JP2016188289A - Automobile cooling module comprising polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an automobile cooling module obtained by injection-molding a polyphenylene sulfide resin composition excellent in dimensional stability, thermal shock resistance and antifreeze liquid resistance.SOLUTION: An automobile cooling module is obtained by injection-molding a polyphenylene sulfide resin composition formed by blending, with respect to (A) a 100 pts.wt polyphenylene sulfide resin, (B-1) a 1-4 pts.wt olefinic copolymer having a glycidyl group, (B-2) a 1-4 pts.wt olefinic copolymer not having a polar functional group and (C) a 150-250 pts.wt inorganic filler.SELECTED DRAWING: None

Description

  The present invention provides an automobile cooling module that is injection-molded with a polyphenylene sulfide resin composition that is excellent in dimensional stability, cold shock resistance and antifreeze resistance.

  Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has a good balance of rigidity, heat resistance, hot water resistance, chemical resistance and molding processability, so it is widely used in electrical and electronic parts, water-borne parts and automobile parts. It is used.

  Attempts have been made to apply the PPS resin moldings to automobile cooling parts by taking advantage of the excellent properties of such PPS resins.

  The antifreeze containing glycols flows in contact with the inner wall of automobile cooling parts, which is low when the engine is started, but gradually increases over time.The flow of antifreeze and the flow rate control require a thermostat. When the antifreeze reaches a high temperature, the wax inside the thermostat gradually dissolves and swells, thereby opening the valve and forming the antifreeze flow path.

  In recent years, a method of controlling the flow rate and flow path with an electric valve has been proposed from this thermostat. In this system, the valve is electrically opened and closed to form an antifreeze liquid flow path so as to achieve an optimum temperature environment. Thus, by controlling the flow rate and flow path, for example, when starting the engine, the valve gradually opens in the thermostat and the flow path is formed before reaching the optimum temperature, so the engine has been cooled. In the system, the valve can be controlled electrically and the flow path can be quickly switched, so that the engine environmental temperature can be raised quickly, and the environmental temperature around the engine can be kept optimal. . Thus, since the fuel consumption is improved, it is expected that the fuel module can be an important and useful cooling module that meets the demand for reducing GHG emissions.

  By the way, for example, Patent Documents 1 and 2 disclose compositions in which an olefin copolymer and an inorganic filler are blended with a PPS resin for the purpose of exhibiting resistance to thermal shock.

    Patent Documents 3 and 4 describe compositions in which an olefin copolymer and an inorganic filler are blended with a PPS resin for the purpose of providing an optimal material for engine cooling system parts.

  Furthermore, in Patent Document 5, an olefin copolymer is blended for the purpose of improving dimensional stability, relaxing stress concentration due to volume shrinkage, and suppressing cracks in the resin part, and adding PPS resin. A foamed composition is described.

JP 2008-075049 A International Publication No. 2011/070968 JP 2006-036824 A JP 2006-036833 A JP2013-092089A

  However, in Patent Documents 1 and 2, although the application to engine cooling system parts is described as an example of use, the amount of the olefin copolymer is large and the dimensional stability is insufficient. The antifreeze resistance is also insufficient. In Patent Documents 3 and 4, although there is a description regarding antifreeze resistance, Patent Document 3 has a small amount of inorganic filler, while Patent Document 4 has a large amount of olefin copolymer and has dimensions. Stability is insufficient. Furthermore, the method of expressing dimensional stability and thermal shock resistance by foaming in Patent Document 5 is disadvantageous in achieving high strength and high rigidity, which are the characteristics of PPS resin, and is an automobile cooling module that is the object of the present invention. It is a technique not suitable for obtaining.

  The present invention provides an automobile cooling module that is injection-molded with a PPS resin composition that is excellent in dimensional stability, cold shock resistance, and antifreeze resistance.

  In recent years, the need for space saving has become stronger with the increase in the number of components mounted. For this reason, the cooling system parts have been downsized, and development has shifted to a module in which a plurality of parts are combined and a plurality of functions are integrated. Along with this, the shape becomes more complicated, and thus it is necessary to have better thermal shock resistance than ever before.

  In addition, in the method of controlling the flow rate and flow path with an electric valve, more accurate flow rate and flow path control is possible. However, because of the complicated shape, resin shrinkage, inorganic filler (for example, glass) The slight dimensional change due to the orientation of the fibers) and the absorption of the antifreeze liquid may cause gaps in the module, which may cause disorder in the control of the flow rate and the flow path and liquid leakage into the engine room.

  Therefore, the automobile cooling module is not only resistant to antifreeze to withstand antifreeze at high temperatures, but also does not crack due to repeated cold shock, and is dimensioned for accurate flow rate and flow path control. Stability is also required.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.

