JP2010195874A - Polyphenylene sulfide resin composition and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition which has a low chlorine content, is excellent in melt fluidity and has high weld strength; and to provide electric and electronic elements comprising injection moldings of the composition. <P>SOLUTION: The polyphenylene sulfide resin composition comprises, based on (A) a 100 pts.wt. polyphenylene sulfide resin having an amount of extracted chloroform being 1.8 wt.% or less and a melt viscosity of 60 Pa s or more (320°C, shear rate of 1,000/s), (B) a 5-30 pts.wt. liquid crystalline resin and (C) a 30-90 pts.wt. filler which are blended. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyphenylene sulfide resin composition having a low chlorine content, excellent melt fluidity and high weld strength, and an electric / electronic component comprising an injection-molded product thereof.

  Polyphenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) belongs to high heat-resistant super engineering plastics, and has mechanical strength, rigidity, flame retardancy, chemical resistance, electrical properties, dimensional stability, etc. Therefore, it is widely used for various electric / electronic parts, home appliance parts, automobile parts and machine parts, mainly for injection molding.

  Particularly in electrical / electronic component applications, high strength, particularly weld strength and excellent melt fluidity are required, and improvements have been studied so far. On the other hand, due to superior corrosion resistance and environmental considerations, reducing halogen compounds such as chlorine and bromine, especially chlorine content, can be used for electrical and electronic parts, especially connectors, connector parts, and capacitor parts. Demands for polyphenylene sulfide resin compositions with low chlorine content and high strength, especially weld strength and excellent melt fluidity, with the progress of densification for electrical and electronic parts applications Is growing.

  Polyphenylene sulfide resin is generally produced industrially by polycondensation of polyhalogenated aromatic compounds such as paradichlorobenzene. Therefore, a halogen compound represented by chlorine is often present at a part of the polymer molecular chain end or a part of the oligomer. In order to reduce this halogen compound, there are a method of increasing the molecular chain length to reduce the number of polymer molecular chain terminals, and a method of reducing low molecular weight compounds such as oligomers. However, all of these have the problem of deteriorating the melt fluidity of the polyphenylene sulfide resin.

  On the other hand, as a method for improving the melt fluidity of the polyphenylene sulfide resin composition, a liquid crystal that exhibits an anisotropic melting form in the vicinity of the melting point of the polyphenylene sulfide resin and that is oriented in the shear direction when subjected to a shearing force, reduces the apparent viscosity. The liquid crystalline resin has low weld strength, so if the amount of liquid crystalline resin is large, especially in electrical and electronic parts such as connectors with many welds, There is a problem that strength decreases.

  Patent Document 1 discloses a resin composition in which a polyphenylene sulfide resin having a specific molecular weight and a polyphenylene sulfide resin having a specific molecular weight lower than this are used in combination, and a liquid crystalline resin and a filler are blended therewith. However, the low molecular weight polyphenylene sulfide resin has a problem that the chlorine content increases due to the large number of molecular chain ends, and by specifying the blending amount of the liquid crystalline resin, high weld strength and high melt fluidity are achieved. There is no disclosure that a good balance can be achieved.

  Patent Document 2 discloses a polyphenylene sulfide resin composition for encapsulating electronic components, which is obtained by blending a polyphenylene sulfide resin having a specific melt viscosity with a liquid crystalline resin exhibiting an anisotropic melt form in a specific temperature range and glass fibers. In the examples, polyphenylene sulfide resin having a melt viscosity of 1000 poise is used, and it is described that the resin is a polyphenylene sulfide resin from which impurities such as chlorine ions have been removed. However, there is no mention of chlorine existing at the molecular chain ends of polymers and oligomers, and the amount of chloroform extracted is 1.8% by weight or less, and it is washed with an organic solvent in the post-treatment step of polymerization. No mention is made of the effectiveness of using polyphenylene sulfide resin.

  In view of the present situation, the present inventors have added 100 parts by weight of a polyphenylene sulfide resin having a chloroform extraction amount of 1.8% by weight or less and a melt viscosity of 60 Pa · s or more (320 ° C., shear rate 1000 / s). On the other hand, the polyphenylene sulfide resin composition formed by blending (B) 5 to 30 parts by weight of a liquid crystalline resin and (C) 30 to 90 parts by weight of a fibrous filler has low chlorine content and high strength. In particular, it has been found that it has both weld strength and excellent melt fluidity.

Japanese Patent Laid-Open No. 7-166056 JP-A 64-74265

  None

  The present invention provides a polyphenylene sulfide resin composition having a low chlorine content, excellent melt fluidity and high weld strength, and an electric / electronic component comprising an injection-molded product thereof.

The present invention provides the following.
1. (A) With respect to 100 parts by weight of polyphenylene sulfide resin having a chloroform extraction amount of 1.8% by weight or less and a melt viscosity of 60 Pa · s or more (320 ° C., shear rate 1000 / s), (B) liquid crystalline resin A polyphenylene sulfide resin composition comprising 5 to 30 parts by weight and 30 to 90 parts by weight of (C) filler.
2. (A) The polyphenylene sulfide resin composition according to the above item 1, wherein the polyphenylene sulfide resin is washed with an organic solvent in a post-treatment step of polymerization.
3. (A) The polyphenylene sulfide resin composition according to any one of the above items 1 and 2, wherein the polyphenylene sulfide resin is substantially linear.
4). 4. The polyphenylene sulfide resin composition as described in any one of 1 to 3 above, wherein the chlorine content is 900 ppm or less.
5). (D) A silane compound having any functional group selected from an epoxy group, an amino group, an isocyanate group, and a hydroxyl group is blended in an amount of 0.05 to 3 parts by weight with respect to 100 parts by weight of (A) polyphenylene sulfide resin. 5. The polyphenylene sulfide resin composition as described in any one of 1 to 4 above.
6). 6. The polyphenylene sulfide resin composition as described in any one of 1 to 5 above, wherein (i) the spiral flow length of the polyphenylene sulfide resin composition is 35 mm or more.
7). (B) The polyphenylene sulfide resin composition as described in any one of 1 to 6 above, wherein (B) the melting point of the liquid crystalline resin is 260 ° C. or higher.
8). 8. A molded article comprising the polyphenylene sulfide resin composition according to any one of 1 to 7 above. A molded article obtained by injection molding the polyphenylene sulfide resin composition according to any one of 1 to 7 above.
10. The molded article according to the above item 8 or 9, wherein the molded article is an electric / electronic component.
11. 11. The molded article according to the above 10, wherein the electrical / electronic component is any one of a connector, a connector component, and a capacitor component.

