JP2010053356A - Polyphenylene sulfide resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition having a low chlorine content and superior melt fluidity and exhibiting good dimension stability in repeated molding operation, and to provide an optical pickup component formed of an injection molded material of the polyphenylene sulfide resin composition. <P>SOLUTION: The polyphenylene sulfide resin composition comprises polyphenylene sulfide resin (A), a non-fibrous filler (B), and a fibrous filler (C) as essential components. For 100 pts.wt. of a resin component in the polyphenylene sulfide resin composition, a total content of the non-fibrous filler (B) and the fibrous filler (C) is 180-300 pts.wt., and a content of the non-fibrous filler (B) is higher than that of the fibrous filler (C). The chlorine content in the polyphenylene sulfide resin composition is 900 ppm or less. <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 excellent dimensional stability during repeated molding, and an optical pickup 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. For this reason, it is widely used for various electric / electronic parts, home appliance parts, automobile parts, machine parts, etc., mainly for injection molding (Patent Documents 1 to 3).

  One such application is an optical pickup component. The application requires special characteristics such as environmental stability of the laser focus (that the laser focus is stable due to changes in the environmental temperature). A phenylene sulfide resin composition that is highly filled and excellent in dimensional stability has often been used.

  On the other hand, DVDs for PCs or recently developed Blu-ray playback / recording models require better dimensional stability than playback-only models, so aluminum die casting is used as an optical pickup component material. Mainly used. However, even in such applications, there is an increasing interest in the application of polyphenylene sulfide resin that is more excellent in dimensional stability and has a high degree of freedom in shape.

  In general, in the injection molding of optical pickup parts, hundreds to tens of thousands of optical pickup parts are obtained per day. Therefore, dimensional stability, particularly dimensional stability during repeated molding to obtain a large number of optical pickup parts is required. One of the major factors affecting the dimensional stability is the mold adhesion gas. If the amount of gas generated by the mold adherence is large, the gas vent provided in the mold is easily clogged, whereby the melt fluidity is disturbed and the dimensions can be changed.

  Low molecular weight components such as oligomers of the polyphenylene sulfide resin composition are greatly involved in the amount of adhesive gas generated in the polyphenylene sulfide resin composition, and if there are many of these, the amount of adhesive gas generated can be increased. 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 particular, since a low molecular weight material such as an oligomer has many chlorine ends, the chlorine content in the polyphenylene sulfide resin composition often reflects the low molecular weight material such as an oligomer, and therefore the chlorine content in the polyphenylene sulfide resin composition. The content can be a measure of the amount of adhesive gas generated in the polyphenylene sulfide resin composition.

  In recent years, in view of excellent corrosion resistance and consideration for the environment, it is required to reduce the content of halogen compounds such as chlorine and bromine, particularly chlorine.

Japanese Patent No. 2003-327828 JP 2004-340237 A JP 2005-48157 A JP 2003-301108 A

  The present invention provides a polyphenylene sulfide resin composition having a low chlorine content, excellent melt fluidity, and excellent dimensional stability during repeated molding, and an optical pickup component comprising the injection molded article.

The present invention provides the following.
1. A polyphenylene sulfide resin composition comprising (A) a polyphenylene sulfide resin, (B) a non-fibrous filler and (C) a fibrous filler, wherein (B) the non-fibrous filler and (C) fibers The total amount of the fibrous filler is 200 parts by weight to 300 parts by weight with respect to 100 parts by weight of the resin component in the polyphenylene sulfide resin composition, and the content of (B) non-fibrous filler is (C) A polyphenylene sulfide resin composition having a content greater than that of the fibrous filler and a chlorine content of the polyphenylene sulfide resin composition of 900 ppm or less.
2. 70. The polyphenylene sulfide resin composition according to the above item 1, wherein 70% by weight or more of the resin component constituting the polyphenylene sulfide resin composition is (A) a polyphenylene sulfide resin.
3. (A) 3 to 50 parts by weight of (D) an amorphous resin having a glass transition temperature of 110 ° C. or higher with respect to 100 parts by weight of the polyphenylene sulfide resin, Polyphenylene sulfide resin composition.
4). Spiral flow length (flow when molding using a spiral flow mold of 1 mm thickness, cylinder temperature 320 ° C., mold temperature 140 ° C., injection speed 230 mm / sec, injection pressure 98 MPa, injection time 5 sec, cooling time 15 sec. 4. The polyphenylene sulfide resin composition according to any one of 1 to 3 above, wherein the length is in the range of 50 mm to 120 mm.
5. The polyphenylene sulfide resin composition as described in any one of 1 to 4 above, wherein the amount of an adhesive gas component when heated at 330 ° C. for 3 hours is 0.06% by weight or less.
6). 6. An optical pickup component obtained by injection molding the polyarylene sulfide resin composition according to any one of 1 to 5 above.
7). 6. An optical pickup component for both reproduction and recording, which is obtained by injection molding the polyarylene sulfide resin composition according to any one of 1 to 5 above.