That is, the present invention provides the following.
(1) (A-1) 1 to 4 parts by weight of an olefin copolymer having a glycidyl group with respect to 100 parts by weight of a polyphenylene sulfide resin, (B-2) an olefin copolymer having no polar functional group A cooling module for automobiles formed by injection-molding a polyphenylene sulfide resin composition comprising 1 to 4 parts by weight of a coalescent and (C) 150 to 250 parts by weight of an inorganic filler.
(2) The automotive cooling module according to (1), wherein the amount of (C-3) mica contained in the polyphenylene sulfide resin composition is less than 5 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin.
(3) The amount of gas generated when the polyphenylene sulfide resin is (a) heated and melted under vacuum at 320 ° C. for 2 hours is 0.3% by weight or less, and (b) the amount of ash when incinerated at 550 ° C. 0.3% by weight or less, (c) 4% by weight of residue when melted in 20-fold weight of 1-chloronaphthalene at 250 ° C. for 5 minutes and filtered under pressure with a PTFE membrane filter having a pore size of 1 μm The automotive cooling module according to (1) or (2), which is a polyphenylene sulfide resin as described below.
(4) The automobile cooling module according to any one of (1) to (3), wherein the automobile cooling module includes a housing, a valve, and at least three or more pipes.
(5) The automobile cooling module according to (4), wherein a flow rate and a flow path of the antifreeze liquid flowing inside the housing of the automobile cooling module are controlled by opening and closing a valve included in the housing.

  The present invention has found that a PPS resin composition having a specific composition has an unknown characteristic that both excellent dimensional stability and high thermal shock resistance and high antifreeze resistance are obtained. It has been found that injection molding of a PPS resin composition is suitable for an automobile cooling module utilizing the characteristics. The PPS resin composition of the present invention is useful for an automobile cooling module, and particularly useful for an automobile cooling module having a small size and a complicated shape.

It is the schematic of the molded article used for evaluation of the dimensional stability in an Example. It is the schematic of the molded article used for evaluation of the cold-heat shock resistance in an Example.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  Since the automobile cooling module of the present invention requires heat resistance, it is composed of a polyphenylene sulfide resin (hereinafter referred to as PPS resin) composition.

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

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.

  The melt viscosity of the (A) PPS resin used in the present invention is in the range of 5 to 50 Pa · s (310 ° C., shear rate 1,216 / s) from the viewpoint of obtaining a resin composition having excellent melt fluidity. The range of 10 to 45 Pa · s is more preferable, and the range of 10 to 40 Pa · s is still more preferable. Two or more PPS resins having different melt viscosities may be used in combination. The melt viscosity of the (A) PPS resin in the present invention is a value measured using a capillograph manufactured by Toyo Seiki Co. under conditions of 310 ° C. and a shear rate of 1,216 / s.

  Although the manufacturing method of (A) PPS resin used for this invention is demonstrated below, if PPS which has the said structure and characteristic is obtained, it will not be limited to the following method. However, a method in which dichlorobenzene and a sulfur source are used as main monomers (90 mol% or more) and polymerization is performed in the presence of an aprotic polar solvent is most preferable in terms of production stability.

  Next, the contents of the polyhalogen aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used in the production 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 Preferably, p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3.5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5- Polychlorobenzene such as tetrachlorobenzene is preferably used, and p-dichlorobenzene is particularly preferably used. . Further, it is possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but a p-dihalogenated aromatic compound represented by p-dichlorobenzene may be used as a main component. preferable.

  The polyhalogenated aromatic compound is used in an amount of 0.8 to 1.023 mol, preferably 0.8 to 1 mol of the sulfidizing agent from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing and low oligomer elution. 1.020 mol, and in the sense of achieving both a degree of polymerization useful for the present invention and low oligomer properties, a range of 0.9 to 1.015 mol is useful. In the case of the above range, a PPS resin in which the above-described chloroform extraction amount is in a preferable range can be obtained.

[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 sulfidizing agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.90 to 1 per mol of the alkali metal hydrosulfide. A range of 50 moles, preferably 0.90 to 1.30 moles, and more preferably 0.95 to 1.20 moles 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. Examples of the monohalogenated compound include monohalogenated benzene, monohalogenated naphthalene, monohalogenated anthracene, monohalogenated compounds containing two or more benzene rings, and monohalogenated heterocyclic compounds. Of these, monohalogenated benzene is preferable from the viewpoint of economy. It is also possible to use a combination of two or more different monohalogenated compounds.

[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 preferred, and sodium and lithium carboxylates and / or water are particularly 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 0.01 mol with respect to 1 mol of the charged sulfidizing agent from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing and oligomer low elution. The range of ˜2 mol is preferable, and the range of 0.010 to 0.088 mol is preferable from the viewpoint of achieving both the degree of polymerization useful for the present invention and the low oligomer property. In the case of the above range, a PPS resin having the above-described melt viscosity in a preferable range can be obtained.

  In addition, when water is used as a polymerization aid, the addition amount is usually in the range of 0.3 to 15 mol with respect to 1 mol of the charged sulfidizing agent, and 0.6 to 10 in the sense of obtaining a higher degree of polymerization. The molar range 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 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, per 1 mol of the charged sulfidizing agent. It is preferable to use it. 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 production method of the (A) PPS resin used in the present invention will be specifically described in the order of the pre-process, the polymerization reaction process, the recovery process, and the post-treatment process.

