JP2009122573A - Information transmission wiring connecting device, or constituent component of the device, and method for manufacturing the device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an information transmission wiring connecting device and its constituent components which comprise a polyphenylene sulfide resin composition, having highly superior dimensional accuracy. <P>SOLUTION: The information transmission wiring connection device or the constituent components of the device are made of a composition comprising (a) a polyphenylene sulfide resin and (b) a filler, with composition ratios of 1 to 60 vol% of the polyphenylene sulfide resin and 99 to 40 vol% of the filler, with respect to total 100 vol% of the both, into which (c) a substance that changes from a solid into a liquid or a gas, in a temperature range of 25 to 250°C is compounded by 0.1 to 30 parts by weight, with respect to 100 parts by weight of the total amount of the polyphenylene sulfide resin and the filler. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an information transmission wiring connecting device and a component thereof comprising a polyphenylene sulfide resin composition that is extremely excellent in molding processability and dimensional accuracy.

  With the progress of the advanced information society in recent years, the demand for wiring for transmitting information such as electrical signals and optical signals has been rapidly increasing, and the demand for wiring connection devices has also been greatly increased. In particular, optical communication with high speed and high information density is rapidly spreading from conventional telecommunication. An optical connector is usually used for connection of an optical fiber in optical communication, and the optical connector is composed of an optical connector positioning component such as a ferrule or a sleeve. Such optical connector components require a high degree of dimensional accuracy because it is necessary to position the optical fiber axes that are abutted with each other with a high degree of accuracy. Stability is also required. At the same time, since the optical connector is repeatedly attached and detached, the optical connector component parts are required to have sufficient mechanical strength, long-term durability, and high dimensional accuracy.

  On the other hand, polyphenylene sulfide (hereinafter abbreviated as PPS) resin has properties suitable for engineering plastics such as excellent heat resistance, barrier properties, chemical resistance, electrical insulation properties, and heat and humidity resistance, and is suitable for injection molding and extrusion molding. It is used for various electric / electronic parts, machine parts and automobile parts.

  The PPS resin is a resin that is relatively compatible with various fillers, and is often used by being highly filled with fillers. High dimensional stability is required for use in optical connector components, and for this purpose, ultra-high filler filling is an effective method. However, if the filler is filled in an extremely high amount, there is a problem that the fluidity is lowered and the injection moldability is impaired. Further, when the fluidity deteriorates, it is necessary to increase the filling pressure, which causes problems such as a drop in the detachability of the molded piece from the mold and a reduction in dimensional accuracy due to unstable filling pressure.

  Application of a PPS resin composition to an optical fiber member has been studied conventionally (Patent Documents 1 to 8 and the like). However, these are merely filled with a high amount of filler, and the present situation is that they cannot meet the demands for higher injection moldability and high dimensional stability that accompany recent technological advances.

On the other hand, as a technique for super-highly filling PPS, a technique of tableting PPS, a filler, and an additive and injection molding is known (Patent Documents 9 to 12, etc.). The idea of applying to components is not disclosed.
International Publication No. WO2002 / 083792 (Claims) JP 2003-138044 A (Claims) JP 2002-350680 A (Claims) JP 2001-264581 A (Claims) JP-A-6-299072 (Claims) JP 2000-204252 A (Claims) JP 2000-273304 A (Claims) JP 2001-174666 A (Claims) JP 2003-41128 A (Claims) JP 2003-41129 A (Claims) JP 2003-41130 A (Claims) Japanese Patent Laying-Open No. 2005-146124 (Claims)

  SUMMARY OF THE INVENTION An object of the present invention is to obtain an information transmission wiring connection device and a component part thereof composed of a polyphenylene sulfide resin composition having extremely excellent dimensional accuracy.

  As a result of investigations to solve the above problems, the present inventors have found that the composition ratio of (a) polyphenylene sulfide resin and (b) filler is 1 to 60% by volume of polyphenylene sulfide resin with respect to a total of 100% by volume of the filler. 99 to 40% by volume, and for 100 parts by weight of the total amount of polyphenylene sulfide resin and filler, (c) 0.1 to 30 specific substances that change from solid to liquid or gas in the temperature range of 25 to 250 ° C. Obtaining a tablet with a blended part by weight and injection molding it to obtain an information transmission wiring connection device and its component parts that are extremely excellent in moldability and dimensional stability, and find out that the above problems can be solved. The invention has been reached.