  According to the present invention, it is possible to provide a polyphenylene sulfide resin composition having a low chlorine content, excellent melt fluidity, and high weld strength, and an electric / electronic component comprising an injection-molded product thereof.

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

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. Moreover, about 30 mol% or less of the repeating unit of the PPS resin may be composed of a repeating unit having the following structure.

  Since the PPS copolymer having a part of such a structure has a low melting point, such a resin composition is advantageous in terms of moldability.

  The (A) PPS resin used in the present invention must have a chloroform extraction amount of 1.8% by weight or less, and needs to be 1.0% by weight or less. PPS resin tends to increase the chlorine content when the chloroform extraction amount exceeds 1.8% by weight, and it is difficult to obtain excellent mechanical strength, particularly excellent weld strength required for electric and electronic parts. Become. In order to obtain a PPS resin having a chloroform extraction amount of 1.8% by weight or less, a method of washing with an organic solvent in a post-treatment step described later is preferably used.

  In the present invention, the amount of chloroform extracted from the (A) PPS resin was extracted with a Soxhlet extractor using a PPS sample amount of about 10 g and chloroform of 200 ml for 5 hours, and the extract was dried at 50 ° C. Is divided by the charged PPS sample amount and multiplied by 100 to express the percentage.

  The melt viscosity of the (A) PPS resin used in the present invention is essential to be 60 Pa · s or higher (320 ° C., shear rate 1000 / s) from the viewpoint of reducing chlorination, and is 70 Pa · s or higher. It is more preferable. Two or more PPS resins having different melt viscosities may be used in combination. In this case, the melt viscosity of the PPS resin mixture in which two or more different PPS resins are mixed may be 60 Pa · s or more.

  In addition, the melt viscosity of the (A) PPS resin in the present invention is a value measured using a Capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of 320 ° C. and a shear rate of 1000 / s.

  Hereinafter, a method for producing the (A) PPS resin used in the present invention will be described. However, the present invention is not limited to the following method as long as the PPS having the above structure is obtained.

  First, the contents of the polyhalogen aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used in the production method will be described.

[Polyhalogenated aromatic compounds]
The polyhalogenated aromatic compound used in the present invention refers to 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, and preferably p-dichlorobenzene is used. Further, it is possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but it is preferable to use a 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 1.5 mol, per mol of the sulfidizing agent, from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing. More preferably, the range of 1.005 to 1.2 mol can be exemplified.

[Sulfiding agent]
Examples of the sulfidizing agent used in the present invention include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.
Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more of these. Preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  In addition, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Moreover, 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. Moreover, 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.

  In the present invention, the amount of the sulfidizing agent charged means the residual amount obtained by subtracting the loss from the actual charged amount when a partial loss of the sulfiding agent occurs before the start of the polymerization reaction due to dehydration operation or the like. Shall.

  An alkali metal hydroxide and / or an alkaline earth metal hydroxide can be used in combination with the sulfidizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof. Specific examples of the metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide is preferably used.

  When an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. A range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.

[Polymerization solvent]
In the present invention, an organic polar solvent is used as a 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, and 1,3-dimethyl-2-imidazolide. Non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric acid triamide, dimethyl sulfone, tetramethylene sulfoxide and the like, and mixtures thereof, and the like are all included. It is preferably used because of its high reaction stability. Of these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

  The amount of the organic polar solvent used is selected in the range of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, more preferably 2.5 to 5.5 mol per mol of the sulfidizing agent. .

[Molecular weight regulator]
In the present invention, a monohalogen compound such as monochlorobenzene (not necessarily an aromatic compound) may be used to form the end of the PPS resin to be produced, or to reduce the chlorine content, adjust the polymerization reaction or the molecular weight. May be used in combination with the polyhalogenated aromatic compound.

[Polymerization aid]
In the present invention, it is also a preferred embodiment to use a polymerization aid for adjusting the degree of polymerization. Here, the polymerization assistant means a substance having an action of increasing the viscosity of the obtained PPS resin. Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earths. Metal phosphates and the like. These may be used alone or in combination of two or more. Of these, organic carboxylates, water, and alkali metal chlorides are preferable. Further, as the organic carboxylates, alkali metal carboxylates are preferable, and as the alkali metal chlorides, lithium chloride is preferable. And / or water and lithium chloride are preferably used.

  The alkali metal carboxylate is a general formula R (COOM) n (wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group). M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3). Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include, for example, 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 an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates, and are allowed to react by adding approximately equal chemical equivalents. You may form by. Among the 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 an appropriate solubility in the polymerization system, is most preferably used.

  When using these alkali metal carboxylates as polymerization aids, the amount used is usually in the range of 0.01 to 2 moles per mole of charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization. The range of 0.1-0.6 mol is preferable, and the range of 0.2-0.5 mol is more preferable.

  Moreover, the addition amount in the case of using water as a polymerization aid is usually in the range of 0.3 mol to 15 mol with respect to 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization, 0.6 to The range of 10 mol is preferable, and the range of 1 to 5 mol is more preferable.

  Of course, two or more kinds of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, a higher molecular weight can be obtained in a smaller amount.

  There is no particular designation as to the timing of addition of these polymerization aids, which may be added at any time during the previous step, polymerization start, polymerization in the middle to be described later, or may be added in multiple times. When using an alkali metal carboxylate as a polymerization aid, it is more preferable to add it at the start of the previous step or at the start of the polymerization from the viewpoint of easy addition. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound during the polymerization reaction after charging.