  According to the present invention, it is possible to provide an optical pickup component comprising a polyphenylene sulfide resin composition having a low chlorine content, excellent melt fluidity, and excellent dimensional stability during repeated molding, and an injection molded product thereof.

It is a figure which shows the optical pick-up model injection molded product used for optical-axis stability evaluation.

(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.

  From the viewpoint of obtaining excellent strength and low chlorination, the (A) PPS resin used in the present invention preferably has a chloroform extraction amount of 1.8 wt% or less, and more preferably 1.0 wt% or less. .

  In order to obtain a PPS resin having a chloroform extraction amount of 1.8 wt% or less, a method of washing with an organic solvent or the like in a post-treatment step described later is preferably used.

  The amount of chloroform extracted in the present invention 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. This is a percentage notation by multiplying by 100.

  Although there is no restriction | limiting in particular in the melt viscosity of (A) PPS resin used by this invention, The melt viscosity is 40 ~ from the viewpoint of making the both outstanding weld strength and good fluidity compatible, and aiming at the low chlorination mentioned later. The range of 2000 Pa · s (320 ° C., shear rate 1000 / s) is preferable, and the range of 40 to 1300 Pa · s or less is more preferable. Two or more polyarylene sulfide resins having different melt viscosities may be used in combination.

  In addition, the melt viscosity in this invention is the value measured using the Toyo Seiki Co., Ltd. capilograph on the conditions of 320 degreeC and the shear rate of 1000 / s. In the polyphenylene sulfide resin composition of the present invention, the chlorine content in the resin composition needs to be 900 ppm or less, more preferably 800 ppm or less, still more preferably 700 ppm or less, and 600 ppm or less. It is even more preferable. The chlorine content in the polyphenylene sulfide resin composition often reflects the amount of low molecular weight substances such as oligomers, so the chlorine content in the polyphenylene sulfide resin composition is a measure of the amount of adhesive gas generated in the polyphenylene sulfide resin composition. obtain. If the chlorine content is in the range exceeding 900 ppm, the amount of the deposit on the mold tends to increase during the injection molding, so that the gas vent provided in the mold tends to be clogged during repeated molding. As a result, the melt fluidity is disturbed, the size is likely to change, and the light for DVD / PCs for recently developed and used for both playback and recording for Blu-ray, which requires particularly excellent dimensional stability. It is no longer suitable for pick-up component materials.

In recent years, in view of excellent corrosion resistance and consideration for the environment, it is required to reduce the content of halogen compounds such as chlorine and bromine, particularly chlorine. The reason why the chlorine content is set to 900 ppm or less is that it is often required that the chlorine content be set to 900 ppm or less from the viewpoints of corrosion resistance and environmental load reduction in electronic component applications.

The chlorine and bromine contents mentioned here are values measured in SGS Taiwan (Kaohsiung) according to the BS EN 14582 method, requested to the SGS Far East Limited Green Testing Center.

  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 (mol) −PHA remaining amount (mol)] / [PHA charge (mol) -PHA excess (mole)]
(B) In cases other than the above (a) 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.

  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.

  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 M3910, M3102, M2900, M2100, L4230, L2840, L2120, M2888, M2588, M2088, T1881, E2280, E2180, E2080, and GR01 manufactured by Toray Industries, Inc.