[pre-process]
In the method for producing the (A) PPS resin used in the present invention, the sulfiding agent is usually used in the form of a hydrate. 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%.

Further, 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, the conversion rate = [PHA charge (mol) −PHA residual quantity (mol)] / [PHA charge (mol) -PHA excess (mole)]
(B) In cases other than (a) above, conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol)]

[Recovery process]
In the method for producing the (A) PPS resin used in the present invention, a solid is recovered from a polymerization reaction product containing a polymer, a solvent and the like after the completion of polymerization. Any known recovery method may be employed 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. When the above recovery method is used, it is possible to obtain a PPS resin in which the aforementioned chloroform extraction amount is in a preferable range.

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 state (usually 250 ° C. or higher, 8 kg / cm ² or higher) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in powder form at the same time as 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.

  Among them, in order to develop a more excellent low oligomer property, a method of slowly cooling after the completion of the polymerization reaction and recovering the particulate polymer is preferably used in order to increase the cleaning effect by the organic solvent described later.

[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 pH 4 solution heated to 80 to 200 ° C. and stirring for 30 minutes. The pH after the treatment 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, still more 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 preferable, and use of N-methyl-2-pyrrolidone is particularly preferable in terms of obtaining an excellent oligomer removal effect. 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. Such washing with an organic solvent is a process suitable for the production of the (A) PPS resin used in the present invention because a high oligomer removal effect is obtained.

  In the present invention, the PPS 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 PPS 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, with respect to 1 kg of the dry PPS 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 PPS resin) depends on the washing time and temperature, but 5 kg or more of warm water containing alkaline earth metal is used per 1 kg of dry PPS. It is 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 washing 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 still more 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.

  In the present invention, it is preferable to use a PPS resin in which the ash content in PPS is reduced to 0.3% by weight or less by deionization treatment or the like in terms of obtaining better toughness and moldability. Specific examples of such deionization treatment include acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment, and these treatments may be used in combination of two or more methods. In addition, the following methods are mentioned here for the measurement of the ash content. About 5 g of dry PPS bulk powder is weighed into a platinum crucible and baked until it becomes a black lump on an electric stove. Next, the firing is continued in the electric furnace set at 550 ° C. until the carbide is completely fired. Thereafter, after cooling in a desiccator, the weight is measured, and the ash content can be calculated from comparison with the initial weight.

  Among these, in the present invention, the PPS resin having the following features (1) to (3) is particularly preferably used in terms of high weld strength and high thermal shock resistance.

  (1) The amount of gas that volatilizes when heated and melted at 320 ° C. for 2 hours under vacuum is 0.3% by weight or less, preferably 0.28% by weight or less, more preferably 0.22% by weight or less. It is desirable to be. A PPS resin having such properties can be obtained by appropriately applying the above washing and thermal oxidation treatment. If the amount of gas generated exceeds 0.3% by weight, the volatile components increase, and the weld strength and the thermal shock resistance decrease, which is not preferable. The lower limit of the gas generation amount after the thermal oxidation treatment is not particularly limited, but it is economically disadvantageous if the time for the thermal oxidation treatment is long until the gas generation amount is reduced, and the time for the thermal oxidation treatment is prolonged. As a result, a gelled product is likely to be formed, which may cause molding defects. The amount of gas generated is preferably small, but the preferred lower limit is 0.01% by weight.

  The gas generation amount means the amount of an adhesive component in which the gas that volatilizes when the PPS resin is heated and melted under vacuum is cooled and liquefied or solidified, and is a glass in which the PPS resin is vacuum-sealed. It is measured by heating the ampule in a tubular furnace. As the shape of the glass ampule, the abdomen is 100 mm × 25 mm, the neck is 255 mm × 12 mm, and the wall thickness is 1 mm. As a specific measurement method, only the barrel of a glass ampoule in which PPS resin is vacuum-sealed is inserted into a 320 ° C. tubular furnace and heated for 2 hours, so that it becomes volatile at the neck of the ampule not heated by the tubular furnace. The gas is cooled and adheres. After the neck is cut out and weighed, the adhering gas is dissolved in chloroform and removed. The neck is then dried and weighed again. The amount of gas generated is determined from the difference in weight between the neck of the ampoule before and after removing the gas.

  (2) The ash content when incinerated at 550 ° C. is 0.3% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less. A PPS resin having such properties can be obtained by appropriately applying the above-described acid cleaning treatment. When the ash content exceeds 0.3% by weight, it means that the metal content of the PPS resin is large. If the metal content is large, it may cause a decrease in strength, a decrease in thermal shock characteristics, and the like. A preferred lower limit of the ash content is 0.01% by weight.

