JP3603433B2 - Polyarylene sulfide resin composition - Google Patents

Description

実施例１〜３は、成分（Ａ）と（Ｂ）の配合量を本発明の範囲内で変化させたものである。いずれも成形品のバリ長は短く、衝撃強度は高かった。（Ａ）の配合量を減らし、（Ｂ）の配合量を増やすと、成形品のバリ長はより短くなる。衝撃強度は低くなる傾向にあったが、本発明の効果を十分に達成し得るものであった。実施例４は、実施例１で使用した（Ａ）に代えて、溶融粘度Ｖ_６ がより高く、非ニュートン指数Ｎがより小さい（Ａ）を用いたものである。バリ長及び衝撃強度はいずれも実施例１とほぼ同じであった。実施例５は、実施例１で使用した（Ａ）に代えて、Ｖ_６ がより低く、Ｎがより小さい（Ａ）を用いたものである。実施例１に比べてバリ長は幾分長く、衝撃強度は多少低いが、本発明の効果を損なうものではなかった。また、実施例６は、無機充填剤としてガラス繊維に加えて更に炭酸カルシウムを加え、かつ無機充填剤の総量を増やしたものである。実施例１と比べて、バリ長は著しく短かった。衝撃強度は低くなったが本発明の効果を十分に達成するものであった。
【００６５】
一方、比較例１はＰＡＳとして実施例１の（Ａ）のみを用いたものであり、比較例２はＰＡＳとして実施例１の（Ｂ）のみを用いたものである。（Ａ）のみ （比較例１）ではバリ長が著しく長く、（Ｂ）のみ（比較例２）では衝撃強度が著しく低かった。比較例１及び２から、本発明の範囲で（Ａ）及び（Ｂ）を配合すれば、（Ａ）の持つ衝撃強度の高さと、（Ｂ）の持つ優れたバリ特性とを良好に発現することができることが分かった。比較例３は、実施例１の（Ｂ）ＰＡＳに代えて、Ｖ_６ 及びＮがいずれも（Ｂ）の範囲未満のＰＡＳ（ＰＣ−３）を用いたものである。実施例１に比べてバリ長が著しく長かった。比較例４は、実施例１の（Ａ）ＰＡＳに代えて、Ｖ_６ が（Ａ）の範囲未満のＰＡＳ（ＰＣ−１）を用いたものである。実施例１に比べてバリ長が著しく長く、かつ衝撃強度も低かった。比較例５は、実施例１の（Ａ）ＰＡＳに代えて、Ｖ_６ 及びＮがいずれも（Ａ）の範囲を超えるＰＡＳ（ＰＣ−２）を用いたものである。成形性が悪く、ショートショットを生じ、衝撃強度は低かった。また、バリ長は測定できなかった。比較例６及び７は、夫々、比較例３及び４において、無機充填剤としてガラス繊維に加えて更に炭酸カルシウムを加え、かつ無機充填剤の総量を増やしたものである。いずれもバリ長は著しく長く、かつ衝撃強度は低かった。
【００６６】
【発明の効果】
本発明は、バリ発生量が少なく、かつ高い衝撃強度を有するポリアリーレンスルフィド樹脂組成物を提供することを目的とする。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyarylene sulfide resin composition.
[0002]
[Prior art]
In recent years, a thermoplastic resin having high heat resistance and chemical resistance has been demanded as a material for electric / electronic equipment parts, automobile equipment parts, chemical equipment parts, and the like. Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) typified by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) has recently attracted attention as one of the resins that meets this requirement. However, this resin has a problem that burrs are easily generated at the time of molding because the melt fluidity is too high.
[0003]
Attempts have been made to increase the melt viscosity by thermally oxidatively crosslinking low molecular weight PAS to increase the molecular weight. The thermally oxidized crosslinked PAS has high non-Newtonian properties, and is considered suitable for injection molding from this viewpoint. However, the PAS was very brittle and had extremely poor mechanical strength.
[0004]
In order to improve the mechanical strength, various improved methods have been proposed for producing a high molecular weight PAS by polymerization alone without a thermal oxidation crosslinking treatment.