  In the present invention, in addition to the polyphenylene sulfide resin, it can depend on the amorphous resin, non-fibrous filler, and the kind and blending amount of the fibrous filler, but the balance of fluidity, toughness, burr, and chlorine content. It is preferable to use two or more types of polyphenylene sulfide resins in combination. In particular, when an amorphous resin, a non-fibrous filler, or a fibrous filler is blended, the melt viscosity of the polyphenylene sulfide resin to be used becomes important because the fluidity deteriorates. The melt viscosity of the polyphenylene sulfide resin suitable for maintaining fluidity is preferably in the range of 5 to 20 Pa · s (320 ° C., shear rate 1000 / s), and 25 to 300 Pa · s for imparting toughness and burrs. The range of s (320 ° C., shear rate 1000 / s) is preferable. Therefore, in order to balance fluidity, toughness, and burrs, it is one of preferred embodiments to use a mixture of both polyphenylene sulfide resins.

  When mixing and using a polyphenylene sulfide resin having a melt viscosity of 5 to 20 Pa · s (320 ° C., shear rate 1000 / s) and a polyphenylene sulfide resin having a melt viscosity of 25 to 300 Pa · s (320 ° C., shear rate 1000 / s) The ratio of polyphenylene sulfide resin is 100% by weight, polyphenylene sulfide resin having a melt viscosity of 5 to 20 Pa · s is 20 to 80% by weight, and polyphenylene sulfide resin having a melt viscosity of 25 to 300 Pa · s is 20 to 80% by weight. More preferably, each is 30 to 70% by weight, and particularly preferably 40 to 60% by weight.

  The polyphenylene sulfide resin composition of the present invention contains (B) a non-fibrous filler and (C) a fibrous filler as essential components together with (A) the polyphenylene sulfide resin.

  Specific examples of such (B) non-fibrous filler include silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, oxidation Metal compounds such as magnesium, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, calcium hydroxide, magnesium hydroxide and aluminum hydroxide Such as hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite, etc., and these may be hollow, and further these fillers Two or more types can be used together A. These 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, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, silicates such as kaolin, clay and talc, alumina and graphite are particularly preferable.

  In the measurement of the chlorine content of the polyphenylene sulfide resin composition of the present invention, it is preferable to blend a non-fibrous filler in order to stabilize the measured value of the chlorine content. In the present invention, calcium carbonate is particularly preferable from the viewpoints of cost, dimensional stability, and stabilization of measured values of chlorine content. The blending amount of the non-fibrous filler in the present invention is preferably 65 parts by weight or more and 165 parts by weight or less, and 100 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the resin component in the polyphenylene sulfide resin composition of the present invention. Is more preferably 115 parts by weight or more and 130 parts by weight or less.

  Specific examples of the (C) fibrous filler include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, A ceramic fiber, asbestos fiber, a stone fiber, a metal fiber, etc. are mentioned, These can also be used together 2 or more types. In addition, using these fillers with a 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 can provide better mechanical strength. Preferred in meaning. Of these, glass fiber and carbon fiber are more preferably used.

  In the present invention, the total amount of (B) non-fibrous filler and (C) fibrous filler is 200 to 300 parts by weight with respect to 100 parts by weight of the resin component in the polyphenylene sulfide resin composition of the present invention. The content is preferably 200 parts by weight or more and 280 parts by weight or less, and more preferably 210 parts by weight or more and 250 parts by weight or less.

When the total amount of (B) non-fibrous filler and (C) fibrous filler is 180 parts by weight or less with respect to 100 parts by weight of the resin component in the polyphenylene sulfide resin composition of the present invention, the environment of laser focus When the stability is insufficient and the amount is 300 parts by weight or more, the melt fluidity is remarkably impaired.

In the present invention, the content of (B) non-fibrous filler needs to be larger than the content of (C) fibrous filler. When the content of (B) non-fibrous filler is less than the content of (C) fibrous filler, the environmental stability of the laser focus becomes insufficient, which is not preferable.

  Furthermore, in the polyphenylene sulfide resin composition of the present invention, (D) an amorphous resin having a glass transition temperature of 110 ° C. or higher is contained in an amount of 3 to 50 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. From the viewpoint of obtaining better environmental stability of the laser focus, the range of 5 to 40 parts by weight is more preferable, and the range of 8 to 30 parts by weight is still more preferable. Here, the glass transition temperature is a value obtained by increasing the temperature at a rate of 20 ° C./min using a differential scanning calorimeter (DSC).