  (3) The amount of residue when dissolved in 1-chloronaphthalene 20 times weight for 5 minutes at 250 ° C. and filtered under pressure with a PTFE membrane filter having a pore size of 1 μm is 4% by weight or less, preferably 4. It is desirable that the content be 0% by weight or less, more preferably 3.5% by weight or less, and particularly preferably 3.0% by weight or less. When the amount of the residue exceeds 4.0% by weight, it means that the thermal oxidation crosslinking of the PPS resin proceeds excessively and the gelled product in the resin increases. Even if the thermal oxidation crosslinking of the PPS resin is excessively advanced, the effect of reducing the volatile matter is small, and on the other hand, it is not preferable because it causes a decrease in melt fluidity, a molding defect due to a gelled product, and a decrease in strength. The lower limit of the amount of the residue is not particularly limited, but is 1.5% by weight or more, preferably 1.7% by weight or more. When the amount of the residue is less than 1.5% by weight, the degree of thermal oxidation cross-linking is too slight, so that the volatile components at the time of melting do not decrease so much, and the volatile matter reducing effect may be small. A PPS resin having such properties can be obtained by appropriately applying the above thermal oxidation crosslinking treatment. A preferred lower limit for the amount of residue is 1.5% by weight.

  The amount of the residue is measured using a SUS test tube equipped with a high-temperature filtration device, a pneumatic cap, and a collecting funnel using a PPS resin formed into a press film of about 80 μm thickness as a sample. Specifically, a membrane filter having a pore size of 1 μm is first set in a SUS test tube, and then PPS resin formed into a press film to a thickness of about 80 μm and 1-chloronaphthalene having a weight of 20 times are weighed and sealed. This is set in a high-temperature filter at 250 ° C. and shaken for 5 minutes. Next, a syringe containing air is connected to the pneumatic cap, the piston of the syringe is pushed out, and hot filtration by pneumatic pressure is performed. As a specific quantification method of the amount of residue, it is determined from the weight difference between the membrane filter before filtration and the membrane filter vacuum-dried at 150 ° C. for 1 hour after filtration.

  For example, by employing the manufacturing method as described above, it is possible to obtain a (A) PPS resin suitable for a PPS resin composition having excellent heat resistance, antifreeze resistance and high weld strength, and the present invention. It is preferable to use (A) PPS resin. Such a PPS resin (A) is preferably blended as a PPS resin to be blended with the PPS resin composition of the present invention, but when at least 10% by weight of the PPS resin is such a PPS resin, The resin composition can have excellent heat resistance, high weld strength, and high thermal shock resistance. At least 30% by weight of the PPS resin blended in the PPS resin composition is preferably such a PPS resin, and more preferably 50% by weight or more.

  The blending amount of the (B-1) olefin copolymer having a glycidyl group in the PPS resin composition of the present invention is 1 to 4 parts by weight with respect to 100 parts by weight of (A) PPS resin, -2) The olefin-type copolymer which does not have a polar functional group is 1-4 weight part with respect to 100 weight part of (A) PPS resin. These are necessary in the sense that the excellent dimensional stability and the thermal shock resistance are arranged side by side, and the proper strength is imparted.

  (A) When 100 parts by weight of the PPS resin is less than 1 part by weight of the (B-1) olefin copolymer having a glycidyl group, it is preferable because appropriate cold-heat shock resistance as a composition cannot be obtained. Absent. Moreover, when (B-1) the olefin copolymer which has a glycidyl group exceeds 4 weight part, since fluidity | liquidity deteriorates and a moldability is impaired, it is unpreferable. Further, it is not preferable because the dimensions of the molded product, for example, roundness varies when molded under the same molding conditions, and appropriate dimensional stability cannot be obtained. In particular, the range of 1 to 4 parts by weight of the olefin copolymer having (B-1) glycidyl group is preferable with respect to 100 parts by weight of (A) PPS resin, and the range of 1.5 to 3.5 parts by weight is particularly preferable. Is preferred. (A) With respect to 100 parts by weight of the PPS resin, (B-1) an olefin copolymer having a glycidyl group is in the range of 1.5 to 3.5 parts by weight, excellent heat resistance and suitable as a composition This is particularly preferable since it has both mechanical strength and dimensional stability.

  On the other hand, when (B) the olefin copolymer having no polar functional group is less than 1 part by weight with respect to 100 parts by weight of the (A) PPS resin, appropriate cold-heat shock resistance as a composition is obtained. Since it is not possible, it is not preferable. When (B-2) the olefin copolymer having no polar functional group exceeds 4 parts by weight, the dimensions of the molded product when molded under the same molding conditions, for example, roundness varies, and the Therefore, it is not preferable because dimensional stability cannot be obtained. In particular, the range of 1 to 4 parts by weight of the olefin copolymer having (B-1) glycidyl group is preferable with respect to 100 parts by weight of (A) PPS resin, and the range of 1.5 to 3.5 parts by weight is particularly preferable. Is preferred. (A) With respect to 100 parts by weight of PPS resin, (B-2) In the range of 1.5 to 3.5 parts by weight of the olefin copolymer having no polar functional group, excellent heat resistance and composition This is particularly preferable because it has appropriate mechanical strength and high thermal shock resistance.

  In addition, (B-1) an olefin copolymer having a glycidyl group and (B-2) an olefin copolymer having no polar functional group are used in combination for excellent fluidity and thermal shock resistance. It is preferable in obtaining. Although there is no restriction | limiting in particular in these ratios, (B-1) / (B-2) = 5/95 weight ratio-95/5 weight ratio are preferable, (B-1) / (B-2) = 10 / The range of 90 weight ratio to 90/10 weight ratio is more preferable because of excellent balance between fluidity during molding and cold shock resistance.