That is, the present invention
1. The composition ratio of (a) polyphenylene sulfide resin and (b) filler is 1 to 60% by volume of polyphenylene sulfide resin and 99 to 40% by volume of filler with respect to the total of 100% by volume of both, and the total amount of polyphenylene sulfide resin and filler For 100 parts by weight, (c) monohydric alcohol ester of fatty acid, fatty acid metal salt, monohydric alcohol ester of polybasic acid, fatty acid of polyhydric alcohol that changes from solid to liquid or gas in the temperature range of 25-250 ° C. 0.1 or more substances selected from esters, derivatives thereof, fatty acid esters of glycerin, silicone resins, phenolic compounds, benzophenone compounds, amide group-containing compounds, cyanurate compounds, phosphate esters and salts thereof Information consisting of a composition containing 30 parts by weight Reaches wiring connection device or component thereof,
2. (C) The information transmission wiring connecting device or the component thereof according to 1, wherein the melting point or softening point of the substance is 40 to 250 ° C.
3. The composition ratio of (a) polyphenylene sulfide resin and (b) filler is 1 to 2 in which (a) the polyphenylene sulfide resin is 5 to 50% by volume and (b) the filler is 95 to 50% by volume with respect to 100% by volume in total. The information transmission wiring connection device according to any of the above or a component thereof,
4). (B) The information transmission wiring connection device or the component thereof according to any one of 1 to 3, wherein at least a part of the filler is alumina.
5). 5. The information transmission wiring connection device or the component thereof has a through hole portion and / or a cylindrical hole, and the average roundness of the through hole portion and / or the cylindrical hole is 5% or less. Information transmission wiring connection device or its components,
6). Any one of 1 to 5 in which the information transmission wiring connecting device or the component thereof has a through-hole portion and / or a cylindrical hole, and the variation in roundness of the through-hole portion and / or the cylindrical hole is 10% or less. Information transmission wiring connection device or its components,
7). (A) polyphenylene sulfide resin, (b) filler and (c) monohydric alcohol ester of fatty acid, fatty acid metal salt, monohydric alcohol ester of polybasic acid, fatty acid ester of polyhydric alcohol, and derivatives thereof, fatty acid of glycerin A composition containing at least one substance selected from esters, silicone resins, phenolic compounds, benzophenone compounds, amide group-containing compounds, cyanurate compounds, phosphate esters and salts thereof is compression molded with a tableting machine. And then manufacturing the tablet, and injection molding the tablet, the information transmission wiring connection device according to any one of 1 to 6 or a method for manufacturing the component,
It is.

  According to the present invention, it is possible to obtain an information transmission wiring connecting device and its constituent parts which are made of a polyphenylene sulfide resin composition which is extremely excellent in dimensional accuracy and extremely small in dimensional accuracy between injection molding shots.

  Hereinafter, embodiments of the present invention will be described in detail.

(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.

  Although there is no restriction | limiting in particular in the melt viscosity of (a) PPS resin used by this invention, The one where the melt viscosity is low is preferable from the meaning which acquires the more outstanding fluidity | liquidity. For example, a range of 1 to 100 Pa · s (310 ° C., shear rate 1000 / s) is preferable, and a range of 2 to 80 Pa · s 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 310 degreeC and the shear rate of 1000 / s.

Hereinafter, a method for producing (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 aromas 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 (not necessarily an aromatic compound) is used as the polyhalogenated aromatic for the purpose of forming the end of the PPS resin to be produced or adjusting the polymerization reaction or molecular weight. Can be used in combination with a 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, alkali metal carboxylates are preferable as organic carboxylates, and lithium chloride is preferable as alkali metal chlorides. 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 molar ratio with respect to 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 the above (A) Conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol)]

[Recovery process]
In the method for producing (a) PPS resin used in the present invention, after the polymerization is completed, a solid is recovered from a polymerization reaction product containing a polymer, a solvent and the like. 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.

  In the present invention, the combination of (C) the polymer obtained by the method of quenching and (D) the method of obtaining the particulate polymer by slow cooling is a suitable method in terms of tablet formation. one of. The blend ratio at that time is not particularly limited, but a suitable range is (c) :( D) = 95: 5 to 50:50.

[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 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.

  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.

  However, the (a) PPS resin used in the present invention is preferably a substantially linear PPS that is not subjected to high molecular weight by thermal oxidation cross-linking treatment in order to achieve the toughness target.

  Examples of suitable PPS products include L4230, M3910, M3102, M2900, M3088, M2888, and M2588 manufactured by Toray Industries, Inc.

(2) Filler The (b) inorganic filler used in the present invention includes fibrous or non-fibrous (plate-like, scale-like, granular, indeterminate shape, crushed product, etc.) fillers. Glass fiber, PAN-type or pitch-type carbon fiber, stainless steel fiber, metal fiber such as aluminum fiber or brass fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide Fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, barium strontium titanate whisker, aluminum borate whisker, silicon nitride whisker, zinc oxide whisker, etc., the type of glass fiber or carbon fiber is If it is generally used for resin reinforcement There is no limitation in particular, For example, it can select and use from a chopped strand, a milled fiber, etc. of a long fiber type or a short fiber type. The filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, a silane compound, a titanate compound, or an aluminum compound.

  Zinc oxide whiskers, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, calcium polyphosphate, graphite, metal powder, metal flakes as non-fibrous filler Examples thereof include metal ribbons, metal oxides (alumina, zinc oxide, titanium oxide, etc.), carbon powder, graphite, carbon flakes, scale-like carbon, and nanocarbon tubes. Moreover, silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, tin etc. can be illustrated as a specific example of the metal seed | species of metal powder, metal flakes, and a metal ribbon.

