JPH08325454A - Polyarylenesulfide resin composition - Google Patents

Abstract

PURPOSE: To obtain a polyarylenesulfide resin compsn. which can provide a molding having mechanical strength, such as toughness, at a weld and free from a significant burr. CONSTITUTION: This resin compsn. comprises (A) 100 pts.wt. polyarylenesulfide having a melt viscosity V6 of 500 to 4800P and a non-Newtonian index N of not less than 1.35, (B) 0.01 to 300 pts.wt. polyarylenesulfide having a melt viscosity V6 of 50 to 500P, (C) 0.01 to 50 pts.wt. organosilane compd., and (D) 0 to 300 pts.wt. inorg. filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin composition, and more particularly to a PAS resin composition suitable for a molded article having a welded portion, especially for a connector. .

[0002]

2. Description of the Related Art In recent years, a thermoplastic resin having high heat resistance and chemical resistance has been required as a material for electric / electronic equipment parts, automobile equipment parts, chemical equipment parts and the like. . Polyarylene sulfide represented by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) is one of the resins that meet this requirement.
It has been receiving attention in recent years. However, when the resin is molded,
There is a drawback in that the mechanical strength such as the toughness of the welded portion, that is, the welded portion where two or more resin flow interface ends meet in the mold cavity becomes extremely low. Therefore, there is a problem that the weld portion is broken when it is subjected to thermal stress or mechanical stress. In particular, the above problem was remarkable when the pins were driven into the connector. Further, since the resin has too high melt fluidity, it has a problem that burrs are likely to be formed at the time of molding the connector.

In view of the above problems, Japanese Patent Laid-Open No. 577015/1982
Japanese Patent Publication No. 7 discloses a resin composition in which glass fibers having a specific size are added to PAS having a predetermined melt flow rate and crosslinking rate. However, the resin composition does not sufficiently improve the mechanical strength such as the toughness of the weld portion and reduce the burr, and the mechanical strength is insufficient, so that the applicable applications are limited, and for example, the connector is used. Was not suitable for use as.

Further, JP-A-64-38211, JP-A-64-63115, and JP-A-64-8920.
Japanese Patent Publication No. 8 discloses a method in which at least one silane compound selected from the group consisting of aminoalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane and vinylalkoxysilane is added to PAS as a coupling agent. However, in this method, improvement of mechanical strength such as toughness of the weld portion and reduction of burrs are not sufficient.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyarylene sulfide resin composition which has a high mechanical strength such as the toughness of the welded portion and is capable of giving a molded product with less burrs. To do.

[0006]

According to the present invention, (A) the melt viscosity V ₆ is 500 poises or more and 4800 poises or less,
And 100 parts by weight of a polyarylene sulfide having a non-Newtonian index N of 1.35 or more, (B) melt viscosity V ₆
Resin composition containing 0.01 to 300 parts by weight of polyarylene sulfide having a porosity of 50 poise or more and less than 500 poise, 0.01 to 50 parts by weight of (C) organosilane compound, and 0 to 300 parts by weight of (D) inorganic filler. It is a thing.

The resin composition of the present invention is characterized by using two kinds of PAS having the above-mentioned characteristics and combining it with an organic silane compound.
The resin composition is useful for a molded product having a weld part. In particular, when it is used for a connector, it has a high mechanical strength such as toughness of a weld portion generated in the connector, and therefore has a characteristic that it does not break from the weld portion when a pin is driven into the connector. In addition, there is little burr generation, and the step of removing the generated burr can be omitted or greatly simplified, which is economically excellent.

The component (A) PAS used in the resin composition of the present invention is a known polymer having an arylene sulfide repeating unit, and particularly preferably PPS. In the present invention, the melt viscosity V ₆ of the component (A) PAS has an upper limit of 4800 poise, preferably 400.
0 poise, particularly preferably 3000 poise, and the lower limit is 500 poise, preferably 800 poise, particularly preferably 1500 poise. If the melt viscosity V ₆ is less than the above lower limit, the mechanical strength such as toughness in the weld portion is lowered, and burrs are remarkably generated during molding. Exceeding the above upper limit is not preferable because the molding processability decreases. Here, the melt viscosity V ₆ is 300 using a flow tester.
It is a viscosity (poise) measured after holding for 6 minutes at L / D = 10 at a temperature of 20 kgf / cm ² and a load of 20 kgf / cm ² .