  Examples of the (B-1) olefin copolymer having a glycidyl group include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene, isobutylene alone or (Co) polymer obtained by polymerizing two or more kinds, α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Copolymer of α, β-unsaturated acid and alkyl ester thereof, such as ethylene / propylene copolymer (“/” represents copolymerization, the same shall apply hereinafter), ethylene / 1-butene copolymer, ethylene / 1-hexene, ethylene / 1-octene, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer Monomer component (functional group) having an epoxy group in a polymer, ethylene / butyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, etc. As an example of the functional group-containing component, a single amount containing an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, or glycidyl citraconic acid Examples include the body. The method for introducing these functional group-containing components is not particularly limited, and the olefinic (co) polymer is copolymerized when (co) polymerizing, or grafted using a radical initiator to the olefinic (co) polymer. Or the like. The amount of the functional group-containing component introduced is in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on all monomers constituting the modified olefinic (co) polymer. Is appropriate. As a specific example of the olefin copolymer having a glycidyl group obtained by introducing a monomer component having an epoxy group into a particularly useful olefin polymer, an ethylene / propylene-g-glycidyl methacrylate copolymer ("" g ″ represents a graft, the same shall apply hereinafter), ethylene / 1-butene-g-glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / In addition to glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, or glycidyl ester of α-olefin and α, β-unsaturated acid such as ethylene and propylene, other monomers Epoxy group-containing olefin copolymers having an essential component are also preferably used. .

  Preferable examples include ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, and the like. Particularly preferred is an ethylene / methyl acrylate / glycidyl methacrylate copolymer.

  On the other hand, (B-2) olefin copolymers having no polar functional group include α-, such as ethylene, propylene, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene, and isobutylene. (Co) polymer obtained by polymerizing olefin alone or two or more types, for example, ethylene / propylene copolymer ("/" represents copolymerization, the same applies hereinafter), ethylene / 1-butene copolymer, ethylene / 1 / hexene copolymer and ethylene / 1-octene copolymer.

  Preferable examples include an ethylene / 1-butene copolymer and an ethylene / 1-octene copolymer. Particularly preferred is an ethylene / 1-octene copolymer.

  The blending amount of the (C) inorganic filler in the PPS resin composition of the present invention is 150 to 250 parts by weight of the (C) inorganic filler with respect to 100 parts by weight of the (A) PPS resin. It is necessary in the sense of having excellent mechanical strength and dimensional stability.

  When (C) the inorganic filler is less than 150 parts by weight relative to 100 parts by weight of the (A) PPS resin, it is not preferable because appropriate dimensional stability as a composition cannot be obtained. On the other hand, when (C) the inorganic filler exceeds 250 parts by weight, the melt fluidity of the composition is lowered, and appropriate molding processability cannot be obtained, and the mechanical strength cannot be obtained. In particular, the range of 150 to 250 parts by weight of (C) inorganic filler is preferable, and the range of 160 to 240 parts by weight is particularly preferable with respect to 100 parts by weight of (A) PPS resin. (A) In the range of 160 to 240 parts by weight of the inorganic filler (C) relative to 100 parts by weight of the PPS resin, it is particularly preferable because it has excellent heat resistance, appropriate mechanical strength as a composition, and dimensional stability.

  Specific examples of the fibrous filler as the inorganic filler (C) include glass fiber, glass milled fiber, glass flat fiber, modified cross-section glass fiber, glass cut fiber, flat glass fiber, stainless steel fiber, and aluminum fiber. And brass fibers, rock wool, PAN and pitch carbon fibers, carbon nanotubes, carbon nanofibers, calcium carbonate whiskers, wollastonite whiskers, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers, aramids Fiber, alumina fiber, silicon carbide fiber, asbestos fiber, gypsum fiber, ceramic fiber, zirconia fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, and the like. It is also possible to. In addition, it is better to use these fibrous fillers after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound. It is preferable in the meaning which obtains.

  Specific examples of the non-fibrous filler as the inorganic filler (C) include talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, hydrotalcite. Silicates such as silicon oxide, glass powder, magnesium oxide, aluminum oxide (alumina), silica (crushed / spherical), quartz, glass beads, glass flakes, crushed / indeterminate shaped glass, glass microballoon, molybdenum disulfide Aluminum oxide (crushed), translucent alumina (fibrous, plate-like, scale-like, granular, irregular shape, crushed product), titanium oxide (crushed), zinc oxide (fibrous, plate-like, scale-like, Oxides such as granular, irregular shape, and crushed products), carbonates such as calcium carbonate, magnesium carbonate, and zinc carbonate, calcium sulfate Sulfates such as calcium and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, silicon carbide, carbon black and silica, graphite, aluminum nitride, translucent aluminum nitride (fibrous and plate-like・ Scale, granular, irregular shape, crushed product), calcium polyphosphate, graphite, metal powder, metal flake, metal ribbon, metal oxide, etc., where the metal species of metal powder, metal flake, metal ribbon Examples include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, tin and the like. Moreover, carbon powder, graphite, carbon flakes, scaly carbon, fullerene, graphene and the like can be mentioned, and these may be hollow, and two or more kinds of these fillers may be used in combination.