  Specific examples of the amorphous resin (D) having a glass transition temperature of 110 ° C. or higher include polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyarylate resins, and polyetherimide resins. Examples thereof include resins and polyamideimide resins, among which polyphenylene ether resins, polyetherimide resins, polysulfone resins and polyethersulfone resins are particularly suitable, and polyphenylene ether resins are particularly preferred.

  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 ester groups, acid anhydride groups, and epoxy groups, polyolefin elastomers , Polyetherester elastomer, polyetheramide elastomer, polyacetal, polyimide, polyketone resin, liquid crystal polymer, polyetherketone resin, poly Oh ether ketone resin, polyether ether ketone resins, polyethylene tetrafluoride resins, epoxy group-containing polyolefin copolymer, polystyrene, etc. Shinji O tack tick polystyrene.

  However, in order to sufficiently exhibit the effects of the present invention, it is preferable that 70% by weight or more of the resin component constituting the polyphenylene sulfide resin composition of the present invention is (A) polyphenylene sulfide resin. Furthermore, the PPS resin composition of the present invention has an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group 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 among them 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.

  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 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.

  Among them, a preferable method for preparing the polyphenylene sulfide resin composition of the present invention is a method of melt-kneading with a biaxial extruder. When melt-kneading with such a twin-screw extruder, the screw rotation speed is preferably controlled to 200 to 400 rpm from the viewpoint of gas reduction, and more preferably 230 to 350 rpm.

  Usually, from the viewpoint of increasing the discharge amount per unit time and increasing the productivity, a method of increasing the screw rotation speed is adopted as long as the torque capacity of the extruder allows. However, since the resin composition of the present invention contains a large amount of filler, when the screw rotation speed is increased too much, decomposition of the resin is promoted by shearing heat generation. An object of the present invention is to obtain a resin composition capable of stably molding an optical pickup component for both reproduction and recording. For this purpose, the decomposition of the resin is suppressed as much as possible by shearing heat generation. It is desirable to reduce the generation amount of cracked gas as much as possible. From that viewpoint, when the polyphenylene sulfide resin composition of the present invention is adjusted by a melt kneading method using a twin-screw extruder, the screw rotation speed is more preferably controlled to 400 rpm or less, preferably less than 350 rpm. However, even if the screw rotation speed is less than 200 rpm, the effect of suppressing the decomposition of the resin due to shearing heat generation is small, and it is preferable to set it to 200 rpm or more in consideration of productivity.

  As a measure of the amount of gas generated from the resin composition, it is also possible to use a method of measuring the amount of an adhesive gas component when heated at 330 ° C. for 3 hours. Specifically, about 1.5 g of the resin composition is precisely weighed in a glass sample tube having a diameter of 18 mm, a depth of 75 mm, and a thickness of 1 mm, and the glass sample tube is adjusted to 330 ° C. ± 0.1 ° C. After inserting into an aluminum block heater (equipment: model number AL-331 manufactured by Synics Corp., having 12 cylindrical grooves with a diameter of 18.3 mm and a depth of 70 mm), a precise balance is placed in the opening of the glass sample tube. Put the finished glass plate. After 3 hours, the glass plate is removed and cooled to room temperature in a desiccator. This glass plate is weighed again, the amount of gas attached to the glass plate is determined from the difference from the original glass plate weight, the amount attached is divided by the amount of resin composition, and multiplied by 100 to give the gas per resin composition amount. The amount of deposits (%) was determined. From the results of the molding evaluation of the resin composition by the user, it is found that if this value is 0.06% by weight or less, preferably 0.05% by weight or less, it can be used as an optical pickup part for both reproduction and recording. It was.