[Polymerization stabilizer]
In the present invention, a polymerization stabilizer may 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 measure of the side reaction is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the alkali metal carboxylate described above also acts as a polymerization stabilizer, it is one of the polymerization stabilizers used in the present invention. In addition, when an alkali metal hydrosulfide is used as a sulfidizing agent, it has been described above that it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

  These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is usually in a proportion of 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, relative to 1 mol of the charged alkali metal sulfide. Is preferably used. If this ratio is small, the stabilizing effect is insufficient. Conversely, if the ratio is too large, it is economically disadvantageous or the polymer yield tends to decrease.

  The addition timing of the polymerization stabilizer is not particularly specified, and may be added at any time during the previous step, at the start of polymerization, or during the polymerization described later, or may be added in multiple times. It is more preferable to add at the start of the process or at the start of polymerization from the viewpoint of easy addition.

  Next, the manufacturing method of (a) PPS resin used in the present invention will be specifically described in the order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process.

[pre-process]
In the method for producing (a) PPS resin used in the present invention, the sulfiding agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the organic polar solvent and the sulfiding agent are added. It is preferable to raise the temperature of the mixture, and to remove an excessive amount of water out of the system.

  As described above, a sulfidizing agent prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank different from the polymerization tank is also used as the sulfidizing agent. Can do. Although there is no particular limitation on this method, desirably an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C., preferably from room temperature to 100 ° C. In addition, there is a method in which the temperature is raised to at least 150 ° C. or more, preferably 180 to 260 ° C. under normal pressure or reduced pressure, and water is distilled off. A polymerization aid may be added at this stage. Moreover, in order to accelerate | stimulate distillation of a water | moisture content, you may react by adding toluene etc.

  The amount of water in the polymerization system in the polymerization reaction is preferably 0.3 to 10.0 moles per mole of the charged sulfidizing agent. Here, the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. In addition, the water to be charged may be in any form such as water, an aqueous solution, and crystal water.

[Polymerization reaction step]
In the present invention, a PPS resin is produced by reacting a sulfidizing 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 sulfidizing agent, and the polyhalogenated aromatic compound are desirably mixed in an inert gas atmosphere at room temperature to 240 ° C., preferably 100 to 230 ° C. . A polymerization aid may be added at this stage. The order in which these raw materials are charged may be out of order or may be simultaneous.
The mixture is usually heated to a temperature in the range of 200 ° C to 290 ° C. Although there is no restriction | limiting in particular in a temperature increase rate, Usually, the speed of 0.01-5 degreeC / min is selected, and the range of 0.1-3 degreeC / min is more preferable.

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

  In the stage before reaching the final temperature, for example, a method of reacting at 200 to 260 ° C. for a certain time and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. Under the present circumstances, as reaction time in 200 to 260 degreeC, the range of 0.25 to 20 hours is normally selected, Preferably the range of 0.25 to 10 hours is selected.

  In order to obtain a polymer having a higher degree of polymerization, it may be effective to perform polymerization in multiple stages. When the polymerization is performed in a plurality of stages, it is effective that the conversion 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 (herein 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 polyhalogenated aromatic compound is added excessively in a molar ratio with respect to the alkali metal sulfide, conversion rate = [PHA charge amount (mol) −PHA remaining amount (mol)] / [PHA charge amount (mol) -PHA excess (mole)]
(B) In cases other than (a) above, conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol)]

[Recovery process]
In the method for producing the (A) PPS resin used in the present invention, a solid is recovered from a polymerization reaction product containing a polymer, a solvent and the like after the completion of polymerization. Any known recovery method may be adopted for the PPS resin used in the present invention.

  For example, after completion of the polymerization reaction, a method of slowly cooling and recovering the particulate polymer may be used. Although there is no restriction | limiting in particular in the slow cooling rate in this case, Usually, it is about 0.1 degree-C / min-about 3 degree-C / min. There is no need for slow cooling at the same rate in the entire process of the slow cooling step, and a method of slow cooling at a rate of 0.1 to 1 ° C./minute until the polymer particles crystallize and then 1 ° C./minute or more is used. It may be adopted.

Moreover, it is also one of the preferable methods to perform said collection | recovery on quenching conditions, As a preferable method of this collection method, the flash method is mentioned. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or more, 8 kg / cm ² or more) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in the form of powder simultaneously with the solvent recovery This is a method, and the term “flash” here means that a polymerization reaction product is ejected from a nozzle. Specific examples of the atmosphere to be flushed include nitrogen or water vapor at normal pressure, and the temperature is usually selected from the range of 150 ° C to 250 ° C.

[Post-processing process]
The (A) PPS resin used in the present invention may be produced through the above polymerization and recovery steps and then subjected to acid treatment, hot water treatment or washing with an organic solvent. From the viewpoint of achieving this, it is preferable to carry out at least one cleaning treatment with an organic solvent.
When acid treatment is performed, it is as follows. The acid used for the acid treatment of the PPS resin in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid. Of these, acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method of immersing the PPS resin in an acid or an acid aqueous solution, and it is possible to appropriately stir or heat as necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous PH4 solution heated to 80 to 200 ° C. and stirring for 30 minutes. The PH after processing may be 4 or more, for example, about PH 4-8. The acid-treated PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

  When performing hot water treatment, it is as follows. In the hot water treatment of the PPS resin used in the present invention, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If it is less than 100 ° C., the effect of preferable chemical modification of the PPS resin is small, which is not preferable.

  The water used is preferably distilled water or deionized water in order to express the preferable chemical modification effect of the PPS resin by the hot water washing of the present invention. There is no particular limitation on the operation of the hot water treatment, and a predetermined amount of PPS resin is put into a predetermined amount of water and heated and stirred in a pressure vessel, or a continuous hot water treatment is performed. The ratio of the PPS resin to water is preferably higher, but usually a bath ratio of 200 g or less of PPS resin is selected for 1 liter of water.

  Further, since the decomposition of the terminal group is not preferable, the treatment atmosphere is preferably an inert atmosphere in order to avoid this. Further, the PPS resin after the hot water treatment operation is preferably washed several times with warm water in order to remove remaining components.

