ( A polyphenylene sulfide resin composition in which the content of component b) is 1 part by weight or more and 40 parts by weight or less, and the content of component (c) is 0.01 part by weight or more and 10 parts by weight or less per 100 parts by weight of component (a). thing. 2. The polyphenylene sulfide resin composition according to claim 1, wherein a bending test conforming to ISO 178 (2010) of a test piece obtained by injection molding the polyphenylene sulfide resin composition has a bending elasticity of 3.0 GPa or less. A polyphenylene sulfide resin composition having a flame retardancy of V-0 as measured in a test piece having a thickness of 1.6 mmt or less in the measurement according to the UL94 standard. The polyphenylene sulfide resin composition according to any one of claims 1 and 2, wherein the flame retardance measured in a test piece having a thickness of 1.0 mmt or less in the measurement according to the UL94 standard is V-0. A polyphenylene sulfide resin composition. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the polyphenylene sulfide resin has a tensile elongation at break of 10% or more in a tensile test according to ISO 527-1,2 (2012). Composition. 5. The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein said component (c) is polytetrafluoroethylene modified with an acrylic acid ester. The polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein in the morphology (phase structure) of the polyphenylene sulfide resin composition, the component (a) forms a continuous phase, and the component (c ) A polyphenylene sulfide resin composition having a phase-separated structure forming a dispersed phase in which the component has a number-average dispersed particle size of 1.0 μm or less. The polyphenylene sulfide resin composition according to any one of claims 1 to 6, wherein the component (d) is at least one selected from phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants. A polyphenylene sulfide resin composition that is a flame retardant. 8. The polyphenylene sulfide resin composition according to any one of claims 1 to 7, wherein the component (a) is measured using a capillograph at 300° C., orifice length L (mm)/orifice diameter D (mm )=10, a polyphenylene sulfide resin composition having a non-Newtonian exponent N calculated by the following formula (1) of 1.30 or more when shear rate and shear stress are measured.
SR= ^K.SSN (1)
(Here, N is the non-Newtonian exponent, SR is the shear rate (1/sec), SS is the shear stress (dynes/cm ² ), and K is a constant.) 9. The polyphenylene sulfide resin composition according to any one of claims 1 to 8, using a capillograph at 300° C. under the conditions of orifice length L (mm)/orifice diameter D (mm)=10. A polyphenylene sulfide resin composition having a melt viscosity of 400 Pa·s or more at a shear rate of 122 s ⁻¹ when measured. 10. The polyphenylene sulfide resin composition according to any one of claims 1 to 9, further comprising (e) an epoxy group, an amino group, a carboxyl group, a carbinol group, and a methacryl group per 100 parts by weight of the component (a). A polyphenylene sulfide resin composition containing 0.1 to 5 parts by weight of a silicone oil having at least one functional group selected from a group, a mercapto group, a phenol group, an isocyanate group and an oxazoline group. A molded article made of the polyphenylene sulfide resin composition according to any one of claims 1 to 10. A molded article made of the polyphenylene sulfide resin composition according to claim 11, the molded article for piping having a hollow shape.