The (A) PAS used in the present invention is
The non-Newtonian index N must be 1.35 or more, preferably 1.50 or more, and particularly preferably 1.5.
It is 5 or more. When it is less than the above value, mechanical strength such as toughness in the weld portion is deteriorated and burrs are remarkably generated during molding, which is not preferable. The upper limit is not particularly limited. Here, the non-Newtonian index N is 300 ° C. using a capillograph and L / D = 40,
It is a value calculated by measuring the shear rate and the shear stress and using the following formula (I). An N value of 1 indicates a Newtonian fluid, and an N value of more than 1 indicates a non-Newtonian fluid.

[0010]

## EQU1 ## SR = K.SS ^N (I) [where, SR is a shear rate (sec ^-1 ), SS is a shear stress (dyne / cm ² ), and K is a constant. ] The above (A) PAS can be preferably produced by the following method. That is, in a method for producing PAS by reacting an alkali metal sulfide and a dihalo aromatic compound in an organic amide solvent, the molar ratio of the alkali metal sulfide and the dihalo aromatic compound is 0.940 to 1.000. age,
Furthermore, 0.35 to 1.0 with respect to the charged alkali metal sulfide
By adding mol% of polyhaloaromatic compound into the polymerization reaction system and cooling the gas phase part of the reaction vessel during the reaction, a part of the gas phase in the reaction vessel is condensed and returned to the liquid phase. Excuse me.

In the above production method, the upper limit of the molar ratio of the alkali metal sulfide and the dihalo aromatic compound is 1.00.
0, preferably 0.980, with a lower limit of 0.940,
It is preferably 0.950. If it is less than the above lower limit, burrs generated during molding become large. If the above upper limit is exceeded,
It is not preferable because the workability during molding is lowered.

In the above production method, the polyhaloaromatic compound added to the polymerization reaction system has an upper limit of 1.00 mol%, preferably 0.80 mol%, based on the charged alkali metal sulfide. The lower limit is 0.35 mol%, preferably 0.40 mol%. Below the above lower limit, in the generated PAS, the non-Newtonian index N decreases,
The burr generated during molding becomes large. Exceeding the above upper limit is not preferable because the workability during molding is reduced.

The method of adding the polyhaloaromatic compound into the polymerization reaction system is not particularly limited. For example, the alkali metal sulfide and the dihaloaromatic compound may be added at the same time, or the polyhaloaromatic compound may be dissolved in an organic solvent such as N-methylpyrrolidone at any time during the reaction, and the reaction vessel may be heated with a high pressure pump. You may press fit in.

As a method for producing PAS by condensing a part of the gas phase in the reaction vessel by cooling the gas phase portion of the reaction vessel and then refluxing this to the liquid phase, JP-A-5-
The method described in JP-A-222196 can be used.

The refluxed liquid has a high water content compared to the liquid phase bulk due to the difference in vapor pressure between water and the amide solvent.
This reflux liquid having a high water content forms a layer having a high water content on the reaction solution. As a result, the residual alkali metal sulfide (for example, Na ₂ S), alkali metal halide (for example, NaCl), oligomer and the like are contained in a large amount in the layer. In the conventional method, at a high temperature of 230 ° C. or higher, when the generated PAS and the raw materials such as Na ₂ S and by-products are uniformly mixed, not only high-molecular-weight PAS cannot be obtained but Depolymerization of PAS also occurred, and thiophenol by-product was observed. However, in the present invention, by positively cooling the gas phase portion of the reaction vessel and returning a large amount of water-rich reflux liquid to the upper portion of the liquid phase, the above-mentioned inconvenient phenomenon can be avoided and the reaction is inhibited. Of high molecular weight PA
It seems that S can be obtained. However, the present invention is not limited only to the effects due to the above-mentioned phenomenon, and high-molecular weight PAS can be obtained by various influences caused by cooling the gas phase portion.