  Further, these inorganic fillers may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, glass fiber, carbon fiber, calcium carbonate, carbon black, and graphite are particularly preferable.

  Moreover, it is preferable that the compounding quantity of (C-3) mica in the PPS resin composition of this invention is less than 5 weight part with respect to 100 weight part of PPS resin. It is preferable that the amount of mica is less than 5 parts by weight, and most preferably, mica is not added, since both excellent mechanical strength and antifreeze resistance can be achieved.

  (A) When 5 parts by weight or more of (C-3) mica is blended with 100 parts by weight of the PPS resin, it may not be possible to obtain appropriate antifreeze resistance, which is not preferable.

  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 alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) amino Ureido group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane , Γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and other isocyanate group-containing alkoxysilane compounds, γ- (2-aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-hydroxypropyltri Examples thereof include hydroxyl group-containing alkoxysilane compounds such as methoxysilane and γ-hydroxypropyltriethoxysilane. Of 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 PPS resin.

  The PPS resin composition of the present invention may further be blended with other resins within the 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, polyolefin-based elastomer, polyetherester elastomer, polyetheramide elastomer, polyamideimide, polyacetal, polyimide, polyetherimide, polyethersulfone , Polysulfone resin, polyallylsulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyester Teruketon resin, polythioether ketone resin, polyether ether ketone resin, polyamide-imide resins, and polytetrafluoroethylene resin.

  In the PPS resin composition of the present invention, other components such as antioxidants and heat stabilizers (hydroquinone) other than the above, weathering agents (resorcinol, salicylate, Benzotriazoles, benzophenones, hindered amines, etc.), mold release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide, bisurea, polyethylene wax, etc.), pigments (cadmium sulfide, Phthalocyanine, carbon black for coloring, etc.), dye (eg, nigrosine), crystal nucleating agent (eg, talc, silica, kaolin, clay), plasticizer (eg, octyl p-oxybenzoate, N-butylbenzenesulfonamide), antistatic Agent (alkyl sulfate type anionic antistatic agent, quaternary Ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (eg red phosphorus, phosphate ester, melamine cyanurate, (Hydroxides such as magnesium hydroxide and aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or combinations of these brominated flame retardants with antimony trioxide) , Heat stabilizer, lubricant such as calcium stearate, aluminum stearate, lithium stearate, bisphenol epoxy resin such as bisphenol A type, novolac phenol type epoxy resin, strength improving material such as cresol novolac type epoxy resin, External agents, coloring agents, can be added conventional additives such as flame retardants and blowing agents.

  The method for preparing the PPS 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 typical example is a method of kneading at a temperature of ˜380 ° C. There are no particular restrictions on the mixing order of the raw materials, and all the raw materials are blended and then melt kneaded by the above method, some raw materials are blended and then melt kneaded by the above method, and the remaining raw materials are blended and melt kneaded. Any method may be used, such as a method of mixing a part of raw materials or a method of mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or twin-screw extruder after compounding. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

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

  The PPS resin composition of the present invention is suitable for an “automobile cooling module”, and the “automobile cooling module” mentioned here preferably includes a housing, a valve, and at least three pipes. The shape may be any shape such as a quadrangular shape, a triangular shape, an elliptical shape, or a composite shape thereof, and a rib, a boss, and a flange may be installed in the housing. Further, the shape of the bulb may be any shape such as a spherical shape or a cylindrical shape, or a composite shape thereof, and the valve may have a hole. Further, the number of valves may be one, or two or more. The shape of the pipe may be straight or bent, and the cross-sectional shape of the pipe may be any shape such as a circular shape, an elliptical shape, or a quadrangular shape. Further, ribs, bosses, and flanges may be installed on the pipe. Further, at least three or more pipes may have the same shape or a combination of different shapes.

  The antifreeze flowing inside the housing is an antifreeze containing alcohols, glycols, glycerin and the like, and the type and concentration thereof are not particularly limited. Moreover, even if it is high temperature or low temperature, these may flow repeatedly.

  As the automobile cooling module, a module in which the flow rate of the antifreeze liquid flowing inside the housing and the flow path are controlled by opening / closing a valve included in the housing is preferable.

  The opening and closing of the valve contained in the housing may use the driving force of the engine or the driving force of the motor.

  As described above, the PPS resin composition of the present invention not only has excellent dimensional stability, but also has excellent balance with respect to thermal shock resistance and antifreeze resistance, so that dimensional accuracy and durability are required. Suitable for molding automotive cooling modules. That is, since the PPS resin composition of the present invention has characteristics such as excellent dimensional stability, resistance to cold shock and antifreeze, it is useful for a cooling module for automobiles. Useful for automotive cooling modules.