  The resin composition of the present invention has a spiral flow length (a spiral flow mold having a thickness of 1 mm, cylinder temperature 320 ° C., mold temperature 140 ° C., injection speed 230 mm / sec, injection pressure 98 MPa, injection time 5 sec, cooling time. The flow length when molded under the condition of 15 sec) is preferably in the range of 50 mm to 120 mm, and more preferably in the range of 70 mm to 100 mm. In order to reduce the amount of low molecular weight components such as oligomers of the polyphenylene sulfide resin composition and the chlorine content, it is desirable to use a PPS resin having a high molecular weight. However, when a PPS resin having a high molecular weight is used, the melt fluidity of the resin composition is deteriorated. Optical pickup parts have a complicated structure, and if the melt fluidity is too low, it is necessary to apply a strong pressure to the resin during molding, which causes stress strain to remain in the resin composition molded body, and during long-term use The residual stress is released, and there is a concern that the size of the molded body is deteriorated. In the case of an optical pickup component for both reproduction and recording that requires particularly high dimensional stability, it is necessary to minimize this residual stress. As a result of various molding evaluations, the present inventors have used a spiral flow length (a spiral flow mold having a thickness of 1 mm as an index of the balance point between the low molecular weight component amount and the chlorine content and the effect of reducing the melt fluidity. And a cylinder length of 320 ° C., a mold temperature of 140 ° C., an injection speed of 230 mm / sec, an injection pressure of 98 MPa, an injection time of 5 sec, and a cooling time of 15 sec. I found it.

  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.

  The injection molded article of the polyphenylene sulfide resin composition of the present invention obtained as described above has a low chlorine content, excellent melt flowability, and excellent dimensional stability during repeated molding. It is particularly suitably used for optical pickup parts, particularly optical pickup parts for both reproduction and recording that require excellent dimensional stability.

  Other applicable applications of the polyphenylene sulfide resin composition of the present invention include, for example, sensors, LED lamps, connectors, connector components, capacitor component sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, and oscillations. Child, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts, etc. Electric / electronic parts represented by: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser disks / compact disks Audio equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office electrical parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts Machine-related parts represented by cleaning jigs, motor parts, lighters, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, precision machine-related parts; water faucet tops, mixing faucets, Water parts such as pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, water meter housings; valve alternator terminals, alternator connectors, IC regulators, light potentiometer bases, exhaust gas valves Etc. , Fuel-related / exhaust / intake system 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 Switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, Various applications such as automobile-related parts such as vehicle speed sensors and cable liners 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 PPS resin in chloroform Using a Soxhlet extractor, extract about 10 g of PPS sample and 200 ml of chloroform for 5 hours, dry the extract at 50 ° C., charge the obtained residue, and add the amount of PPS sample. This is a percentage notation by multiplying by 100.

(2) Melt viscosity of PPS resin This 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.

(3) Bending strength Measurement was performed according to ASTM D790. Specifically, the measurement was performed as follows. The resin composition pellets of the present invention are supplied to an injection molding machine (SG75-HIPRO · MIII) manufactured by Sumitomo-Nestal Co., which is set at a cylinder temperature of 320 ° C., and injection pressure = low molding pressure + 5 kgf / cm ² gauge pressure. Injection molding was performed to obtain a test piece having a width of 12.7 mm, a height of 6.4 mm, and a length of 127 mm. Using this test piece, measurement was performed under the conditions of a span of 100 mm and a strain rate of 3 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50%.

(4) Spiral flow length Using a spiral flow mold having a thickness of 1 mm, molding was performed under conditions of a cylinder temperature of 320 ° C., a mold temperature of 140 ° C., an injection speed of 230 mm / sec, an injection pressure of 98 MPa, an injection time of 5 sec, and a cooling time of 15 sec. The flow length was measured (use molding machine: “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.

(5) Chlorine and bromine content
Measurements were made at SGS Taiwan (Kaohsiung) according to the BS EN 14582 method by requesting the SGS Far East Limited Green Testing Center.

(6) Adhesive gas component amount About 1.5 g of the resin composition is precisely weighed in a glass sample tube having a diameter of 18 mm, a depth of 75 mm, and a wall thickness of 1 mm. After being inserted into an aluminum block heater (equipment: model number AL-331, manufactured by Synics Corporation, having 12 cylindrical grooves having a diameter of 18.3 mm and a depth of 70 mm), the glass sample tube is opened at the opening. Put a precisely weighed glass plate. After 3 hours, the glass plate is removed and cooled to room temperature in a desiccator. This glass plate is weighed again, the amount of gas attached to the glass plate is determined from the difference from the original glass plate weight, the amount attached is divided by the amount of resin composition, and multiplied by 100 to give the gas per resin composition amount. The amount of deposits (%) was determined.