In this method, it is not necessary to add water during the reaction. However, the addition of water is not excluded at all. However, with the addition of water, some of the advantages of this method are lost. Therefore,
Preferably, the total amount of water in the polymerization reaction system is constant during the reaction.

The gas phase portion of the reactor can be cooled either 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 into an internal coil installed in the upper part of the reaction can, a method of flowing a cooling medium into an external coil or jacket wound around the upper part of the outside of the reaction can, and a reflux condenser installed in the upper part of the reaction can are used. The method may be such as sprinkling water or blowing gas (air, nitrogen, etc.) on the upper part of the outside of the reaction can. Any method is effective as long as it has the effect of increasing the reflux amount in the can. May be used. If the outside air temperature is relatively low (for example, room temperature), it is also possible to perform appropriate cooling by removing the heat insulating material conventionally provided on the upper part of the reaction can. In the case of external cooling, water condensed on the reactor wall surface
The amide-based solvent mixture enters the liquid phase along the wall of the reaction vessel. Thus, the water-rich mixture pools on top of the liquid phase,
Keep the water content there relatively high. For internal cooling,
The mixture condensed on the cooling surface likewise travels along the surface of the cooling device or the wall of the reaction vessel into the liquid phase.

On the other hand, the temperature of the liquid phase bulk is maintained at a predetermined constant temperature or controlled according to a predetermined temperature profile. 230 to 275 for constant temperature
It is preferable to carry out the reaction at a temperature of ° C for 0.1 to 20 hours. More preferably, the temperature is 240 to 265 ° C. and the time is 1 to 6 hours. To obtain higher molecular weight PAS, it is preferable to use a reaction temperature profile of two or more steps. This 2
When carrying out the stepwise operation, the first step is preferably carried out at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too slow, which is not practical. If the temperature is higher than 240 ° C., the reaction rate is too fast, PAS having a sufficiently high molecular weight cannot be obtained, and the side reaction rate remarkably increases. The end of the first stage is
Dihalo aromatic compound residual rate in the polymerization reaction system is 1 mol% to 40
It is preferable to carry out at a time of mol% and a molecular weight in the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo-aromatic compound in the polymerization reaction system is 2 mol% to 15 mol% and the molecular weight is 5,000 to 15,000. Residual rate is 40 mol%
When it is more than 1, the side reaction such as depolymerization is likely to occur in the second step reaction, while when it is less than 1 mol%, the high molecular weight P is finally obtained.
It is difficult to get AS. Thereafter, the temperature is raised, and the reaction in the final stage is preferably carried out at a reaction temperature of 240 to 270 ° C. for 1 to 10 hours. PAS with sufficiently high molecular weight at low temperature
At a temperature higher than 270 ° C., side reactions such as depolymerization are likely to occur, making it difficult to stably obtain a high molecular weight product.

As a practical operation, first, dehydration or water addition is carried out in an inert gas atmosphere so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount, if necessary. The water content is preferably alkali metal sulfide 1
The amount is 0.5 to 2.5 mol, especially 0.8 to 1.2 mol per mol.
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 it is less than 0.5 mol, the reaction rate is too fast to obtain a sufficiently high molecular weight product.

In the case of the one-step reaction at a constant temperature, the cooling of the gas phase portion during the reaction is preferably performed from the start of the reaction, but must be performed at least during the temperature increase of 250 ° C. or less. 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 after the completion of the first-stage reaction. Regarding the degree of cooling effect, the pressure inside the reaction vessel is usually the most suitable index. The absolute value of the pressure varies depending on the characteristics of the reaction vessel, the stirring state, the water content in the system, the molar ratio of the dihalo aromatic compound to the alkali metal sulfide, and the like. However, as compared with the case of not cooling under the same reaction conditions, if the reactor pressure is decreased, the amount of reflux liquid is increased, which means that the temperature at the reaction solution gas-liquid interface is decreased. It is considered that the degree of relative decrease indicates the degree of separation between the layer having a high water content and the layer having no water content. Therefore, it is preferable to cool the reactor so that the internal pressure of the reactor becomes 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.