[0005]
For example, a composition is formed by contacting a sulfur source, p-dihalobenzene, an organic amide, a base and an alkali metal carboxylate described in JP-B-52-12240, and maintaining the composition under polymerization conditions. In producing a PAS by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent as described in JP-A-61-7332, The reaction is carried out at 180 to 235 ° C. in the presence of 0.5 to 2.4 mol of water per mol of alkali metal sulfide to obtain a dihalo aromatic compound having a conversion of 50 to 98 mol% and a melt viscosity of 5 to 300 poise. There is known a method in which PAS is produced, and in the second step, water is added and reacted at 245 to 290 ° C. in the presence of 2.5 to 7.0 mol of water. However, these high molecular weight PASs have a substantially linear molecular structure and are close to Newtonian fluids, so that they have poor burr characteristics. In addition, the cost is high in terms of manufacturing, and this is also extremely disadvantageous.
[0006]
JP-B 5-48786, JP-A-64-9266 and JP-A-2-107666 each disclose mixing two types of PAS having greatly different melt viscosities in order to reduce the formation of burrs. Resin compositions are disclosed. However, these inventions do not use the two different PASs defined in the present invention. In addition, even with the resin composition, reduction of burrs could not be said to be sufficient. JP-A-3-255162 and JP-A-3-292335 each disclose a resin composition obtained by mixing two types of PAS having different properties. In the former, each PAS is a PAS having a substantially linear structure, which is different from the thermally oxidized crosslinked PAS used in the present invention. In the latter, one of the PASs is an uncured PAS, which is different from the use of a thermally oxidized crosslinked PAS in the present invention. In any of the above, it was difficult to reduce the occurrence of burrs.
[0007]
JP-A-3-146556 discloses that a molding material containing a predetermined amount of each of a PAS, a glass fiber, a crystalline zeolite, and an organosiloxane obtained by curing a substantially linear PAS before curing is used as the PAS. It is disclosed that a PAS hardened by mixing a high flow rate PAS and a low flow rate PAS in a predetermined amount can be used (claim 11). However, the publication does not disclose the use of a special method of separately curing the above PASs and then mixing them. When cured after mixing PAS, viscosity adjustment becomes difficult, and low molecular weight PAS is not sufficiently crosslinked. Further, a non-Newtonian index N effective for reducing the occurrence of burrs may not be obtained. Also, the molding material aims to shorten the molding cycle time.
[0008]
JP-A-2-28178 and JP-A-2-286746 disclose that a PPS composition having a small change in molecular weight or melt viscosity and a high stability under high temperature or high energy is used as a stabilizer for PPS. Those containing structural sulfur-containing compounds are described. However, even in these compositions, the control of the viscosity was not sufficient, and the generation of burrs could not be sufficiently suppressed.
[0009]
Further, a resin composition obtained by adding an aluminum compound having a specific structure to PAS in order to reduce the occurrence of burrs during molding (Japanese Patent Application Laid-Open No. 2-191666), a resin composition containing PAS and hydrotalcites (JP-A-2-218754), PAS, a resin composition comprising an alkaline earth metal salt of phosphoric acid and an inorganic fibrous reinforcing agent (JP-A-3-12454), PAS, a silane compound and an inorganic filler (JP-A-64-89208) has been proposed. However, in any case, the improvement of burr generation cannot be said to be sufficient, and further, there is a disadvantage that the cost is increased due to the use of the additive and the operation becomes complicated.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyarylene sulfide resin composition having a low burr generation amount and high impact strength.
[0011]
[Means for Solving the Problems]
The present inventors have attempted various improvements in order to solve the above-mentioned drawbacks. As a result, when blending two different PAS having a following predetermined melt viscosity V ₆ and non-Newtonian index N by a predetermined amount, the less burr amount, and the resin composition having good impact strength can be obtained And completed the present invention.
[0012]
That is, the present invention
(1) (A) melt viscosity _{V 6} is obtained by heat treatment at polyarylene sulfide (a) under vapor phase oxidizing atmosphere is 250 to 2000 poise, a melt viscosity _{V 6} is 800 to 5,000 poises, and polyarylene sulfide 20 to 90 parts by weight non-Newtonian index N is 1.15 to 1.34, and (B) a melt viscosity _{V 6} is 40 to 200 poise polyarylene sulfide (B), gas-phase oxidation obtained by heating treatment under sexual atmosphere, melt viscosity _{V 6} is 800 to 5,000 poise, and a resin composition containing the polyarylene sulfide 80 to 10 parts by weight of non-Newtonian index N is 1.40 to 2.00 Things.
[0013]
The resin composition of the present invention is characterized by using two types of PAS having the above-mentioned properties in combination. By this combination, it is possible to reduce the occurrence of burrs in the resin composition and to improve the impact resistance. Even if a PAS not having the above characteristics is used, or if only one of the PASs having the above characteristics is used, the above effect cannot be exhibited.