Also possible for non-fibrous fillers are surface treatment agents such as thermoplastic resins such as ethylene / vinyl acetate copolymers, thermosetting resins such as epoxy resins, silane compounds, titanate compounds, and aluminum compounds. It may be processed.
Among these, alumina, graphite or silica is preferable from the viewpoint of obtaining excellent moldability and dimensional stability, alumina and graphite are particularly preferable, and alumina is more preferable.

  In addition, for example, high heat conductive fillers are preferably used for applications that require high heat dissipation simultaneously. Specifically, metal powder, metal flakes, metal ribbons, metal fibers, metal oxides (alumina, zinc oxide, etc.) ), Carbon powder, graphite, PAN-based or pitch-based carbon fiber, carbon flake, scaly carbon, carbon nanotube, boron nitride, aluminum nitride, silicon nitride, silicon carbide and the like.

  Here, specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope) and ZnO (aluminum dope), and these include titanate, aluminum and silane. The surface treatment may be performed with the surface treatment agent.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, and the like based on the raw materials and the production method. The carbon powder that can be used in the present invention is not particularly limited in terms of its raw material and production method, and among them, acetylene black and furnace black are particularly preferably used. Further, as the carbon powder, various carbon powders having different characteristics such as particle diameter, surface area, DBP (dibutyl phthalate) oil absorption and ash content are manufactured and commercially available. The carbon powder that can be used in the present invention is not particularly limited with respect to these properties, but from the viewpoint of the balance between strength and electrical conductivity, the average primary particle size is 500 nm or less, particularly 5 to 100 nm, It is preferable that it exists in the range of 10-70 nm. The surface area (BET method) is preferably in the range of 10 m ² / g or more, more preferably 30 m ² / g or more. Furthermore, the DBP oil supply amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. Furthermore, it is preferable that the ash content is 0.5% or less, particularly 0.3% or less.

  Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminum, and silane. Moreover, it is also possible to use what was granulated in order to improve melt-kneading workability | operativity with resin.

  In the present invention, in order to achieve a balance between strength and fluidity at a high level, a combination of two or more fibrous and non-fibrous forms is also a preferred embodiment. Specifically, (b) one or more combinations selected from graphite and carbon fiber, glass fiber, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker and zinc oxide whisker, or (b) One or more combinations selected from alumina and carbon fiber, glass fiber, potassium titanate whisker, barium titanate whisker, aluminum borate whisker and silicon nitride whisker, or (c) graphite and carbon fiber, zinc oxide whisker and / or One or more combinations selected from non-fibrous fillers can be mentioned.

  In the present invention, the ratio of (a) thermoplastic resin to (b) filler is blended from the viewpoint of balance between lockability, injection moldability and dimensional stability, and (a) polyphenylene sulfide resin and (b) (A) 1 to 60% by volume of polyphenylene sulfide resin and (b) 99 to 40% by volume of filler, preferably (a) 5 to 55% by volume of polyphenylene sulfide resin, (b) ) Filler 95 to 45% by volume, more preferably (a) 5 to 50% by volume of polyphenylene sulfide resin, (b) 95 to 50% by volume of inorganic filler, and further (a) 10 to 50% by volume of polyphenylene sulfide resin, ( b) 90-50% by weight of filler is preferred.

  Further, when using a fibrous filler and a non-fibrous filler in combination, it is preferable that the non-fibrous filler is more than the fibrous filler in terms of the balance of molding fluidity and mechanical strength, specifically, It is preferably 2% by volume or more, more preferably 5% by volume or more.

  In the present invention, since the filler is highly filled, the lubricity between the fillers is important, and the particle size distribution for that purpose is ideal to have a uniform distribution over a wide particle size range, a so-called trapezoidal distribution. However, it is also preferable to have a multimodal particle size distribution such as bimodal and trimodal having two mountain distributions. Furthermore, in the case of multimodality, it is preferable that the peak on the coarse particle side is higher in terms of strength improvement.

  In order to make the filler used in the present invention have such a particle size distribution as described above, for example, two or more fillers having different average particle diameters or particle size distributions are used together, or those fractionated for each particle size by sieving, A method of mixing to obtain a desired particle size distribution, a method of using two or more fillers having different particle size distributions, and the like can be employed.

  The particle size distribution is indicated by a curve in which the amount of particles (%) in each particle size interval measured by a laser diffraction particle size distribution measuring device is plotted. The cumulative particle size distribution curve is equal to or less than the particle size. It is a curve obtained by accumulating the amount of particles (%), and represents the percentage of the total amount of particles having a specific particle diameter or less.

  The present invention also includes (c) a monohydric alcohol of a fatty acid that changes from solid to liquid or gas in the temperature range of 25 to 250 ° C. from the viewpoint of imparting filler interface and improving flowability during processing. Esters, fatty acid metal salts, monobasic alcohol esters of polybasic acids, fatty acid esters of polyhydric alcohols and their derivatives, fatty acid esters of glycerin, silicone resins, phenolic compounds, benzophenone compounds, amide group-containing compounds, cyanurate compounds It is necessary to add at least one substance selected from phosphate esters and salts thereof.