  When washing with an organic solvent, it is as follows. The organic solvent used for washing the PPS resin in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1, 3 -Nitrogen-containing polar solvents such as dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide-sulfon solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, Ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, teto Halogen solvents such as chloroethane, perchlorethane, chlorobenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and benzene, Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene. Among these organic solvents, use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. There is no particular limitation on the cleaning time. Depending on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect can be obtained usually by cleaning for 5 minutes or more. It is also possible to wash in a continuous manner.

  In the present invention, the polyphenylene sulfide resin obtained as described above may be treated by washing with water containing an alkaline earth metal salt.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with water containing an alkaline earth metal salt. There are no particular restrictions on the type of alkaline earth metal salt, but alkaline earth metal salts of water-soluble organic carboxylic acids such as calcium acetate and magnesium acetate, and alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide. Are preferable examples, and alkaline earth metal salts of water-soluble organic carboxylic acids such as calcium acetate and magnesium acetate are particularly preferable. The temperature of the water is preferably room temperature to 200 ° C, more preferably 50 to 90 ° C. The amount of the alkaline earth metal salt used in the water is preferably 0.1 g to 50 g, more preferably 0.5 g to 30 g, relative to 1 kg of the dried polyphenylene sulfide resin. The cleaning time is preferably 0.5 hours or longer, and more preferably 1.0 hour or longer. The preferred washing bath ratio (weight of warm water containing alkaline earth metal salt per unit weight of dry polyphenylene sulfide resin) depends on the washing time and temperature, but warm water containing the above alkaline earth metal per kg of dry polyphenylene sulfide is preferred. It is preferable to wash using 5 kg or more, and it is more preferable to wash using 10 kg or more. There is no restriction | limiting in particular as an upper limit, Although it may be high, it is preferable that it is 100 kg or less from the point of the usage-amount and the effect acquired. Such warm water cleaning may be performed a plurality of times.

  The (A) PPS resin used in the present invention can be used after having been polymerized to have a high molecular weight by heating in an oxygen atmosphere and thermal oxidation crosslinking treatment by heating with addition of a crosslinking agent such as peroxide. .

  When the 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. The oxygen concentration is preferably 5% by volume or more, more preferably 8% by volume or more. Although there is no restriction | limiting in particular in the upper limit of oxygen concentration, About 50 volume% is a limit. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and further preferably 2 to 25 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  However, from the viewpoint of achieving both high weld strength and excellent melt fluidity, the introduction of a crosslinked structure is not very preferable, and a linear PPS is preferable.

  In addition, it is possible to carry out dry heat treatment for the purpose of suppressing thermal oxidative crosslinking and removing volatile matter. The temperature is preferably 130 to 250 ° C, and more preferably 160 to 250 ° C. In this case, the oxygen concentration is preferably less than 5% by volume, and more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and further preferably 1 to 10 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  Examples of such suitable PPS resin products include M2588, M2088, T1881, E2280, E2180, E2080, and GR01 manufactured by Toray Industries, Inc.

  In the present invention, it is essential to blend 5 to 30 parts by weight of (B) liquid crystalline resin with respect to 100 parts by weight of (A) polyphenylene sulfide resin, and a range of 5 to 20 parts by weight is more preferable, and 7 to A range of 16 parts by weight is more preferred. (B) When the blending amount of the liquid crystalline resin exceeds 30 parts by weight, the weld strength is remarkably lowered. On the other hand, when it is less than 5 parts by weight, the melt fluidity decreases, which is not preferable.

  Examples of the (B) liquid crystalline resin include liquid crystalline polyesters and liquid crystalline polyester amides that form an anisotropic melt phase. Specific examples thereof include aromatic oxycarbonyl units, aromatic dioxy units, aromatics. Liquid crystalline polyester that forms an anisotropic melt phase composed of structural units selected from dicarbonyl units, ethylenedioxy units, etc., and the above structural units and aromatic iminocarbonyl units, aromatic diimino units, aromatic iminooxy units, etc. And a liquid crystalline polyester amide that forms an anisotropic molten phase comprising a structural unit selected from

  Examples of the liquid crystalline polyester that forms the anisotropic melt phase are preferably liquid crystalline polyesters comprising the following structural units (I), (II), and (IV), (I), (II), ( Examples thereof include liquid crystalline polyesters composed of structural units III) and (IV) and liquid crystalline polyesters composed of structural units (I), (III) and (IV).

(However, R1 in the formula is

One or more groups selected from: R2 is

One or more groups selected from

In the formula, X represents a hydrogen atom or a chlorine atom, and the sum of the structural units (II) and (III) and the structural unit (IV) are substantially equimolar. )

  The structural unit (I) is a structural unit of a polyester formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl. -4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4 , 4′-dihydroxydiphenyl ether selected from one or more aromatic dihydroxy compounds, the structural unit (III) is a structural unit generated from ethylene glycol, the structural unit (IV) is terephthalic acid, Isophthalic acid, 4,4'-diphenyldicarboxylic acid 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid and 1,2-bis (2-chlorophenoxy) ethane-4 Each of the structural units formed from one or more aromatic dicarboxylic acids selected from 4,4′-dicarboxylic acid is shown. Of these, R1 is

And R2 is

Are particularly preferred.

  Examples of liquid crystalline polyesteramides include 6-hydroxy-2-naphthoic acid, liquid crystalline polyesteramide formed from p-aminophenol and terephthalic acid, p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and terephthalic acid. Examples thereof include liquid crystalline polyesteramides (Japanese Patent Laid-Open No. 64-33123) produced from acids, p-aminobenzoic acid and polyethylene terephthalate.

  The liquid crystalline polyester that can be preferably used in the present invention is a copolymer comprising the above structural units (I), (II) and (IV), or comprising (I), (II), (III) and (IV). It is a copolymer, and the copolymerization amount of the structural units (I), (II), (III) and (IV) is arbitrary. However, the following copolymerization amount is preferable from the viewpoint of fluidity.

  That is, when the structural unit (III) is included, the total of the structural units (I) and (II) is the structural units (I) and (II) from the viewpoint of heat resistance, flame retardancy and mechanical properties. 60-95 mol% is preferable with respect to the sum total of (III) and 75-93 mol% is more preferable. Further, the structural unit (III) is preferably 40 to 5 mol%, more preferably 25 to 7 mol%, based on the total of the structural units (I), (II) and (III). The molar ratio [(I) / (II)] of the structural unit (I) to the structural unit (II) is preferably 75/25 to 95/5 from the viewpoint of the balance between heat resistance and fluidity. Preferably it is 78 / 22-93 / 7. The structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (III).