[0014]
As a preferred embodiment of the present invention,
(2) (A) melt viscosity _{V 6} of the polyarylene sulfide is from 1,000 to 3,500 poise above (1) resin composition according,
(3) (A) The resin composition according to the above (1) or (2), wherein the non-Newton index N of the polyarylene sulfide is 1.20 to 1.30.
(4) (B) melt viscosity _{V 6} of the polyarylene sulfide is from 1000 to 3500 poise above (1) to the resin composition according to any one of (3),
(5) (B) The resin composition according to any one of the above (1) to (4), wherein the non-Newton index N of the polyarylene sulfide is 1.50 to 1.70.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
The components (A) and (B) PAS used in the resin composition of the present invention are all known polymers having an arylene sulfide repeating unit, and particularly preferably PPS.
[0016]
In the present invention, the melt viscosity _{V 6} of the PAS obtained by heat treatment under component (A) gas phase oxidizing atmosphere, the upper limit is 5000 poises, preferably 3500 poises, particularly preferably 3000 poise, lower Is 800 poises, preferably 1000 poises, and particularly preferably 1500 poises. It is less than the melt viscosity V ₆ is the lower limit, the occurrence of burrs is significant at the time of molding, leading to deterioration of the impact strength of the resin composition. Exceeding the above range is not preferred because the moldability of the resin composition is reduced.
[0017]
(A) In the PAS, the lower limit of the non-Newton index N is 1.15, preferably 1.20, and the upper limit is 1.34, preferably 1.30. Below the lower limit, burrs are remarkably generated during molding. If the upper limit is exceeded, the molding processability of the resin composition is reduced.
[0018]
The above (A) PAS is obtained by heat treatment PAS with (a) under vapor phase oxidizing atmosphere having a melt viscosity V ₆ below.
[0019]
The melt viscosity _{V 6} of the PAS (A), the upper limit is 2000 poise, preferably 1500 poises, particularly preferably 1000 poises, the lower limit is 250 poises, preferably 270 poise, particularly preferably 300 poise. Below the lower limit, the impact resistance of the resin composition decreases. If the upper limit is exceeded, the non-Newton index N of the PAS obtained by the heat treatment cannot be in the range of the (A) PAS of the present invention.
[0020]
Further, melt viscosity _{V 6} of the PAS obtained by heat treatment under component (B) gas phase oxidizing atmosphere, the upper limit is 5000 poises, preferably 3500 poises, particularly preferably 3000 poise, the lower limit is 800 poise , Preferably 1000 poise, particularly preferably 1500 poise. The melt viscosity V ₆ is lower than the lower limit, the generation of burr is significantly during the molding, deteriorating the impact strength of the resin composition. Exceeding the above range is not preferred because the moldability of the resin composition is reduced.
[0021]
(B) In the PAS, the lower limit of the non-Newton index N is 1.40, preferably 1.50, and the upper limit is 2.00, preferably 1.70. If it is less than the above lower limit, burrs are remarkably generated during molding, and the impact strength of the resin composition is reduced. If the upper limit is exceeded, the moldability of the resin composition will be reduced.
[0022]
The above (B) PAS can be obtained by heat treatment PAS and (b) under vapor phase oxidizing atmosphere having a melt viscosity V ₆ below.
[0023]
The melt viscosity _{V 6} of the PAS (b), the upper limit of 200 poises, preferably 180 poises, particularly preferably 150 poise, the lower limit is 40 poise, preferably 50 poise, particularly preferably 60 poise. Below the lower limit, the impact strength of the PAS obtained by the heat treatment is low, and the impact resistance of the resin composition cannot be increased. If the upper limit is exceeded, the burr characteristics of the resin composition will be reduced, and the burr length of the molded product cannot be shortened.
[0024]
In the present invention, the melt viscosity _{V 6} is, 300 ° C. using a flow tester, a viscosity measured after holding at a load ^{20kgf / cm 2, L / D} = 10 6 min (poise).
[0025]
The non-Newton index N is a value calculated by using the following formula (I) by measuring the shear rate and the shear stress under the conditions of 300 ° C. and L / D = 40 using a capillograph. As the N value is closer to 1, the PAS has a more linear structure, and as the N value is higher, the PAS has a more branched structure.