  Other applicable applications of the PPS resin composition of the present invention include, for example, sensors, LED lamps, consumer connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, oscillators, various terminal boards, Transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts Electronic parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademark) / compact discs, lighting parts, refrigerator parts, Home Con parts, typewriter parts, typified by a word processor parts, application to the Secretary-electric product parts is also possible. Other machine-related parts such as office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, etc .: microscopes, binoculars, cameras, watches, etc. Optical equipment, precision machinery-related parts represented by; water faucet tops, mixing faucets, pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, water meter housings, etc. Alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, fuel-related / exhaust / intake-related pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant Jo Carburetor main body, carburetor spacer, exhaust gas sensor, cooling water 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 holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, starter relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch boards, coils for fuel related electromagnetic valves, Fuse connector, horn terminal, electrical component insulation board, step motor rotor, Pusoketto, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, a vehicle speed sensor, various applications such as automotive-related parts such as the cable liner 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.

[Measurement method of characteristics of PPS resin]
(1) Gas generation amount
3 g of PPS resin was weighed into a glass ampoule having an abdomen of 100 mm × 25 mm, a neck of 255 mm × 12 mm, and a wall thickness of 1 mm, followed by vacuum sealing. Only the barrel of this glass ampoule was inserted into a ceramic electric tubular furnace ARF-30K manufactured by Asahi Rika Seisakusho and heated at 320 ° C. for 2 hours. After the ampoule was taken out, the neck of the ampoule that was not heated by the tubular furnace and was attached with volatile gas was cut out with a file and weighed. Next, the adhering gas was dissolved and removed with 5 g of chloroform, dried for 1 hour in a glass dryer at 60 ° C., and then weighed again. The difference in weight between the neck of the ampoule before and after removing the gas was defined as the amount of gas generated (% by weight).

(2) Ash content rate 5 g of a sample (PPS resin) was precisely weighed in a crucible previously baked at 550 ° C., and placed in an electric furnace at 550 ° C. for 24 hours for ashing. The amount of ash remaining in the crucible was precisely weighed, and the ratio to the amount of sample before ashing was defined as the ash content (% by weight).

(3) Residue amount 100 mg of PPS resin formed into a press film of about 80 μm thickness by placing a pre-weighed PTFE membrane filter with a pore size of 1 μm in a SUS test tube made by Senshu Kagaku equipped with a pneumatic cap and a collecting funnel. And 2 g of 1-chloronaphthalene were weighed in and sealed. This was inserted into a high-temperature filtration device SSC-9300 manufactured by Senshu Kagaku, and the PPS resin was dissolved in 1-chloronaphthalene by heating and shaking at 250 ° C. for 5 minutes. After connecting a 20 mL syringe containing air to the pneumatic cap, the piston was extruded and the solution was filtered through a membrane filter. The membrane filter was taken out, vacuum-dried at 150 ° C. for 1 hour, and then weighed. The difference in membrane filter weight before and after filtration was defined as the amount of residue (% by weight).

(4) Melt flow rate (MFR)
The measurement temperature was 315.5 ° C. and the load was 5000 g, and the measurement was performed by a method according to ASTM-D1238-70.

[Reference Example 1] Polymerization of PPS (PPS-1)
In an autoclave with a stirrer and a valve at the bottom, 8267.4 g (70.0 mol) of 47.5% sodium hydrosulfide, 2925.0 g (70.2 mol) of 96% sodium hydroxide, N-methyl-2- 13860.0 g (140.0 mol) of pyrrolidone (NMP), 1894.2 g (23.1 mol) of sodium acetate, and 10500.0 g of ion-exchanged water were charged, and the mixture was passed through nitrogen at normal pressure to 240 ° C. over about 3 hours. After gradually heating to distill water 14772.1 g and NMP 280.0 g, 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 1.08 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.023 mol per mol of the alkali metal sulfide charged.

  Next, 10466.7 g (72.4 mol) of p-dichlorobenzene (p-DCB) and 6444.9 g (65.1 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 0.6 ° C./min and held at 270 ° C. for 70 minutes. The extraction valve at the bottom of the autoclave was opened, and 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 53 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 having a pore size of 10 to 16 μm. Next, 60 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter having a pore size of 10 to 16 μm, and suction filtered to obtain 18000 g of PPS resin cake (including 7550 g of PPS resin).

  The PPS resin cake (18000 g), ion-exchanged water (40 liters), and acetic acid (43 g) were charged into an autoclave equipped with a stirrer, the inside of the autoclave was replaced with nitrogen, the temperature was raised to 192 ° C., and maintained for 30 minutes for acid treatment. The pH during the acid treatment was 7. After cooling the autoclave, the contents were filtered through a glass filter having a pore size of 10 to 16 μm. Next, 60 liters of ion exchange water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake. The obtained cake was dried at 120 ° C. for 4 hours under a nitrogen stream to obtain an acid-treated PPS resin powder. Subsequently, this PPS resin powder was put into a heating apparatus with a stirrer having a volume of 100 liters, and subjected to thermal oxidation treatment at 200 ° C. and an oxygen concentration of 21% for 2 hours. The thermal oxidation treatment was performed in an air atmosphere of 1.96 liters / minute of air to obtain PPS-1. The obtained polymer had a gas generation amount of 0.16% by weight, an ash content of 0.14% by weight, a residue amount of 1.9% by weight, and an MFR of 554 g / 10 minutes.