  Such additives include sodium stearate, calcium stearate, magnesium stearate, potassium stearate, lithium stearate, zinc stearate, barium stearate, aluminum stearate, sodium montanate, calcium montanate, magnesium montanate Fatty acid metal salts such as potassium montanate, lithium montanate, zinc montanate, barium montanate, aluminum montanate, and derivatives thereof, such as methyl stearate and stearate stearate, stearates, myristyl myristate, etc. Methacrylic acid esters such as myristic acid ester, montanic acid ester, behenyl methacrylate, pentaerythritol monostearate, 2-ethylhexanoic acid , Palm fatty acid methyl, methyl laurate, isopropyl myristate, octyldodecyl myristate, butyl stearate, 2-ethylhexyl stearate, isotridecyl stearate, methyl caprate, methyl myristate, methyl oleate, octyl oleate, olein Monohydric alcohol esters and derivatives of fatty acids such as lauryl oleate, oleyl oleate, 2-ethylhexyl oleate, decyl oleate, octidodecyl oleate, isobutyl oleate, distearyl phthalate, distearyl trimellitic acid, adipic acid Dimethyl, dioleyl adipate, adipate ester, ditridecyl phthalate, diisobutyl adipate, diisodecyl adipate, dibutyl glycol adipate, 2-phthalate Fatty acid esters of polybasic acids such as tilhexyl, diisononyl phthalate, didecyl phthalate, tri-2-ethylhexyl trimellitic acid, triisodecyl trimellitic acid, stearic acid monoglyceride, palmitic acid / stearic acid monoglyceride, stearic acid mono-diglyceride, stearic acid -Fatty acid esters of glycerin such as oleic acid, mono-diglyceride, behenic acid monoglyceride and their derivatives, sorbitan tristearate, sorbitan monostearate, sorbitan monostearate, sorbitan distearate, sorbitan monopalmitate, sorbitan monostearate Rate, polyethylene glycol monostearate, polyethylene glycol distearate, polypropylene glycol monostearate Rate, pentaerythritol monostearate, sorbitan monolaurate, sorbitan trioleate, sorbitan monooleate, sorbitan sexolate, sorbitan monolaurate, polyoxymethylene sorbitan monolaurate, polyoxymethylene sorbitan monopalinate, polyoxymethylene sorbitan Monostearate, polyoxymethylene sorbitan monooleate, polyoxymethylene sorbitan tetraoleate, polyethylene glycol, polyethylene glycol monolaurate, polyethylene glycol monooleate, polyoxyethylene bisphenol A laurate, pentaerythritol, pentaerythritol monooleate, etc. Fatty acid esters of polyhydric alcohols and their derivatives, ethylene Amide group-containing compounds such as stearylamide, ethylenebisoleylamide, stearyl erucamide, novolak phenyl type, bisphenol type monofunctional and polyfunctional epoxy compounds, aromatic phosphate esters such as triphenyl phosphate, aromatic condensed phosphoric acid Examples thereof include phosphate esters such as esters.

  Among these, phosphate esters are preferred from the viewpoint of obtaining excellent injection moldability. Examples of such suitable phosphoric acid esters include monoesters, diesters, triesters, and tetraesters of phosphoric acid, and particularly preferred are those represented by the following formula (1).

  First, the structure of the phosphate ester represented by the formula (1) will be described. In the formula of the formula (1), n is an integer of 0 or more, preferably 0 to 10, particularly preferably 0 to 5. The upper limit is preferably 40 or less from the viewpoint of dispersibility.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

In the formula (1), R ^{3 to} R ¹⁰ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-pentyl group, Among them, hydrogen, methyl group, and ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with an organic residue containing no halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group.

  Specific examples of such phosphate esters are selected from Daihachi Chemical Co., Ltd. PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR-747, TCP, TXP, CDP. One or more selected from the group consisting of PX-200, TPP, CR-733S, CR-741, and CR-747, particularly preferably PX-200. , CR-733S and CR-741 can be used, but PX-200 is most preferable.

  In the present invention, (c) monohydric alcohol ester of fatty acid, fatty acid metal salt, monohydric alcohol ester of polybasic acid, fatty acid ester of polyhydric alcohol, and derivatives thereof, fatty acid ester of glycerin, silicone resin, phenolic compound , A benzophenone compound, an amide group-containing compound, a cyanurate compound, a phosphate ester and a salt thereof may be any one kind or a mixture of two or more kinds. The amount of such an additive is 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 100 parts by weight of the total amount of (a) polyphenylene sulfide resin and (b) filler. Is selected in the range of 1 to 5 parts by weight.