[0026]
(Equation 1)
SR = K · SS ^N (I)
[Where SR is the shear rate (sec- ¹ ), SS is the shear stress (dynes / cm ² ), and K is a constant. ]
The above-mentioned PAS (a) or (b) can be heat-treated in a gas phase oxidizing atmosphere to obtain (A) or (B) PAS, respectively, by any known method. The temperature at which the heat treatment is performed is preferably 100 to 280 ° C, particularly preferably 170 to 250 ° C. When the temperature is lower than the above range, the time required for the heat treatment increases, and when the temperature is higher than the above range, thermal stability during melting is poor. The time required for thermal oxidation treatment vary by melt viscosity _{V 6} and non-Newtonian index N of the heating temperature or the desired PAS, preferably 0.5 to 120 hours, particularly preferably 1 to 90 hours. Said time is less than the above range can not be obtained PAS having a desired V ₆ and N, exceed the above range, the microgel is increased undesirably during processing the PAS.
[0027]
The above-mentioned heat treatment is preferably carried out in a gas-phase oxidizing atmosphere of an oxygen-containing gas such as air, pure oxygen or the like and a mixture thereof with any suitable inert gas. Examples of the inert gas include steam, nitrogen, carbon dioxide, and the like, and a mixture thereof. The concentration of oxygen in the oxygen-containing gas is preferably 0.5 to 50% by volume, particularly preferably 10 to 25% by volume. If the oxygen concentration exceeds the above range, the amount of generated radicals increases and the viscosity at the time of melting becomes remarkable, and the hue becomes dark, which is not preferable. If the oxygen concentration is lower than the above range, the thermal oxidation rate becomes slow, which is not preferable.
[0028]
The apparatus for performing the heat treatment may be a batch type or a continuous type, and a known apparatus can be used. For example, a device for bringing PAS into contact with an oxygen-containing gas in a closed vessel equipped with a stirrer can be used, and a fluidized bed thermal oxidation treatment apparatus equipped with a stirrer is preferably used. The use of such a device makes it possible to reduce the temperature distribution in the bath. As a result, the thermal oxidation can be promoted and the non-uniformity of the molecular weight can be prevented.
[0029]
The method for producing the PASs (a) and (b) of the present invention is not particularly limited. For example, a method of reacting a dihalo aromatic compound with an alkali metal sulfide in an organic amide solvent (Japanese Patent Publication No. 45-3368) can be used.
[0030]
Preferably, in the method described in JP-A-5-222196 for producing a PAS by reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent, the gas phase of the reaction vessel during the reaction is preferably used. A method can be used in which a part of the gas phase in the reaction vessel is condensed by cooling the part, and this is refluxed to a liquid phase. By using the method, it is possible to manufacture a relatively high melt viscosity V ₆ PAS, therefore, preferable since it is possible to obtain a high resin composition having mechanical strength of impact strength and the like.
[0031]
The refluxed liquid has a higher water content than liquid bulk due to the vapor pressure difference between water and the amide solvent. The high water content reflux liquid forms a high water content layer above the reaction solution. As a result, the layer contains a large amount of residual alkali metal sulfide (eg, Na ₂ S), alkali metal halide (eg, NaCl), oligomers, and the like. In the conventional method, at a high temperature of 230 ° C. or higher, in a state where the produced PAS and the raw materials such as Na ₂ S and by-products are uniformly mixed, not only a high molecular weight PAS cannot be obtained, but The depolymerized PAS also occurs, and thiophenol by-product is observed. However, in the present invention, the above disadvantageous phenomenon can be avoided by actively cooling the gas phase portion of the reaction vessel and returning a large amount of the reflux liquid rich in water to the upper part of the liquid phase so as to inhibit the reaction. It can be considered that such factors can be effectively eliminated and a high molecular weight PAS can be obtained. However, the present invention is not limited only to the effect of the above phenomenon, and a high molecular weight PAS can be obtained by various effects caused by cooling the gas phase portion.
[0032]
In this method, it is not necessary to add water during the reaction. However, this does not preclude the addition of water at all. However, if the operation of adding water is performed, some of the advantages of this method are lost. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout the reaction.