On the other hand, when the structural unit (III) is not included, the structural unit (I) is preferably 40 to 90 mol% based on the total of the structural units (I) and (II) from the viewpoint of fluidity. Particularly preferred is 60 to 88 mol%. The structural unit (IV) is preferably substantially equimolar with the structural unit (II).
In the above, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is an equimolar dioxy unit and the dicarbonyl unit, but the unit constituting the terminal is not necessarily equimolar. Means not limited.

  In addition, when polycondensating the liquid crystalline polyester that can be preferably used in the present invention, in addition to the components constituting the structural units (I) to (IV), 3,3′-diphenyldicarboxylic acid, 2,2 ′ Aromatic dicarboxylic acids such as diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4, Aromatic diols such as 4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxybenzophenone, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4 -Cyclohexanediol, 1,4-cyclohexane dimethyl In addition, an aliphatic group such as a diol, an alicyclic diol, an aromatic hydroxycarboxylic acid such as an m-hydroxybenzoic acid and a 2,6-hydroxynaphthoic acid, and the like are further added in a small proportion within a range that does not impair the object of the present invention. It can be polymerized.

  Further, as the liquid crystalline polyester amide, those obtained by further copolymerizing p-aminophenol and / or p-aminobenzoic acid with the above preferred liquid crystalline polyester are also preferably used.

  The method for producing the liquid crystalline resin in the present invention is not particularly limited, and can be produced according to a known polyester polycondensation method.

  For example, in the production of the liquid crystalline polyester that is preferably used, when the structural unit (III) is not included, the following production methods (1) and (2) may include the structural unit (III): The following production method (3) is preferably employed.

  (1) Deacetic acid polycondensation reaction from diacylated products of aromatic dihydroxy compounds such as p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl, 4,4′-diacetoxybenzene, and aromatic dicarboxylic acids such as terephthalic acid A method for producing a liquid crystalline polyester.

  (2) Acetic anhydride is reacted with p-hydroxybenzoic acid, aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid to acylate phenolic hydroxyl groups. And then producing a liquid crystalline polyester by a deacetic acid polycondensation reaction.

  (3) In the presence of a polyester polymer such as polyethylene terephthalate, an oligomer, or a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate, by the method of (1) or (2) A method for producing a liquid crystalline polyester.

  Although these polycondensation reactions proceed even without a catalyst, it is sometimes preferable to add a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metal magnesium.

  The (b) melting point of the (B) liquid crystalline resin in the present invention is preferably 260 ° C. or higher, more preferably 265 ° C. or higher, and particularly preferably 270 ° C. or higher. Soldering is generally used to mount electronic components such as connectors, connector components, and capacitor components mounted on a printed wiring board. Solder is placed on the substrate to improve integration on the printed circuit board. There is an increasing number of methods in which an electronic component is placed thereon and then passed through a reflow furnace set at a high temperature to melt and fix the solder. At this time, since the temperature in the reflow furnace is 250 ° C. or higher, if the melting point of the (B) liquid crystalline resin is less than 260 ° C., the heat resistance of the polyphenylene sulfide resin composition is lowered, and melting or deformation occurs when passing through the reflow furnace. Since it occurs, it is not preferable.

  In the present invention, the (B) melting point (Tm) of the liquid crystalline resin (B) is the endothermic peak temperature observed when the liquid crystalline resin is measured at room temperature from the room temperature by differential calorimetry at 20 ° C./min. After observing Tm1, the temperature was raised to Tm1 + 20 ° C., held at the same temperature for 5 minutes, cooled to room temperature under a temperature drop condition of 20 ° C./min, and then measured again under a temperature rise condition of 20 ° C./min. It refers to the endothermic peak temperature observed at the time.

  Some (B) liquid crystalline resins in the present invention can measure logarithmic viscosity in pentafluorophenol. In that case, logarithm when measured at 60 ° C. at a concentration of 0.1 g / dl. The viscosity is preferably 0.5 dl / g or more, particularly 1.0 to 3.0 dl / g when the structural unit (III) is included, and 2.0 when the structural unit (III) is not included. ˜10.0 dl / g is preferred.

  In addition, the melt viscosity of the (B) liquid crystalline resin in the present invention is preferably 1 to 2000 Pa · s, and more preferably 2 to 1000 Pa · s.

  The melt viscosity of the liquid crystalline resin (B) in the present invention is a value measured using a Capillograph manufactured by Toyo Seiki Co. under the condition of the melting point (Tm) of the liquid crystalline resin + 10 ° C. and a shear rate of 1000 / s. It is.

  In the present invention, it is essential to blend 30 to 90 parts by weight of the (C) filler with respect to 100 parts by weight of the (A) polyphenylene sulfide resin, and the range of 40 to 90 parts by weight is more preferable. A range of ˜85 parts by weight is more preferable. (C) When the blending amount of the filler is less than 30 parts by weight, the mechanical strength is not sufficiently exhibited, and when it exceeds 90 parts by weight, the melt fluidity is remarkably deteriorated.

  Specific examples of the filler (C) include, as a fibrous filler, glass fiber, carbon fiber, potassium titanate whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, Asbestos fibers, stone-kow fibers, zinc oxide whiskers, ceramic fibers, barium sulfate whiskers, barium titanate whiskers, metal fibers, and the like are used, and these can be used in combination of two or more. In addition, it is better to use these fibrous fillers after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound. It is preferable in the meaning which obtains.

  Specific examples of non-fibrous fillers include talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, silicates such as alumina silicate, silicon oxide, magnesium oxide, etc. Metal compounds, carbonates such as calcium carbonate and magnesium carbonate, sulfates such as calcium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass beads, glass flakes, glass powder, silicon carbide, carbon Black, silica, graphite, alumina, zirconium oxide, titanium oxide, iron oxide, dolomite, barium sulfate, barium carbonate, barium titanate, ceramic beads, boron nitride, zinc oxide, etc. are used, and these may be hollow And even these fillers It can be used in combination of two or more. These non-fibrous fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, silicates such as calcium carbonate, kaolin, clay and talc, carbon black, and graphite are particularly preferable.