(7) Evaluation of optical axis stability The resin pellets are supplied to an injection molding machine (SG75-HIPRO · MIII) manufactured by Sumitomo-Nestal Co., which is set at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., and a molding lower limit pressure + 5 kgf / cm ^2. Injection molding was performed under gauge conditions to obtain an optical pickup model injection molded product 1 having the shape shown in FIG. A half mirror 2 is installed in the central cutout portion of the optical pickup model injection molded product 1, and a laser beam oscillated from a semiconductor laser autocollimator having a focal length of 200 mm, a wavelength of 650 nm, and an output of 0.3 mW is applied in a thermostatic chamber, The reflected laser beam was received by a CCD camera.

  Using the position of the reflected laser beam at 30 ° C. as the origin, the temperature was raised to 70 ° C. over 30 minutes, and the optical axis fluctuation value after being left for 30 minutes was measured. It can be said that the smaller this value, the better the environmental stability of the laser focus.

  FIG. 1 is a perspective view of an injection molded product in which a half mirror 2 is installed. The half mirror 2 is installed in a central cutout portion of the injection molded product 1. The laser light oscillated from the semiconductor laser autocollimator is incident on the surface of the half mirror 2 at a right angle and reflected.

[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 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, and had a melt viscosity of 100 Pa · s (320 ° C., shear rate of 1000 / s), a chloroform extraction amount of 0.43%, and a chlorine content of 1200 ppm.

[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 several times with 56000 g of ion-exchanged water, filtered, and 0.05 wt. The solution was washed with 70,000 g of acetic acid aqueous solution 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, and had a melt viscosity of 120 Pa · s (320 ° C., shear rate of 1000 / s), a chloroform extraction amount of 1.70%, and a chlorine content of 2800 ppm.

[Reference Example 3] Polymerization of PPS (PPS-3)
M3910 manufactured by Toray Industries, Inc. was treated in a hot air oven at 210 ° C. for 1 hour. The obtained PPS was a crosslinked type, and had a melt viscosity of 15 Pa · s (320 ° C., shear rate of 1000 / s), a chloroform extraction amount of 2.50%, and a chlorine content of 2800 ppm.

[Reference Example 4] Polymerization of PPS (PPS-4)
L2840 manufactured by Toray Industries, Inc. was treated in a hot air oven at 210 ° C. for 9 hours. The obtained PPS was a crosslinked type, and had a melt viscosity of 100 Pa · s (320 ° C., shear rate of 1000 / s), a chloroform extraction amount of 2.20%, and a chlorine content of 2500 ppm.

[Reference Example 5] Polymerization of PPS (PPS-5)
Toray Industries, Inc. L4230 was treated in a hot air oven at 210 ° C. for 2 hours. The obtained PPS was a crosslinked type, and had a melt viscosity of 15 Pa · s (320 ° C., shear rate of 1000 / s), a chloroform extraction amount of 2.50%, and a chlorine content of 4500 ppm.

  [Reference Example 6] Polymerization of PPS (PPS-6) In a 70 liter autoclave equipped with a stirrer and a bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2. 91 kg (69.80 mol), N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), and 10.5 kg of ion-exchanged water were charged, and about 3 hours to 245 ° C. through nitrogen at normal pressure. After gradually distilling off 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200 ° 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, 10.37 kg (70.52 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and a rate of 0.6 ° C./min with stirring at 240 rpm. The temperature was raised from 200 ° C to 270 ° C. After reacting at 270 ° C. for 60 minutes, the bottom plug valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer over 15 minutes while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of NMP. .

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

  The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and 2000 ppm of calcium acetate monohydrate was added. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

  The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS. The obtained PPS was linear, and had a melt viscosity of 15 Pa · s (320 ° C., shear rate of 1000 / s), a chloroform extraction amount of 2.50%, and a chlorine content of 2700 ppm.

[Reference Example 7] Polymerization of PPS (PPS-7)
M3910 manufactured by Toray Industries, Inc. was treated in a hot air oven at 210 ° C. for 10 hours. The obtained PPS was a crosslinked type, and had a melt viscosity of 60 Pa · s (320 ° C., shear rate of 1000 / s), a chloroform extraction amount of 2.20%, and a chlorine content of 2900 ppm.