[0033]
Cooling of the gas phase portion of the reaction vessel can be performed by external cooling or internal cooling, and can be performed by a cooling means known per se. For example, a method of flowing a cooling medium through an internal coil installed at an upper portion in a reaction vessel, a method of flowing a cooling medium through an external coil or a jacket wrapped around an upper portion of the outside of the reaction vessel, and using a reflux condenser installed at the top of the reaction vessel Methods, such as spraying water or blowing gas (air, nitrogen, etc.) on the upper part of the outside of the reaction vessel, are conceivable. However, any method that results in increasing the amount of reflux in the vessel can be considered. May be used. If the outside air temperature is relatively low (for example, normal temperature), appropriate cooling can be performed by removing a heat insulating material conventionally provided on the upper part of the reaction vessel. In the case of external cooling, the water / amide-based solvent mixture condensed on the reactor wall enters the liquid phase along the reactor wall. The water-rich mixture therefore accumulates in the upper part of the liquid phase, keeping the water content relatively high. In the case of internal cooling, the mixture condensed on the cooling surface likewise travels on the cooling device surface or on the reactor wall and enters the liquid phase.
[0034]
On the other hand, the temperature of the liquid phase bulk is kept at a predetermined constant temperature or controlled according to a predetermined temperature profile. When the temperature is kept constant, it is preferable to carry out the reaction at a temperature of 230 to 275 ° C for 0.1 to 20 hours. More preferably, it is at a temperature of 240 to 265 ° C for 1 to 6 hours. In order to obtain a higher molecular weight PAS, it is preferable to use a reaction temperature profile of two or more steps. When performing this two-step operation, the first step is preferably performed at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too low and is not practical. If the temperature is higher than 240 ° C., the reaction rate is too high, so that not only PAS having a sufficiently high molecular weight cannot be obtained, but also the side reaction rate significantly increases. The first stage is preferably terminated when the residual ratio of the dihalo aromatic compound in the polymerization reaction system is 1 mol% to 40 mol% and the molecular weight is in the range of 3,000 to 20,000. More preferably, the residual ratio of the dihaloaromatic compound in the polymerization reaction system is in the range of 2 mol% to 15 mol%, and the molecular weight is in the range of 5,000 to 15,000. If the residual ratio exceeds 40 mol%, side reactions such as depolymerization tend to occur in the second stage reaction, while if it is less than 1 mol%, it is difficult to finally obtain a high molecular weight PAS. Thereafter, the temperature is raised, and the reaction in the final stage is preferably performed at a reaction temperature of 240 to 270 ° C. for 1 hour to 10 hours. If the temperature is low, it is not possible to obtain a PAS having a sufficiently high molecular weight, and if the temperature is higher than 270 ° C., side reactions such as depolymerization are liable to occur, making it difficult to obtain a high molecular weight product stably.
[0035]
As an actual operation, first, under an inert gas atmosphere, dehydration or water addition is performed as necessary so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount. The water content is preferably 0.5 to 2.5 mol, particularly 0.8 to 1.2 mol, per 1 mol of alkali metal sulfide. If it exceeds 2.5 moles, the reaction rate will be low, and the amount of by-products such as phenol will increase in the filtrate after the reaction, and the degree of polymerization will not increase. If the amount is less than 0.5 mol, the reaction rate is too high, and a product having a sufficient high molecular weight cannot be obtained.
[0036]
In the case of a one-stage reaction at a constant temperature, the cooling of the gas phase during the reaction is desirably performed from the start of the reaction, but must be performed at least during the temperature rise of 250 ° C. or lower. In the multi-stage reaction, it is preferable to perform cooling from the first-stage reaction, but it is preferable to perform cooling at the latest at the middle of the temperature rise after completion of the first-stage reaction. The degree of the cooling effect is usually the most suitable index of the pressure in the reactor. The absolute value of the pressure differs depending on the characteristics of the reaction vessel, the stirring state, the amount of water in the system, the molar ratio of the dihalo aromatic compound to the alkali metal sulfide, and the like. However, when the pressure in the reaction vessel is reduced as compared with the case where the reaction vessel is not cooled under the same reaction conditions, the amount of the reflux liquid increases, which means that the temperature at the gas-liquid interface of the reaction solution decreases. It is considered that the relative degree of decrease indicates the degree of separation between a layer having a high water content and a layer having no water content. Therefore, it is preferable to perform cooling to such an extent that the internal pressure of the reaction vessel is lower than that in the case where no cooling is performed. The degree of cooling can be appropriately set by those skilled in the art according to the equipment used, operating conditions, and the like.
[0037]
The organic amide solvents used herein are known for PAS polymerization, such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, and the like, and mixtures thereof. And N-methylpyrrolidone is preferred. They all have a lower vapor pressure than water. Alkali metal sulfides are also known, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof. These hydrates and aqueous solutions may be used. Hydrosulfides and hydrates respectively corresponding to these can be used after being neutralized with the corresponding hydroxides. Inexpensive sodium sulfide is preferred.