  In the present invention, as the filler (C) which is an essential constituent component, glass fibers and carbon fibers are particularly preferably used from the viewpoint of obtaining high mechanical strength.

  In the present invention, a filler having a specific gravity of 3.5 or more may be blended as the filler (C) for the purpose of achieving both mechanical strength and melt fluidity. Specific examples of the filler having a specific gravity of 3.5 or more include zinc oxide whisker, ceramic fiber, barium sulfate whisker, barium titanate whisker, and metal fiber as the fibrous filler. Examples of non-fibrous fillers include alumina, zirconium oxide, titanium oxide, iron oxide, dolomite, barium sulfate, barium carbonate, barium titanate, ceramic beads, boron nitride, and zinc oxide. These may be hollow, and two or more of these fillers can be used in combination. Further, these fillers may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. From the viewpoint of obtaining high melt fluidity, a non-fibrous filler is particularly preferably used, and barium sulfate is most preferably used among them because of the balance between high specific gravity and economy. In particular, precipitated barium sulfate is preferred. This is because the use of precipitated barium sulfate has the advantages of stability during molding, surface gloss of the molded product, and high dimensional accuracy.

  Furthermore, the polyphenylene sulfide resin composition of the present invention includes an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido for the purpose of improving mechanical strength, toughness and the like within a range not impairing the effects of the present invention. A silane compound having at least one functional group selected from the group may be added. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) ) Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2- Amino group-containing alkoxysilane compounds such as aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-hydroxypropyltrimethoxysilane, γ- Examples thereof include a hydroxyl group-containing alkoxysilane compound such as hydroxypropyltriethoxysilane. Among these, an alkoxysilane having an epoxy group, amino group, isocyanate group or hydroxyl group is particularly suitable for obtaining an excellent weld strength.

  A suitable addition amount of the silane compound is selected in the range of 0.05 to 3 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin.

  The polyphenylene sulfide resin composition of the present invention may further be blended with other resins within a range not impairing the effects of the present invention. The blendable resin is not particularly limited, and specific examples thereof include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, polyamide such as aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, poly Polyester resins such as cyclohexyldimethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, olefin copolymers having functional groups such as carboxyl groups, carboxylic acid ester groups, acid anhydrides and epoxy groups, polyolefin elastomers, Polyetherester elastomer, polyetheramide elastomer, polyamideimide, polyacetal, polyimide, polyetherimide, polyethersulfone, Polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyamideimide resin, tetrafluoropolyethylene resin, Examples thereof include an epoxy group-containing polyolefin copolymer.

  In the polyphenylene sulfide resin composition of the present invention, other components such as antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and substitutions thereof) are included within the range not impairing the effects of the present invention. Body), weathering agent (resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based, etc.), release agent and lubricant (montanic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearamide, Various bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (eg, nigrosine), crystal nucleating agents (talc, silica, kaolin, clays, etc.), plasticizers (p- Octyl oxybenzoate, N-butylbenze Sulfonamides, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric charging Inhibitors), flame retardants (eg, red phosphorus, phosphate esters, melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, Brominated epoxy resins or combinations of these brominated flame retardants and antimony trioxide), heat stabilizers, lubricants such as calcium stearate, aluminum stearate, lithium stearate, UV inhibitors, colorants, flame retardants and foaming Normal additives such as agents It can be added.

  The polyphenylene sulfide resin composition of the present invention can provide an excellent low chlorine, low bromine polyphenylene sulfide resin composition from the viewpoint of imparting corrosion resistance and consideration for the environment, and in particular, electrical and electronic parts, It is suitably used in connectors, connector components, and capacitor components. The polyphenylene sulfide resin composition of the present invention preferably has a chlorine and bromine content of 900 ppm or less, particularly preferably in the range of 800 ppm or less.

  The chlorine and bromine contents mentioned here are values measured by the SGS Far East Limited Green Testing Center according to the BS EN 14582 method.

  In the present invention, (i) spiral flow length of polyphenylene sulfide resin composition (using a spiral flow mold having a thickness of 0.5 mm, cylinder temperature 320 ° C., mold temperature 140 ° C., injection speed 230 mm / sec, injection pressure 98 MPa, The flow length formed under the conditions of an injection time of 5 sec and a cooling time of 15 sec) is preferably 35 mm or more, and more preferably 37 mm or more. When the polyphenylene sulfide resin composition is used for, for example, a connector part, the dimensions are often 0.5 mm or less and the length is often about 30 mm or more. Therefore, when the polyphenylene sulfide resin composition is applied to the electronic component field, the spiral flow length (0.5 mm thickness) is often required to be 35 mm or more. For reference, “Torelina” A604 spiral flow length (0.5 mm thick spiral flow mold, cylinder temperature 320 ° C., mold temperature 140 ° C., injection speed 230 mm / sec, injection, for reference. The flow length formed under the conditions of a pressure of 98 MPa, an injection time of 5 seconds, and a cooling time of 15 seconds is 33 mm.

  The method for preparing the polyphenylene sulfide resin composition of the present invention is not particularly limited, but each raw material is supplied to a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll, A representative example is a method of kneading at a temperature of 280 to 380 ° C. There are no particular restrictions on the mixing order of the raw materials, a method in which all raw materials are blended and melt kneaded by the above method, a part of the raw materials are melted and kneaded by the above method, and the remaining raw materials are further blended and melt kneaded. Any method may be used, such as a method of mixing a part of raw materials or a method of mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or twin-screw extruder after compounding. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

  The polyphenylene sulfide resin composition of the present invention thus obtained can be used for various moldings such as injection molding, extrusion molding, blow molding, transfer molding, and is particularly suitable for injection molding applications.

  As described above, the polyphenylene sulfide resin composition of the present invention has a low chlorine content, excellent melt flowability, and high weld strength.For example, among electrical and electronic parts, particularly, connectors, connector components, It is suitably used for capacitor components.