The organic amide solvent used here is PA
Known for S-polymerization, such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, etc., and mixtures thereof can be used, with N-methylpyrrolidone being 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. Further, hydrosulfides and hydrates corresponding to these can be used after being neutralized with the corresponding hydroxides. Inexpensive sodium sulfide is preferred.

The dihalo aromatic compound is, for example, Japanese Patent Publication No.
It can be selected from those described in JP-A-5-3368, but is preferably p-dichlorobenzene. Further, a copolymer can be obtained by using a small amount (20 mol% or less) of one or more kinds of para, meta or orthodihalo compounds of diphenyl ether, diphenyl sulfone or biphenyl. For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenyl sulfone, m, p'-dichlorodiphenyl sulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
It is dichlorobiphenyl.

The polyhaloaromatic 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, 1,2,4-trichlorobenzene,
1,3,5-trichlorobenzene is preferred.

Further, as a small amount of other additives, a terminal terminating agent and a monohalo compound as a modifying agent can be used in combination.

The high molecular weight PAS thus obtained is separated from by-products by post-treatment methods known to those skilled in the art.

Further, in the present invention, the PAS obtained as described above can be preferably subjected to an acid treatment. The acid treatment is carried out at a temperature of 100 ° C. or lower, preferably 40 to 80 ° C. If the temperature exceeds the above upper limit, the PAS molecular weight after acid treatment decreases, which is not preferable. On the other hand, if the temperature is lower than 40 ° C., the remaining inorganic salt is deposited to reduce the fluidity of the slurry and hinder the continuous treatment process, which is not preferable. The concentration of the acid solution used for the acid treatment is preferably 0.01 to 5.0% by weight. The pH of the acid solution is preferably 4.0 to 5.0 after the acid treatment. By adopting the above concentration and pH, it is possible to convert most of -SX (X represents an alkali metal) and -COOX terminal in PAS which is the object to be processed to -SH and -COOH terminals. It is preferable because it can prevent corrosion of plant equipment. The time required for the acid treatment depends on the acid treatment temperature and the concentration of the acid solution, but preferably 5 minutes or more,
Particularly preferably, it is 10 minutes or more. Below the above, P
-SH and -COOX ends in AS are -SH and -CO
It is not preferable because it cannot be sufficiently converted to the OH terminal. For the acid treatment, for example, acetic acid, formic acid, oxalic acid, phthalic acid, hydrochloric acid,
Phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, boric acid, carbonic acid and the like are used, and acetic acid is particularly preferable. By performing the processing, P
It is possible to reduce impurities such as alkali metals, such as sodium, in AS. Therefore, the elution of alkali metal, such as sodium, during use of the product and the deterioration of electrical insulation can be suppressed.

Component (B) PAS used in the present invention
Is preferably PPS. In the present invention, the melt viscosity V ₆ of the component (B) PAS is less than 500 poise, preferably 400 poise or less, and 50 poise or more, preferably 80 poise or more. When the melt viscosity V ₆ is less than the above range, mechanical strength such as toughness in the weld portion is deteriorated and burrs are remarkably generated during molding. When it exceeds the above range, the fluidity is deteriorated, the moldability is deteriorated, and burrs are significantly generated. Here, the melt viscosity V ₆ is a value measured by the same method as above. The non-Newtonian index N of the component (B) PAS is preferably 1.05 or more.

The component (B) PAS can be produced by a known method, for example, the method described in JP-B-45-3368. Also, as in the above case, an acid treatment can be applied. As the component (B), a commercially available product can be used. For example, PPS and H manufactured by Topren Co., Ltd.
-0 (trademark, V ₆ = 50 poise), H-1 (trademark, V ₆₎
= 100 poise), T-1 (trademark, V ₆ = 300 poise, semi-crosslinked PPS), K-1 (trademark, V ₆ = 360 poise, crosslinked PPS), LN-03 (trademark, V ₆ = 25)
0 poise, linear PPS) and the like.