[0038]
The dihalo aromatic compound can be selected from, for example, those described in JP-B-45-3368, but is preferably p-dichlorobenzene. In addition, a copolymer can be obtained using one or more kinds of paraphenyl, meta or ortho dihalo compounds of diphenyl ether, diphenyl sulfone or biphenyl in a small amount (20 mol% or less). For example, m-dichlorobenzene, o-dichlorobenzene, p, p'-dichlorodiphenylether, m, p'-dichlorodiphenylether, m, m'-dichlorodiphenylether, p, p'-dichlorodiphenylsulfone, m, p'- Dichlorodiphenylsulfone, m, m'-dichlorodiphenylsulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl and m, m'-dichlorobiphenyl.
[0039]
To increase the molecular weight of the PAS, the polyhaloaromatic compound can be used, preferably at a concentration of 5 mol% or less based on the dihaloaromatic compound. The polyhalo aromatic compound is a compound having three or more halogen substituents in one molecule, for example, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene. , 1,3-dichloro-5-bromobenzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene, 1,3,5-trichloro-2,4,6- Trimethylbenzene, 2,2 ', 4,4'-tetrachlorobiphenyl, 2,2', 6,6'-tetrabromo-3,3 ', 5,5'-tetramethylbiphenyl, 1,2,3,4 -Tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene and the like, and mixtures thereof, and 1,2,4-trichlorobenzene and 1,3,5-trichlorobenzene Masui.
[0040]
In addition, a terminal stopper and a monohalide as a modifying agent can be used in combination as other small amount additives.
[0041]
The PASs (a) and (b) thus obtained can be separated from by-products by post-treatment methods known to those skilled in the art.
[0042]
The resin composition of the present invention comprises 20 to 90 parts by weight of component (A) and 80 to 10 parts by weight of component (B), preferably 30 to 80 parts by weight of (A) and 70 to 20 parts by weight of (B). Contains (A) 40 to 70 parts by weight and (B) 60 to 30 parts by weight. If the component (A) is less than the above lower limit and (B) exceeds the above upper limit, the impact strength is not sufficiently improved, and if the component (A) exceeds the above upper limit and (B) is below the above lower limit, the burr length of the molded product will be insufficient. It is not preferable because it becomes longer.
[0043]
The resin composition of the present invention may further contain an inorganic filler as an optional component. The inorganic filler is not particularly limited, but for example, a powdery / flaky filler, a fibrous filler and the like can be used. Examples of the powdery / flaky filler include silica, alumina, talc, mica, kaolin, clay, silica alumina, titanium oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, Examples include silicon nitride, glass, hydrotalcite, zirconium oxide, glass beads, carbon black, and the like. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. In addition, a filler such as a ZnO tetrapot, a metal salt (eg, zinc chloride, lead sulfate, etc.), an oxide (eg, iron oxide, molybdenum dioxide, etc.), and a metal (eg, aluminum, stainless steel, etc.) may be used. it can. These can be used alone or in combination of two or more. The surface of the inorganic filler may be treated with a silane coupling agent or a titanate coupling agent. The inorganic filler is used in an amount of 400 parts by weight or less, preferably 300 parts by weight or less based on 100 parts by weight of the total of (A) and (B). If the amount of the inorganic filler exceeds the above-mentioned value, the change in viscosity may be so large that molding may not be possible. In order to increase the mechanical strength, it is preferable to add 0.01 parts by weight or more.
[0044]
Further, if necessary, in addition to the above components, known additives and fillers such as antioxidants, ultraviolet absorbers, release agents, heat stabilizers, lubricants, coloring agents, and the like can be blended. .
[0045]
The method for producing the resin composition of the present invention is not particularly limited. For example, the components described above can be mixed in advance by a mixer such as a Henschel mixer and then melt-kneaded by a conventional apparatus such as an extruder, extruded, and pelletized.
[0046]
The resin composition of the present invention can be used as a material for automobile equipment parts, electric / electronic equipment parts, chemical equipment parts, and the like.
[0047]
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[0048]
【Example】
In embodiments, the flow tester used in the melt viscosity of the PPS _{V 6} measurements are Shimadzu Flow Tester CFT-500C.
[0049]
The capillograph used for the measurement of the non-Newton index N is Toyo Seiki Seisakusho's Capillograph 1B PC.