  Other applicable applications of the polyphenylene sulfide resin composition of the present invention include, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, oscillators, various terminal boards, and transformations. Electricity / electronics such as devices, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts Parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts Houses represented by air conditioner parts, typewriter parts, word processor parts, office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, Machine-related parts such as typewriters: Optical instruments such as microscopes, binoculars, cameras, watches, precision machine-related parts; water faucet tops, mixing faucets, pump parts, pipe joints, water control valves, relief Water-related parts such as valves, hot water sensors, water sensors, water meter housings; valve alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, exhaust gas valves, and other fuel related / exhaust systems / Various intake pipes Air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad Wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer Nozzle, air conditioner panel switch board, fuel-related electromagnetic valve carp , Fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, vehicle speed sensor, cable liner, etc. Various uses such as vehicle-related parts can be exemplified.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.

[Measuring method]
(1) Extraction amount of polyphenylene sulfide resin with chloroform Using a Soxhlet extractor, extract polyphenylene sulfide resin sample amount of about 10 g and 200 ml of chloroform for 5 hours, dry the extract at 50 ° C., charge the obtained residue, and add polyphenylene The percentage was calculated by dividing the amount of the sulfide resin sample and multiplying by 100.

(2) Melt viscosity of polyphenylene sulfide resin It was measured using a capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of 320 ° C. and a shear rate of 1000 / s.

(3) Melting point of liquid crystalline resin After observing the endothermic peak temperature Tm1 observed when the liquid crystalline resin is measured at room temperature from 20 ° C / min by differential calorimetry, the temperature is raised to a temperature of Tm1 + 20 ° C. After holding at the same temperature for 5 minutes, after cooling to room temperature under a temperature drop condition of 20 ° C./min, the endothermic peak temperature observed when measured again under a temperature rise condition of 20 ° C./min is the melting point (Tm) It was.

(4) Melt Viscosity of Liquid Crystalline Resin Melt viscosity was measured using a Capillograph manufactured by Toyo Seiki Co., Ltd. under the condition of melting point (Tm) of liquid crystalline resin + 10 ° C. and shear rate of 1000 / s.

(5) Chlorine and bromine contents The SGS Far East Limited Green Testing Center was requested and measured according to the BS EN 14582 method.

(6) Spiral flow length Using a 0.5mm thick spiral flow mold, molding is performed under the conditions of cylinder temperature 320 ° C, mold temperature 140 ° C, injection speed 230mm / sec, injection pressure 98MPa, injection time 5sec, cooling time 15sec. Then, the flow length was measured (molding machine used: “SE-30D” manufactured by Sumitomo Heavy Industries). It can be said that the larger the value of the flow length, the better the melt fluidity.

(7) Weld strength ASTM No. 1 dumbbell piece having gates at both ends and having a weld line near the center of the test piece was molded using an injection molding machine at a cylinder temperature of 320 ° C and a mold temperature of 135 ° C. Tensile strength was measured under the conditions of a strain rate of 5 mm / min and a fulcrum distance of 114 mm.

[Raw materials used]
[Reference Example 1] Polymerization of PPS (PPS-1)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 2583.00 g (31.50 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours under nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS was linear, the melt viscosity was 180 Pa · s (320 ° C., shear rate 1000 / s), and the chloroform extraction amount was 0.27%.

[Reference Example 2] Polymerization of PPS (PPS-2)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 1722.00 g (21.00 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours while flowing nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.
Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS was linear, the melt viscosity was 100 Pa · s (320 ° C., shear rate 1000 / s), and the chloroform extraction amount was 0.43%.

[Reference Example 3] Polymerization of PPS (PPS-3)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 861.00 g (10.5 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours while passing nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS was linear, the melt viscosity was 50 Pa · s (320 ° C., shear rate 1000 / s), and the chloroform extraction amount was 0.57%.

[Reference Example 4] Polymerization of PPS (PPS-4)
M3910 manufactured by Toray Industries, Inc. was treated in a hot air oven at 210 ° C. for 15 hours. The obtained PPS was a crosslinked type, and had a melt viscosity of 100 Pa · s (320 ° C., shear rate of 1000 / s) and a chloroform extraction amount of 2.50%.

[Reference Example 5] PPS mixture (PPS-5)
70% PPS (PPS-2) obtained in Reference Example 2 and 30% PPS (PPS-3) obtained in Reference Example 3 were dry blended. The melt viscosity of the obtained PPS was 80 Pa · s (320 ° C., shear rate 1000 / s), and the chloroform extraction amount was 0.47%.

[Reference Example 5] Polymerization of liquid crystalline resin (B-1)
994 parts by weight of p-hydroxybenzoic acid, 168 parts by weight of 4,4′-dihydroxybiphenyl, 150 parts by weight of terephthalic acid, 173 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and 1011 parts by weight of acetic anhydride were stirred. A reaction vessel equipped with a blade and a distilling tube was charged, while stirring in a nitrogen gas atmosphere, the reaction was carried out for 3 hours while raising the temperature from room temperature to 150 ° C., and the temperature was raised from 150 ° C. to 250 ° C. in 2 hours. Then, the temperature was raised to 335 ° C. over 1.5 hours, and then the pressure was reduced to 6.5 × 10 ⁻³ Pa at 335 ° C. over 1.5 hours. . Melting point 328 ° C., melt viscosity 18 Pa · s (338 ° C., orifice 0) consisting of 80 molar equivalents of aromatic oxycarbonyl units, 10 molar equivalents of aromatic dioxy units, 10 molar equivalents of ethylene dioxy units, and 20 molar equivalents of aromatic dicarboxylic acid units A liquid crystalline polyester having a diameter of 5 mm × 10 mm and a shear rate of 1000 / s was obtained.