The blending amount of the above-mentioned (B) PAS is (A) 1
With respect to 00 parts by weight, the upper limit is 300 parts by weight, preferably 200 parts by weight, particularly preferably 150 parts by weight, and the lower limit is 0.01 parts by weight, preferably 0.1 parts by weight, particularly preferably 1 part by weight. Is. If the content exceeds the above upper limit, burrs generated at the time of molding becomes large, and if it is less than the above lower limit, the fluidity decreases and the moldability deteriorates.

Next, examples of the (C) organosilane compound used in the present invention include compounds used as silane coupling agents. For example, alkoxysilanes are preferred and more preferably selected from aminoalkoxysilanes, epoxyalkoxysilanes and mercaptoalkoxysilanes. Examples of aminoalkoxysilanes include γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ -Aminopropyltriethoxysilane, N-β
(Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyl Examples include triethoxysilane. Examples of the epoxyalkoxysilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl)
Examples thereof include ethyltrimethoxysilane. Examples of the mercaptoalkoxysilane include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. In addition to these, haloalkoxysilanes such as γ-chloropropyltrimethoxysilane and γ-chloropropyltriethoxysilane; isocyanate alkoxysilanes such as γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane; It is also possible to use vinylalkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane and the like. The above organosilane compounds may be used alone or in combination of two or more.

The compounding amount of the (C) organosilane compound is
With respect to 100 parts by weight of (A), the upper limit is 50 parts by weight, preferably 40 parts by weight, and the lower limit is 0.01 parts by weight, preferably 0.1 parts by weight. If the blending amount of the organic silane compound exceeds the above upper limit, the change in viscosity is large and it becomes difficult to mold, and if it is less than the above lower limit, the effect of reducing burrs is small.

The resin composition of the present invention may further contain (D) an inorganic filler as an optional component. The inorganic filler is not particularly limited, but powdery / scaly fillers, fibrous fillers and the like can be used. Examples of the powdery / scaly filler include silica, alumina, talc, mica, kaolin, clay, silica-alumina, titanium oxide, calcium carbonate, calcium silicate,
Examples thereof include calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, silicon nitride, glass, hydrotalcite, zirconium oxide, glass beads and carbon black. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber,
Examples thereof include silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. In addition to this, a filler such as ZnO tetrapot, metal salt (eg, zinc chloride, lead sulfate, etc.), oxide (eg, iron oxide, molybdenum dioxide, etc.), 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 (D) is used in an amount of 300 parts by weight or less, preferably 200 parts by weight or less, based on 100 parts by weight of (A). If the amount of the inorganic filler exceeds the above value, the change in viscosity becomes large and molding may not be possible. Further, in order to increase the mechanical strength, it is preferable to add 10 parts by weight or more.

In the resin composition of the present invention, in addition to the above-mentioned components, known additives such as antioxidants, ultraviolet absorbers, release agents, heat stabilizers, lubricants, colorants and the like may be added, if desired. Can be blended.

The method for producing the resin composition of the present invention is not particularly limited. For example, (A) and (B) are mixed in advance with a mixer such as a Henschel mixer, then mixed with other components, and then melt-kneaded with a conventional device such as an extruder (for example, 320
It can be extruded and pelletized. Alternatively, after mixing (A) and (B) and pelletizing,
It is also possible to mix with other components and melt-knead. Also,
It can also be mixed / molded as a masterbatch. Further, each component of the composition may be separately charged into an extruder and melt-mixed.