  (C) fatty acid monohydric alcohol ester, fatty acid metal salt, polybasic acid monohydric alcohol ester, polyhydric alcohol fatty acid ester, and derivatives thereof, glycerin fatty acid ester, silicone resin, phenolic compound, benzophenone compound The addition amount of at least one compound selected from amide group-containing compounds, cyanurate compounds, phosphate esters and salts thereof is 30 weights per 100 weight parts of the total amount of (a) polyphenylene sulfide resin and (b) filler. When the amount is more than the part, the surface of the obtained molded product bleeds out, thereby causing peeling of the interface between the polyphenylene sulfide resin and the filler, and the mechanical properties tend to be lowered. (C) fatty acid monohydric alcohol ester, fatty acid metal salt, polybasic acid monohydric alcohol ester, polyhydric alcohol fatty acid ester, and derivatives thereof, glycerin fatty acid ester, silicone resin, phenolic compound, benzophenone series The addition amount of at least one compound selected from a compound, an amide group-containing compound, a cyanurate compound, a phosphate ester and a salt thereof is 100 parts by weight in total of (a) polyphenylene sulfide resin and (b) filler. If it is less than 0.1, injection molding processability is remarkably inferior.

  In the highly filled polyphenylene sulfide resin composition in the present invention, other components such as antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based, and the like) can be used as long as the effects of the present invention are not impaired. Substitutes, etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), release agents and lubricants (montanic acid and its metal salts, esters, half esters, 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- Tilbenzenesulfonamide, 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 type Amphoteric antistatic agents, etc.), flame retardants (eg red phosphorus, phosphate esters, melamine cyanurate, magnesium hydroxide, aluminum hydroxide hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated Polycarbonate, brominated epoxy resin or a combination of these brominated flame retardants and antimony trioxide, etc.) can be added.

  Furthermore, a resin other than PPS may be added and blended in the highly filled polyphenylene sulfide resin composition of the present invention as long as the effects of the present invention are not impaired. Specific examples thereof include polyetherimide, polyethersulfone, polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, Examples include polyether ketone resins, polythioether ketone resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, tetrafluoropolyethylene resins, and epoxy group-containing polyolefin copolymers. Furthermore, the highly filled polyphenylene sulfide resin composition of the present invention includes an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto for the purpose of improving mechanical strength, toughness and the like within a range not impairing the effects of the present invention. An alkoxysilane having at least one functional group selected from a group and a ureido 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.

  A suitable addition amount of the silane compound is selected in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin.

  In the present invention, an information transmission wiring connection device having excellent dimensional accuracy or a component thereof can be obtained by injection molding after filling the highly filled polyphenylene sulfide resin composition into a tablet. As a manufacturing method of this tablet, the method of compressing and molding the raw material (filler highly filled polyphenylene sulfide resin composition) can be mentioned. In particular, the method of tableting the raw material by compression with a tableting machine is preferred from the viewpoint of the quality stability of the obtained composition.

In the present invention, a tablet refers to a granular material obtained by compacting a raw material containing a powdery raw material in a solid phase. Such a tablet can be obtained by compression molding a raw material containing a powdery raw material in a solid phase. Can do. In the above description, the solid phase state means that the polyphenylene sulfide resin component contained in the raw material is not melted.
Examples of the compression molding include a method using a molding machine having a compression roll such as a rotary type, single shot type, double type, triple type tablet press or briquette machine. Among them, a tablet press from the viewpoint of obtaining a stable tablet. The method using is preferable.

  As a specific method of tableting, for example, polyphenylene sulfide resin powder and filler are uniformly blended in a solid phase using a Banbury mixer, kneader, roll, single-screw or twin-screw extruder, and tableting machine or compression is used. A method of forming a tablet with a molding machine having a roll is mentioned.

Also, polyphenylene sulfide resin and filler are dry-blended in advance using a Banbury mixer, kneader, or roll, or not dry blended, and once melt-kneaded using a single or twin screw extruder, etc., cooled and pulverized After making it into a powder form, it is also possible to form tablets using a tableting machine or a molding machine having a compression roll. In this case, the polyphenylene sulfide resin component to be used for melt kneading is not particularly limited as long as it can be melt kneaded, either in the form of powder or pellets. A pulverized product is preferred. In addition, when the composition previously melt-kneaded using a single-screw or twin-screw extruder is powdered, if the amount of inorganic filler used is large, the fluidity deteriorates, so the pellet cannot be extruded from the die. However, in this case, as described in JP-A-8-1663, kneading and extrusion can be performed with the head portion of the extruder being opened. When the amount of the filler is large, a flaky composition may be obtained. In the present invention, if necessary, the pellet or flake composition obtained by melt-kneading in advance by these methods can be cooled and pulverized to form a powder and then tableted. In addition, these methods can be combined into tablets. That is, a raw material selected from the following (A) to (D) can be adjusted to have a desired content and tableted.
(A) (a) PPS resin (b) (b) Filler (c) Any one or more of (c) components (d) Two or more selected from (a) to (c) components, A composition obtained by melt-kneading a component that essentially comprises the component (a) or (b), preferably a lump and a powder thereof.

  Among the above methods, the process is simple, and the mixture obtained by uniformly blending the raw materials (a) and (b) and the raw material (c) in a solid phase state with a tableting machine or a molding machine having a compression roll. A method of making a tablet is preferred.