[0050]
Synthesis Example 1
A 150-liter autoclave was charged with 19.222 kg of flaky sodium sulfide (60.8% by weight Na ₂ S) and 45.0 kg of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP). The temperature was raised to 204 ° C. while stirring under a nitrogen stream to distill 4.600 kg of water (the remaining water content was 1.08 mol per mol of sodium sulfide). Thereafter, the autoclave was sealed and cooled to 180 ° C., and 22.014 kg of p-dichlorobenzene (hereinafter sometimes abbreviated as p-DCB) and 18.0 kg of NMP were charged. At a liquid temperature of 150 ° C., the pressure was increased to 1 kg / cm ² G using nitrogen gas, and the temperature was raised. When the liquid temperature reached 255 ° C., the temperature was stopped and the reaction was allowed to proceed with stirring for 3 hours.
[0051]
The obtained slurry was repeatedly filtered and washed with warm water by a conventional method, and dried at 120 ° C. for about 5 hours in a circulating hot air drier to obtain a white powdery PPS. The melt viscosity _{V 6} of the obtained PPS (corresponding to P-01, PAS (i)) was 490 poise.
[0052]
Synthesis Example 2
All the procedures were carried out in the same manner as in Synthesis Example 1 except that the amount of p-DCB charged was 22.463 kg. The melt viscosity _{V 6} of the obtained PPS (corresponding to P-02, PAS (i)) was 320 poise.
[0053]
Synthesis Example 3
The same procedure as in Synthesis Example 1 was carried out except that the amount of p-DCB charged was 23.211 kg. The melt viscosity _{V 6} of the obtained PPS (P-03, PAS (corresponding to b)) was 90 poise.
[0054]
Synthesis Example 4
The PPS (P-01) obtained in Synthesis Example 1 was thermally oxidized at 230 ° C. for 20 hours. The melt viscosity _{V 6} of the obtained PPS (corresponding to P-1, PAS (A) ) is 2300 poise, the non-Newtonian index N of 1.24.
[0055]
Synthesis Example 5
The PPS (P-02) obtained in Synthesis Example 2 was subjected to a thermal oxidation treatment at 230 ° C. for 21 hours. The melt viscosity _{V 6} of the obtained PPS (corresponding to P-2, PAS (A) ) is 1020 poise, the non-Newtonian index N of 1.22.
[0056]
Synthesis Example 6
The PPS (P-02) obtained in Synthesis Example 2 was thermally oxidized at 230 ° C. for 34 hours. The melt viscosity _{V 6} of the obtained PPS (P-3, which corresponds to the PAS (A)) is 2120 poise, the non-Newtonian index N was 1.30.
[0057]
Synthesis Example 7
The PPS (P-03) obtained in Synthesis Example 3 was subjected to a thermal oxidation treatment at 230 ° C. for 67 hours. The melt viscosity _{V 6} of the obtained PPS (P-4, PAS (corresponding to B)) is 2530 poise, the non-Newtonian index N was 1.61.
[0058]
Synthesis Example 8
The PPS (P-02) obtained in Synthesis Example 2 was thermally oxidized at 230 ° C. for 16 hours. The resulting PPS (PC-1, Comparative component) melt viscosity _{V 6} of a 720 poise, the non-Newtonian index N was 1.15.
[0059]
Synthesis Example 9
The PPS (P-02) obtained in Synthesis Example 2 was subjected to a thermal oxidation treatment at 230 ° C. for 52 hours. The resulting PPS (PC-2, Comparative component) melt viscosity _{V 6} of a 7100 poise, the non-Newtonian index N was 1.58.
[0060]
Synthesis Example 10
The PPS (P-03) obtained in Synthesis Example 3 was thermally oxidized at 230 ° C. for 33 hours. The resulting PPS (PC-3, compared component) melt viscosity _{V 6} of a 690 poise, the non-Newtonian index N was 1.38.
[0061]
Examples 1 to 6 and Comparative Examples 1 to 7
The glass fibers and calcium carbonate used in the examples and comparative examples are as follows.
<Glass fiber>
・ CS 3PE945S, trademark, manufactured by Nitto Boseki Co., Ltd. <Calcium carbonate>
-SL-1000, trademark, manufactured by Takehara Chemical Industry Co., Ltd. In each of Examples and Comparative Examples, each component was blended in the amount (parts by weight) shown in Table 1, and premixed using a Henschel mixer for 5 minutes to be uniform. After that, the mixture was melt-kneaded at a temperature of 300.degree.