The resin composition of the present invention is a molding material particularly suitable for moldings having a weld portion. The weld portion is a portion that is molded by an injection molding method, and two or more resin flow interface ends of the resin flows merge and are fused in the mold cavity. The weld portion is likely to occur when the molded product has a void portion or when the wall thickness is changed and the material cannot be unidirectionally flowed from the thick portion to the thin portion. If there are two or more gates, or even if a single-point gate is used, the formation of welds is unavoidable when forming a ring-shaped, circular, or rectangular tubular product. The welded portion can generally be identified by the appearance of linear color unevenness on the surface of the molded product or the appearance of a pattern in which the resin flows merge. The molded product having the weld portion as described above includes, for example, a connector, a coil bobbin as an electronic component, a printed circuit board, a chassis for electronic components, a lamp socket as an electric heating component, a dryer grill, a thermostat base, a thermostat case, and a motor. Brush holder as a part,
Claws for copying machines as precision equipment such as bearings and motor cases, diaphragm parts for cameras, watch cases, timepiece base plates, exhaust gas circulation valves as car parts, carburetors, alternator terminal blocks, tachometer housings, battery housings, etc., or Cleansing frame, insulator, pipe bracket as chemical equipment parts,
There are many functional parts such as pump casings, tower fills, etc. The resin composition of the present invention is useful in the above-mentioned molded article, particularly as a connector. Also,
Although the above-mentioned molded article does not always have a weld portion, it is difficult to avoid the weld portion due to its function. Further, the above-mentioned molded product is an example, and the molded product having the weld portion is not limited to these.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0038]

EXAMPLES In the examples, the flow tester used for measuring the melt viscosity V ₆ was Shimadzu Flow Tester C.
It is FT-500C. The capillograph used for obtaining the non-Newtonian index N is Capillograph 1B-PC manufactured by Toyo Seiki Seisakusho.

The PPS used as the component (B) was manufactured by Topren Co., Ltd., H-1 (trademark, V ₆ = 10).
0 Poise), T-1 (Trademark, V ₆ = 300 Poise), K
-1 (trademark, V ₆ = 360 poise) and LN-03 (trademark, V ₆ = 250 poise).

In the synthesis example, p-dichlorobenzene (hereinafter sometimes abbreviated as p-DCB), 1,3,
The reaction rate of 5-trichlorobenzene (hereinafter sometimes abbreviated as 1,3,5-TCB) was calculated from the measurement result by gas chromatography. Where p-DCB and 1,3,5-T
The reaction rate of CB was calculated by the following formula.

[0041]

## EQU00002 ## Reaction rate of p-DCB (%) = (1-remaining p-DCB
Weight / p-DCB weight) × 100

[0042]

[Equation 3] 1,3,5-TCB reaction rate (%) = (1-remaining 1,3,
5-TCB weight / charged 1,3,5-TCB weight) × 100 Synthesis example 1 In a 150 liter autoclave, flakes of sodium sulfide (60.9 wt% Na ₂ S) 19.222 kg and N-methyl-2-pyrrolidone (hereinafter 45.0 kg
Was charged. While stirring under a nitrogen stream, the temperature was raised to 204 ° C., and 4.600 kg of water was distilled off (the residual water content was 1.08 mol per mol of sodium sulfide). After that, the autoclave was sealed and cooled to 180 ° C, p-DCB 22.500 kg
(Molar ratio of Na ₂ S and p-DCB is about 0.980), 1,3,5-
0.136 kg of TCB (about 0.5 mol% with respect to sodium sulfide) and 18.0 kg of NMP were charged. The temperature was started by pressurizing to 1 kg / cm ² G with nitrogen gas at a liquid temperature of 150 ° C. While stirring at a liquid temperature of 220 ° C. for 3 hours, a cooling medium of 80 ° C. was flowed around the coil wound around the upper part of the autoclave to cool it. After that, the temperature was raised, the liquid was stirred at 260 ° C. for 3 hours, then the temperature was lowered, and the cooling of the upper part of the autoclave was stopped.
During cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. The maximum pressure during the reaction is 8.75 kg / cm ²
It was G.

The obtained slurry was filtered and washed with warm water twice by a conventional method, and then dried in a hot air circulation dryer at 120 ° C. for about 5 hours to obtain a white powdery product. The obtained PPS
The melt viscosity V ₆ (designated R-1) was 3000 poise and the non-Newtonian index N was 1.45.

The reaction rate of p-DCB is 98.4%,
The reaction rate of 1,3,5-TCB was 100%.