  As the powders of the above components (a) and (c), those available in powder form such as polyphenylene sulfide resin may be used. It can also be obtained by pulverizing the pellets at room temperature or by freeze pulverization. The freeze pulverization can be carried out by using a generally known hammer type pulverizer, cutter type pulverizer, or stone mill type pulverizer after being frozen with dry ice or liquid nitrogen. As the polyphenylene sulfide resin powder used in the present invention, the particle size when measured based on the laser diffraction particle size distribution measurement method is used in order to make the composition uniform between the obtained tablets and to improve the handleability of the obtained tablets. The number average particle size of the maximum major axis is preferably 1000 μm or less, more preferably 800 μm or less, and even more preferably 500 μm or less. In order to obtain a powder having such a particle size, the powder obtained by pulverization or the like may be appropriately sieved using a sieve having a desired size.

  The tablet shape of the highly filled polyphenylene sulfide resin composition of the present invention is, for example, cylindrical, elliptical columnar, frustoconical, spherical, elliptical when considering shape retention during transportation and easy crushability during molding. Examples include a spherical shape, an egg shape, a Macek shape, a disk shape, a cubic shape, and a prismatic shape. Among these, a cylindrical shape, an elliptical column shape, a truncated cone shape, a spherical shape, an elliptic spherical shape, an egg shape, and a Macek shape are preferable from the viewpoint of measurement stability during processing.

  Further, the tablet size of the tablet is preferably a bottom surface of 15 mm diameter or less × length of 20 mm or less, in particular, the maximum value of the bottom surface diameter or length (height) is preferably less than 15 mm, and the minimum value is 1 mm or more. It is preferable that As for the method of defining the maximum diameter and the minimum diameter with respect to those having a bottom surface that is not circular, when the maximum diameter of the circumscribed circle is specified, the maximum diameter is preferably less than 15 mm, 1 mm or more, more preferably 12 mm. Hereinafter, it is 1.5 mm or more.

  In addition, in order to keep the shape stable during transportation, the compression fracture strength value (crush strength value) when pressure is applied perpendicularly to the side of the tableting surface of the tablet or the compression surface of the compression roll, Preferably it is 5-100N, More preferably, it is 15-80N. As a method for obtaining a preferable crushing strength value, for example, it is most dependent on the raw material composition. By adding the component (c) or in the tableting process, the raw material is supplied uniformly to the raw material supply pocket, compression High by reducing the number of rotations of the roll and extending the pressurization time of the material on the compression roll, using a feed screw in the hopper, and effective deaeration and pre-compression before roll compression with the screw. Tablet density is obtained and high crushing strength is obtained. The crushing strength value is measured by placing a tablet on a strain gauge such as a load cell, and lowering the indenter at a low speed (preferably 0.1 to 2.0 mm / sec), and straining the tablet at the time of compressive fracture. A method of measuring the pressure indicated by the gauge can be used.

  As the molding method for molding the information transmission wiring connection device and its constituent parts using the highly filled resin composition tablet of the present invention, an injection molding method is selected from the viewpoints of benign formation and economy. Moreover, when it has a welding part, it is possible to use general welding methods, such as a hot plate, a vibration, an ultrasonic wave, and a laser.

  The molded product obtained by the present invention has exceptionally excellent dimensional stability, and is suitably used for wiring connection parts in telecommunications and optical communications by taking advantage of the characteristics. In particular, it can be suitably used for optical connector components for connecting optical fibers, for example, optical connector components such as ferrules and sleeves.

  Such optical connector components need to be positioned with high accuracy between the optical fiber axes, so that high roundness is required, and it is necessary to be able to stably mold it. Therefore, when the optical connector component of the present invention has a through-hole part and / or a cylindrical hole, the average roundness of the through-hole and / or cylindrical hole part is preferably 5% or less, preferably 4% or less, More preferably, it is 3% or less. Further, the variation in roundness of the through hole and / or the cylindrical hole is preferably 10% or less, more preferably 8% or less, and even more preferably 7% or less.

The roundness is determined in accordance with JIS B0621. That is, the roundness is obtained when the interval between two concentric circles is minimized when the circular shape (D) 1 mm inside from the entrance of the through hole and / or the cylindrical hole is sandwiched between two concentric geometric circles. , Defined by the radius difference (F) between the two circles. Roundness means the average value (Eave.) Of the inner concentric diameter (Ea) and the outer concentric diameter (Eb).
Eave. = (Ea + Eb) / 2
It is defined as the ratio of the radius difference (F) to the value, that is, the value obtained by the following equation.
Roundness (%) = F (μm) / Eave. (Μm) × 100

The average roundness is defined as an average value obtained by continuously injection-molding a connector component having a through-hole and / or a cylindrical hole, and obtaining the roundness of each connector component. It means that the smaller the average roundness, the higher the roundness and the smaller the round-to-shot variation.
Variation of roundness of the through-hole and / or cylindrical hole portion A connector component having a through-hole portion is continuously shot by 50 shots to obtain the roundness of each connector component, and the maximum value (Fmax) among them. And the minimum value (Fmin) is defined as the ratio of the diameter (Eb) of the concentric circles to the average value (Eave.).
Variation in roundness (%) = (Fmax−Fmin) / Eave. × 100

  If this value is small, it means that particularly large shot-to-shot variation is small and the yield is high.