(B) Non-fibrous filler B-1: calcium carbonate KSS-1000 (D50 = 4.2μ) manufactured by Konpei Mining Co., Ltd. Specific gravity 2.7.

(C) Fibrous filler C-1: Glass fiber T747GH (average fiber diameter of 10 μm) manufactured by Asahi Fiber Glass Co., specific gravity 2.5.

(D) Amorphous resin D-1 having a glass transition temperature of 110 ° C. or higher: Polyphenylene ether YPX-100F (manufactured by Mitsubishi Engineering Plastics, glass transition temperature 205 ° C.).

[Examples 1-2, 4-6]
Each component shown in Table 1 is dry blended at the ratio shown in Table 1, and then melt-kneaded at a screw rotation speed of 250 rpm and a cylinder set temperature of 320 ° C. using a TEX44 type twin screw extruder manufactured by Nippon Steel Works, and a strand cutter. Pelletized. The pellets dried overnight at 120 ° C. were used for molding and evaluation.

[Comparative Examples 1-4]
Each component shown in Table 1 is dry blended at the ratio shown in Table 1, and then melt-kneaded at a screw rotation speed of 250 rpm and a cylinder set temperature of 320 ° C. using a TEX44 type twin screw extruder manufactured by Nippon Steel, Ltd., and a strand cutter Pelletized. The pellets dried overnight at 120 ° C. were used for molding and evaluation.

[Example 3]
Each component shown in Table 1 is dry blended at the ratio shown in Table 1, and then melt-kneaded at a screw rotation speed of 350 rpm and a cylinder set temperature of 320 ° C. using a TEX44 type twin screw extruder manufactured by Nippon Steel Works, and a strand cutter. Pelletized. The pellets dried overnight at 120 ° C. were used for molding and evaluation.

  In addition, the resin compositions of Examples 2 and 3 were used for the user, and optical pickup parts for both reproduction and recording were molded. At the beginning of molding, good products were obtained for both the molded products of Examples 2 and 3. However, since 1000 molded products were obtained, the composition of Example 3 had dimensional variations and no good products were obtained. As a result of disassembling the mold, it was found that mold vent clogging occurred.

  INDUSTRIAL APPLICABILITY The present invention is particularly suitably used for an optical pickup component comprising a polyphenylene sulfide resin composition having a low chlorine content, excellent melt fluidity, and excellent dimensional stability during repeated molding, and an injection molded product thereof.

Claims (7)

A polyphenylene sulfide resin composition comprising (A) a polyphenylene sulfide resin, (B) a non-fibrous filler and (C) a fibrous filler, wherein (B) the non-fibrous filler and (C) fibers The total amount of the fibrous filler is 200 parts by weight to 300 parts by weight with respect to 100 parts by weight of the resin component in the polyphenylene sulfide resin composition, and the content of (B) non-fibrous filler is (C) A polyphenylene sulfide resin composition having a content greater than that of the fibrous filler and a chlorine content of the polyphenylene sulfide resin composition of 900 ppm or less. 2. The polyphenylene sulfide resin composition according to claim 1, wherein 70% by weight or more of the resin component constituting the polyphenylene sulfide resin composition is (A) a polyphenylene sulfide resin. (A) 3 to 50 weight part of (D) amorphous resin with a glass transition temperature of 110 degreeC or more is mix | blended with respect to 100 weight part of polyphenylene sulfide resin, The any one of Claims 1-2 characterized by the above-mentioned. The polyphenylene sulfide resin composition described. Spiral flow length (flow when molding using a spiral flow mold of 1 mm thickness, cylinder temperature 320 ° C., mold temperature 140 ° C., injection speed 230 mm / sec, injection pressure 98 MPa, injection time 5 sec, cooling time 15 sec. 4. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the length is in the range of 50 mm to 120 mm. The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein an amount of an adhering gas component at 330 ° C for 3 hours is 0.06% by weight or less. An optical pick-up component obtained by injection molding the polyarylene sulfide resin composition according to any one of claims 1 to 5. An optical pickup component for both reproduction and recording, wherein the polyarylene sulfide resin composition according to any one of claims 1 to 5 is injection-molded.

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