[Reference Example 6] Polymerization of liquid crystalline resin (B-2)
994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and 960 parts by weight of acetic anhydride are stirred. A reaction vessel equipped with a blade and a distilling tube was charged, while stirring in a nitrogen gas atmosphere, the reaction was carried out for 3 hours while raising the temperature from room temperature to 150 ° C., and the temperature was raised from 150 ° C. to 250 ° C. in 2 hours. After raising the temperature from ℃ to 330 ℃ in 1.5 hours, the pressure was reduced to 6.5 × 10 ^-3 Pa at 325 ℃ and 1.5 hours, and further stirring was continued for about 0.25 hours to perform polycondensation It was. Melting point 314 ° C., melt viscosity 25 Pa · s (324) consisting of 80 molar equivalents of aromatic oxycarbonyl units, 7.5 molar equivalents of aromatic dioxy units, 12.5 molar equivalents of ethylene dioxy units, 20 molar equivalents of aromatic dicarboxylic acid units Liquid crystalline polyester having an orifice of 0.5 mm diameter × 10 mm and a shear rate of 1000 / s was obtained.

[Reference Example 7] Polymerization of liquid crystalline resin (B-3)
870 parts by weight of p-hydroxybenzoic acid, 327 parts by weight of 4,4′-dihydroxybiphenyl, 89 parts by weight of hydroquinone, 292 parts by weight of terephthalic acid, 157 parts by weight of isophthalic acid and 1367 parts by weight of acetic anhydride (1. 03 equivalents) was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and stirred for 2 hours while raising the temperature from room temperature to 145 ° C. while stirring in a nitrogen gas atmosphere, and from 145 ° C. to 320 ° C. for 4 hours. The temperature was raised. Thereafter, the polymerization temperature was reduced to 133 Pa at 320 ° C. for 1.0 hour, and the mixture was further stirred for about 1.5 hours to perform polycondensation. The p-oxybenzoate unit is 70 molar equivalents relative to the sum of the p-oxybenzoate unit, 4,4′-dioxybiphenyl unit and 1,4-dioxybenzene unit, and 4,4′-dioxybiphenyl unit is 4 Melting point 314 ° C., melting point of 70 molar equivalents relative to the total of 4,4′-dioxybiphenyl units and 1,4-dioxybenzene units, 65 molar equivalents of terephthalate units relative to the total of terephthalate units and isophthalate units A liquid crystalline polyester having a viscosity of 25 Pa · s (324 ° C., orifice 0.5 mm diameter × 10 mm, shear rate 1000 / s) was obtained.

[(C) Filler]
C-1: Glass fiber Asahi Fiber Glass Co., Ltd. T747 (average fiber diameter 13μ) Specific gravity 2.5
C-2: Barium sulfate B-54 specific gravity 4.5 manufactured by Sakai Chemical Industry Co., Ltd.

[(D) Silane compound]
D-1: 3-isocyanatopropyltriethoxysilane, Shin-Etsu Silicone KBE9007
D-2: γ-glycidoxypropyltrimethoxysilane KBM403 manufactured by Shin-Etsu Silicone Co., Ltd.
D-3: γ-aminopropyltriethoxysilane Shin-Etsu Silicone KBE903
D-4: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane KBM303 manufactured by Shin-Etsu Silicone.

[Examples 1 to 12]
After dry blending the components shown in Table 1 at the ratios shown in Table 1, using a TEX30α type twin screw extruder (L / D = 45.5) manufactured by Nippon Steel Works, the cylinder discharge resin temperature at a screw speed of 300 rpm Was set to 330 ° C., melted and kneaded, and pelletized with a strand cutter. The pellets dried overnight at 120 ° C. were used for molding and evaluation.

[Comparative Examples 1-4]
After dry blending the components shown in Table 2 at the ratios shown in Table 2, using a TEX30α type twin screw extruder (L / D = 45.5) manufactured by Nippon Steel Works, the cylinder discharge resin temperature at a screw speed of 300 rpm Was set to 330 ° C., melted and kneaded, and pelletized with a strand cutter. The pellets dried overnight at 120 ° C. were used for molding and evaluation.

[Example 13]
Using a PS20E2ASE molding machine manufactured by Nissei Plastic Industrial Co., Ltd., 50 rows of pin holes (pin hole spacing 1.27 mm) are arranged in one row, the inner glue is 68 mm x 5 mm x height 7 mm, and the glue is 70 mm x 7 mm X A connector molded product having a box shape with a height of 9.3 mm and a shape in which ribs are provided at both ends in the longitudinal direction was molded. The connector has two rows of 50 pin holes per row. The gate is a pin gate.

  When the composition of Example 2 was used and molded at a mold temperature of 135 ° C. and a resin temperature of 320 ° C., a normal molded piece was obtained.

[Comparative Example 5]
When the composition of Comparative Example 3 was used and molded at a mold temperature of 135 ° C. and a resin temperature of 320 ° C., the resin could not completely fill the molded piece even at the maximum injection pressure.

  The present invention relates to a polyphenylene sulfide resin composition having a low chlorine content, excellent melt fluidity, and high weld strength, and an electric / electronic component comprising an injection-molded product thereof, and is particularly suitable for electric / electronic component applications. Used.

Claims (11)

(A) With respect to 100 parts by weight of polyphenylene sulfide resin having a chloroform extraction amount of 1.8% by weight or less and a melt viscosity of 60 Pa · s or more (320 ° C., shear rate 1000 / s), (B) liquid crystalline resin A polyphenylene sulfide resin composition comprising 5 to 30 parts by weight and (C) 30 to 90 parts by weight of a filler. 2. The polyphenylene sulfide resin composition according to claim 1, wherein the (A) polyphenylene sulfide resin is washed with an organic solvent in a post-treatment step of polymerization. (A) The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin is substantially linear. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the chlorine content is 900 ppm or less. (D) A silane compound having any functional group selected from an epoxy group, an amino group, an isocyanate group, and a hydroxyl group is blended in an amount of 0.05 to 3 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to any one of claims 1 to 4. 6. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin composition has (i) a spiral flow length of 35 mm or more.
The polyphenylene sulfide resin composition according to claim 1, wherein (B) the liquid crystalline resin has a (b) melting point of 260 ° C. or higher. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 7. A molded article formed by injection molding the polyphenylene sulfide resin composition according to claim 1. The molded article according to claim 8 or 9, wherein the molded article is an electric / electronic component. The molded article according to claim 10, wherein the electrical / electronic component is any one of a connector, a connector component, and a capacitor component.