  The present invention will be described more specifically with reference to the following examples.

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

Evaluation method (1) Evaluation of average roundness: A roundness was determined according to JIS B0621 using a Nikon stereo microscope. The roundness is the difference in radius between two circles when the circular shape (D) inside the entrance of the through hole is sandwiched between two concentric geometric circles and the interval between the two concentric circles is minimized (F ). Roundness means the average value (Eave.) Of the inner concentric diameter (Ea) and the outer concentric diameter (Eb).
Eave. = (Ea + Eb) / 2
The ratio of the difference in radius (F) with respect to, that is, the following equation.
Roundness (%) = F (μm) / Eave. (Μm) × 100
For the average roundness, a ferrule having a through hole was continuously injected by 50 shots (the first 10 shots were discarded), the roundness of the ferrule was determined, and the average value was determined. It means that the smaller the average roundness, the higher the roundness and the smaller the roundness variation between shots.
The evaluation sample was molded using a horizontal injection molding machine (resin temperature: 330 ° C., mold temperature: 150 ° C.) with a mold 30t, and a four-core ferrule (dimensions of about 6 mm × 8 mm × as shown in FIGS. 2 and 3). 2.5 mm) was obtained. At this time, the diameter of the guide hole formed in the ferrule was 700 μm. The above evaluation was performed on this ferrule.

(2) Evaluation of variation in roundness: 50 shots of ferrules having through holes are continuously injection-molded (the first 10 shots are discarded), and the roundness of each ferrule is obtained by the same method as the average roundness, The difference between the maximum value (Fmax) and the minimum value (Fmin) was divided by the average value (Eave.) Of concentric circle diameters (Eb).
Variation in roundness (%) = (Fmax−Fmin) / Eave. × 100
If this value is small, it means that particularly large shot-to-shot variation is small and the yield is high.

(3) Fluidity Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.) (resin temperature 330 ° C., mold temperature 150 ° C.), a 100 × 100 × 3 mm thick (film gate) corner forming product can be filled. The minimum pressure was measured.

(4) Bending strength Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.) (resin temperature 330 ° C., mold temperature 150 ° C.), a 100 × 100 × 3 mm thick (film gate) corner forming product is minimum pressure + 5 MPa Then, two sheets were cut from the center in the flow direction to a width of 12.7 mm, and the bending strength was measured according to ASTM D790.

Reference Example 1 (a) Polyphenylene sulfide resin PPS-1 (linear type): M3910 (manufactured by Toray Industries, Inc.) was pulverized with a sample mill (SK-M type, manufactured by Kyoritsu Riko Co., Ltd.) and passed through a sieve to 60 mesh pass Then, classification was performed with 150 mesh on to obtain a number average particle size of 200 μm.
PPS-2 (Linear type): M2888 (manufactured by Toray Industries, Inc.) is pulverized with a sample mill (SK-M type, manufactured by Kyoritsu Riko Co., Ltd.) and classified by a sieve with 16 mesh pass and 32 mesh on. An average particle size of 800 μm was obtained. In the above, the number average particle size was measured using a laser diffraction particle size distribution measuring device manufactured by Shimadzu Corporation.

Reference Example 2 (b) Filler alumina (Al-1): EA-10 (manufactured by Sumitomo Chemical Co., Ltd.) Average particle size: 17 μm
Alumina (Al-2): Al-32B (manufactured by Sumitomo Chemical) Average particle size 2.9 μm
Glass fiber (GF): EPDM70M10A (fibrous filler, manufactured by NEC Glass)
Graphite (KS): KS-75 (scaly filler, manufactured by Timcal Japan)
Silica particles (S-1): fused silica particles having an average particle size of 0.5 μm (manufactured by Izumi Tech, SCM QZ fused)
Silica particles (S-2): fused silica particles having an average particle size of 5 μm (manufactured by Izumi Tech Co., Ltd.)
Zinc oxide whisker (S-3): Panatetra manufactured by Matsushita Amtec. It has a tetrapot shape, and each needle-like portion extending from the center has an average length of 15 μm and an average diameter of 2 μm.
In addition, the filler size in the table | surface mentioned later represents that it did not remain on a sieve, when a 500-g sample was taken and classified using the sieve of the roughness corresponding to the size.

Reference Example 3 (c) Substance BPD: Polyoxyethylene bisphenol A lauric acid ester “Exepal” BP-DL (manufactured by Kao) Viscosity at 25 ° C. 280 mPa · s
MAR: Tetratridecyl-4,4′-butylidenebis- (3-methyl-6-tert-butylphenol) -di-phosphite “MARK” 260 (manufactured by Adeka Argus) 1100 mPa · s viscosity at 25 ° C.
DBP: Dibutyl phthalate DBP (manufactured by Daihachi Chemical Co., Ltd.), viscosity at 25 ° C., 16 mPa · s
Phosphoric acid ester PX: PX-200 (Powdered aromatic condensed phosphoric acid ester, CAS No. 139189-30-3, manufactured by Daihachi Chemical Industry Co., Ltd.) (using 42 mesh pass through sieve). Melting point 95 ° C.