[0062]
The Izod impact strength and burr length of the resin composition were measured as described below. <Izod impact strength>
The pellets obtained as described above were supplied to an injection molding machine, and dumbbell pieces were molded at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and measured according to ASTM D256.
<Burr length>
Under the same conditions as the Izod impact strength measurement, a connector having a width of 20 mm, a length of 40 mm, a thickness of 3 mm, 16 pin holes, and a pin hole size of 2 × 2 mm was molded, and a burr length generated in the pin hole portion (clearance 20 μm). Was measured and evaluated.
[0063]
Table 1 shows the above results.
[0064]
[Table 1]

In Examples 1 to 3, the amounts of components (A) and (B) were varied within the scope of the present invention. In each case, the burr length of the molded product was short, and the impact strength was high. When the amount of (A) is reduced and the amount of (B) is increased, the burr length of the molded product becomes shorter. Although the impact strength tended to be low, the effect of the present invention could be sufficiently achieved. Example 4, instead of the used in Example 1 (A), melt viscosity V ₆ is higher, non-Newtonian index N is one using a smaller (A). The burr length and impact strength were almost the same as in Example 1. Example 5, instead of the used in Example 1 (A), V ₆ is lower, in which N is used a smaller (A). The burr length was somewhat longer than in Example 1, and the impact strength was somewhat lower, but did not impair the effects of the present invention. In Example 6, calcium carbonate was further added in addition to glass fiber as an inorganic filler, and the total amount of the inorganic filler was increased. The burr length was significantly shorter than that of Example 1. Although the impact strength was low, the effect of the present invention was sufficiently achieved.
[0065]
On the other hand, Comparative Example 1 uses only (A) of Example 1 as a PAS, and Comparative Example 2 uses only (B) of Example 1 as a PAS. Only (A) (Comparative Example 1) had a significantly longer burr length, and only (B) (Comparative Example 2) had a significantly lower impact strength. From Comparative Examples 1 and 2, when (A) and (B) are blended within the scope of the present invention, the high impact strength of (A) and the excellent burr characteristics of (B) are well exhibited. I found that I could do it. Comparative Example 3 uses PAS (PC-3) in which both V ₆ and N are less than the range of (B), instead of (B) PAS of Example 1. The burr length was significantly longer than in Example 1. Comparative Example 4 in place of the (A) PAS of Example 1, in _{which V 6} was used PAS less than the range of (A) (PC-1) . As compared with Example 1, the burr length was significantly longer and the impact strength was lower. Comparative Example 5, instead of the (A) PAS in Example 1, but _{V 6} and N using PAS (PC-2) beyond the range of both (A). Formability was poor, short shots occurred, and impact strength was low. Also, the burr length could not be measured. Comparative Examples 6 and 7 are the same as Comparative Examples 3 and 4, respectively, except that calcium carbonate was further added to the glass fiber as an inorganic filler, and the total amount of the inorganic filler was increased. In each case, the burr length was extremely long, and the impact strength was low.
[0066]
【The invention's effect】
An object of the present invention is to provide a polyarylene sulfide resin composition having a low burr generation amount and a high impact strength.

Claims (5)

(A) a melt viscosity _{V 6} is obtained by heat treatment at polyarylene sulfide under vapor phase oxidizing atmosphere (a) is 250 to 2000 poise, the melt viscosity _{V 6} is 800 to 5,000 poise, and non-Newtonian polyarylene sulfide 20 to 90 parts by weight index N is 1.15 to 1.34, and (B) the melt viscosity _{V 6} is 40 to 200 poise polyarylene sulfide (B), gas-phase oxidative atmosphere in heat treatment obtained, melt viscosity _{V 6} is 800 to 5,000 poise, and non-Newtonian index N is polyarylene sulfide 80 to 10 parts by weight of the resin composition comprising a 1.40 to 2.00. (A) polyarylene sulfide resin composition according to claim 1, wherein the melt viscosity _{V 6} is 1000 to 3500 poise. 3. The resin composition according to claim 1, wherein (A) the non-Newtonian index N of the polyarylene sulfide is 1.20 to 1.30. (B) polyarylene melt viscosity _{V 6} of the sulfide resin composition according to any one of claims 1 to 3 which is from 1000 to 3500 poise. (B) The resin composition according to any one of claims 1 to 4, wherein the non-Newton index N of the polyarylene sulfide is 1.50 to 1.70.