[0045]

Examples 1 to 5 and Comparative Examples 1 to 6 (A) PPS (R-1) obtained in Synthesis Example 1 and (B) Each PPS (H-1, T-1, K-1, LN-0
3), (C) organosilane compound and (D) glass fiber (CS 3PE945, trademark, manufactured by Nitto Boseki Co., Ltd., fiber diameter 13 μm, fiber length 3 mm) were mixed in the proportions shown in Table 1 and mixed with a Henschel mixer to 5 30 minutes after premixing
Using a mmφ twin-screw extruder, melt extrusion was carried out at a cylinder temperature of 320 ° C. and a rotation speed of 250 rpm to prepare pellets. Further, the pellets thus formed were molded by an injection molding machine set at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and test pieces were prepared and subjected to various properties tests. Comparative Example 6
(A) Instead of PPS, PPS (LN-4, trademark, manufactured by Topren Co., Ltd., V ₆ = 2500 poise, N = 1.31) having a non-Newtonian index N less than the range of the present invention was used.

Various characteristics were evaluated by the following test methods.・ Weld strength was obtained by molding a flat plate with a width of 60 mm × a length of 180 mm × a thickness of 3 mm using a mold having side gates on both sides, and then cutting this into a strip with a width of 20 mm. Then, the tensile strength was measured and evaluated according to ASTM D638.・ The burr characteristics are width 10mm, length 140mm, thickness 15
mm, 95 pin holes, and a pin hole size of 0.5 × 3.5 mm were prepared, and the burr length generated in the pin hole portion (gap 15 μm) was measured and evaluated.

The above results are shown in Table 1.

[0048]

[Table 1] In Examples 1 to 4, the melt viscosity V ₆ of (B) PPS was changed within the scope of the present invention under the same conditions.
In all cases, the weld strength (tensile strength) was large and the burr length was short. Example 5, under the same conditions as Example 1,
(C) The type of the organic silane compound is changed. Similar to Example 1, the weld strength was high and the burr length was short.

On the other hand, in Comparative Example 1, (A) PPS was not mixed. The weld strength was low and the burr length was long. In Comparative Example 2, the compounding amount of (B) PPS exceeds the range of the present invention. The weld strength was low and the burr length was long. In Comparative Example 3, the compounding amount of the (D) glass fiber exceeds the range of the present invention. It was found that when the glass fiber was excessive, the composition had a high melt viscosity and could not be molded. Comparative Example 4 was prepared under the same conditions as in Example 1,
(C) The organosilane compound was not added.
Compared with Example 1, the weld strength was low and the burr length was long. Comparative Example 5 was prepared under the same conditions as in Example 1, except that (C)
The compounding amount of is beyond the range of the present invention. The composition had a high melt viscosity and could not be molded. Comparative Example 6
Under the same conditions as in Example 1, (A) PPS was replaced with PPS having N less than the range of the present invention. The burr length was longer than that in Example 1.

[0050]

EFFECTS OF THE INVENTION The resin composition of the present invention can provide a molded product having high mechanical strength such as toughness of the weld portion and less burrs.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kanichi Kido 3-1, Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Tonen Kagaku Co., Ltd. Technology Development Center

Claims (6)

[Claims] (A) Melt viscosity V ₆ is 500 poise or more 4
Polyarylene sulfide having a poise of 800 poise or less and a non-Newtonian index N of 1.35 or more 100
Parts by weight, (B) polyarylene sulfide having a melt viscosity V ₆ of 50 poises or more and less than 500 poises 0.01 to
300 parts by weight (C) organosilane compound 0.01 to 50
Resin composition containing 0 to 300 parts by weight of (D) inorganic filler. 2. The non-Newtonian index N of (A) polyarylene sulfide is 1.50 or more.
The resin composition described. 3. The resin composition according to claim 1, wherein the polyarylene sulfide (A) has a melt viscosity V ₆ of 800 to 4000 poise. 4. The polyarylene sulfide (B) having a melt viscosity V ₆ of 80 to 400 poise.
The resin composition according to any one of items 1 to 3. 5. The resin composition according to claim 1, wherein the organosilane compound (C) is a silane compound selected from aminoalkoxysilanes, epoxyalkoxysilanes and mercaptoalkoxysilanes. 6. The resin composition according to claim 1, which is used for a connector.