Examples 1-9
A predetermined amount shown in Table 1 was blended with (a) PPS resin in Reference Example 1, (b) filler shown in Reference Example 2 and (c) substance shown in Reference Example 3 in a ribbon blender, and a rotary manufactured by Tsukishima Kikai A tablet having a diameter of 10 mm and a length of 5 mm was obtained using a tableting machine. Then, after drying for 3 hours with a 140 ° C. hot air dryer, molding and evaluation were performed.

Comparative Examples 1-2
A predetermined amount shown in Table 1 was blended with (a) PPS resin in Reference Example 1, (b) filler shown in Reference Example 2 and (c) substance shown in Reference Example 3 in a ribbon blender, and a rotary manufactured by Tsukishima Kikai Tablets with a diameter of 10 mm and a length of 5 mm were obtained using a tableting machine. Then, after drying for 3 hours with a 140 ° C. hot air dryer, molding and evaluation were performed.

Comparative Examples 3-4
(A) PPS resin in Reference Example 1, (b) Filler shown in Reference Example 2 This mixture is supplied to a biaxial extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.) and melt-kneaded to obtain a pellet-shaped resin composition. Obtained. Then, after drying for 3 hours with a 140 ° C. hot air dryer, molding and evaluation were performed.

  As can be seen from Tables 1 and 2, the ferrules obtained using this tablet have excellent injection moldability, small variations in average roundness and roundness, and high-dimensional precision ferrules can be obtained with good reproducibility. I understand.

  Since the PPS resin composition of the present invention is extremely excellent in toughness, it is particularly useful for extrusion molding applications such as films and fibers in addition to injection molding applications. In addition, taking advantage of this feature, it is also suitable for general equipment, automobile pipes, structures such as cases, and metal insert molded articles for electrical and electronic use.

It is explanatory drawing of the parameter which defines roundness. It is a perspective view which shows the state before the coupling | bonding of the MT optical connector which applies the ferrule as an optical fiber positioning component. It is a perspective view which shows the state after the coupling | bonding of the MT optical connector which applies the ferrule as an optical fiber positioning component. It is a perspective view which shows the MPO optical connector which applies the ferrule as an optical fiber positioning component. FIG. 5 is an enlarged perspective view showing the ferrule of FIG.

Explanation of symbols

3, 16 ... Ferrule.

Claims (7)

The composition ratio of (a) polyphenylene sulfide resin and (b) filler is 1 to 60% by volume of polyphenylene sulfide resin and 99 to 40% by volume of filler with respect to 100% by volume in total, and the total amount of polyphenylene sulfide resin and filler For 100 parts by weight, (c) monohydric alcohol ester of fatty acid, fatty acid metal salt, monohydric alcohol ester of polybasic acid, fatty acid of polyhydric alcohol that changes from solid to liquid or gas in the temperature range of 25-250 ° C. 0.1 or more substances selected from esters and derivatives thereof, fatty acid esters of glycerin, silicone resins, phenolic compounds, benzophenone compounds, amide group-containing compounds, cyanurate compounds, phosphate esters and salts thereof Information consisting of a composition containing 30 parts by weight It reaches wiring connection device or component thereof. (C) Melting | fusing point or softening point of a substance is 40-250 degreeC, The information transmission wiring connection apparatus or its component of Claim 1 characterized by the above-mentioned. 2. The composition ratio of (a) polyphenylene sulfide resin and (b) filler is (a) 5-50% by volume of polyphenylene sulfide resin and (b) 95-50% by volume of filler with respect to a total of 100% by volume of both. The information transmission wiring connection device according to any one of -2 or a component thereof. (B) At least one part of a filler is an alumina, The information transmission wiring connection apparatus in any one of Claims 1-3, or its component. The information transmission wiring connecting device or its component parts have a through hole and / or a cylindrical hole, and the average roundness of the through hole and / or the cylindrical hole is 5% or less. The information transmission wiring connection device or its component parts described. The information transmission wiring connecting device or its component parts have a through hole portion and / or a cylindrical hole, and the roundness variation of the through hole portion and / or the cylindrical hole is 10% or less. Or an information transmission wiring connecting device or a component thereof. (A) polyphenylene sulfide resin, (b) filler and (c) fatty acid monohydric alcohol ester, fatty acid metal salt, polybasic acid monohydric alcohol ester, polyhydric alcohol fatty acid ester, and derivatives thereof, glycerin fatty acid Compression molding of a composition containing at least one substance selected from esters, silicone resins, phenolic compounds, benzophenone compounds, amide group-containing compounds, cyanurate compounds, phosphate esters and salts thereof with a tableting machine Then, the tablet is manufactured, and the tablet is injection-molded. The information transmission wiring connection device according to any one of claims 1 to 6, or the manufacturing method of the component part.

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