[Reference Example 2] Polymerization of PPS (PPS-2)
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 -Charged 11.45 kg (115.50 mol) of pyrrolidone (NMP) and 10.5 kg of ion-exchanged water and gradually heated to 245 ° C. over about 3 hours while passing nitrogen at normal pressure to obtain 14.78 kg of water and NMP0 After distilling 28 kg, the reaction vessel was cooled to 200 ° C. The amount of water remaining in the system per mole 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.

  Thereafter, the mixture was cooled to 200 ° C., 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After reacting at 270 ° C. for 100 minutes, the bottom valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer 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 acetic acid was added so that the pH was 7. 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.
This was heat-treated at 200 ° C. in an oxygen stream until the MFR value reached 400 g / 10 minutes, to obtain PPS-2. The amount of gas generated in the obtained polymer was 0.39% by weight, the ash content was 0.01% by weight, and the amount of residue was 4.3% by weight.

[Compounding materials used in Examples and Comparative Examples]
The formulations used in the examples and comparative examples are as follows.

(A) PPS resin PPS-1: PPS resin polymerized by the method described in Reference Example 1 PPS-2: PPS resin polymerized by the method described in Reference Example 2

(B) Olefin Copolymer B-1: Ethylene / glycidyl methacrylate / methyl acrylate copolymer (Sumitomo Chemical Bond First 7M)
B-2: Ethylene / 1-octene copolymer (engaged 8842 manufactured by Dow Chemical Company)

(C) Inorganic filler C-1: Chopped strand (manufactured by Nippon Electric Glass Co., Ltd. T-760H 3 mm length, average fiber diameter 10.5 μm)
C-2: Heavy calcium carbonate (KSS Fine 1000 KSS-1000 50% average particle size 4.2 μm)
C-3: Gold mica (manufactured by Repco S-220HG weight average particle size 55 μm weight average aspect ratio 55)

[Measurement Evaluation Method of PPS Resin Composition]
The measurement evaluation methods in Examples and Comparative Examples are as follows.

(1) Tensile strength Measurement was performed according to ISO 527-1, 2 method. Specifically, the measurement was performed as follows. After the PPS resin composition pellets were dried at 130 ° C. for 3 hours using a hot air dryer, an injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. (SE-) was set at a cylinder temperature of 310 ° C. and a mold temperature of 145 ° C. 50D), and using a mold having the shape of a type A1 test piece defined in ISO 20553, injection molding is performed under the condition that the average speed of the molten resin passing through the cross-sectional area of the central parallel portion is 400 ± 50 mm / s. A test piece was obtained. The test piece was conditioned for 16 hours under the conditions of 23 ° C. and 50% relative humidity, then in an atmosphere of 23 ° C. and 50% relative humidity, the distance between the grips: 114 mm, and the test speed: 5 mm / s. The tensile strength was measured at.

(2) Bending strength Measurement was performed according to ISO 178 method. Specifically, the measurement was performed as follows. The PPS resin composition pellets are dried at 130 ° C. for 3 hours using a hot air dryer, and then supplied to an injection molding machine (SE-50D) manufactured by Sumitomo Heavy Industries set at a cylinder temperature of 310 ° C. and a mold temperature of 145 ° C. Then, using a mold of the type A1 test piece shape defined in ISO20753, injection molding was performed under the condition that the average speed of the molten resin passing through the cross-sectional area of the central parallel part was 400 ± 50 mm / s, and the test piece was Obtained. The central parallel part of this test piece was cut out to obtain a type B2 test piece. The test piece was conditioned for 16 hours under conditions of 23 ° C. and 50% relative humidity, and then subjected to bending strength measurement under the conditions of 23 ° C. and 50% relative humidity, span of 64 mm, and test speed: 2 mm / s. Was done.

(3) Fluidity
Using a 1mm-thick spiral flow mold, 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. (Used injection molding machine: “SE-30D” manufactured by Sumitomo Heavy Industries). The larger this value, the better the fluidity.

(4) Weld strength
An ASTM No. 4 dumbbell piece (1.6 mmt) having gates at both ends and a weld line near the center of the test piece was molded using an injection molding machine at a cylinder temperature of 320 ° C. and a mold temperature of 135 ° C. After 100 molded pieces were molded and the mold was forcibly contaminated, 10 samples for measurement were obtained, and the tensile strength was measured under the conditions of test speed: 10 mm / min and distance between grips: 64 mm. .

(5-1) Dimensional stability-1
Using an injection molding machine (SE-30D) manufactured by Sumitomo Heavy Industries, a molded product having a cylindrical portion shown in FIG. 1 was molded. Molding conditions were a cylinder temperature of 320 ° C., a mold temperature of 130 ° C., a filling time of 0.4 seconds, a holding pressure of 40 MPa, and other conditions were molded under general molding conditions. The roundness of the inner diameter of a portion 10 mm from the end face of the cylindrical opening far from the gate of the molded product was measured, and this value was defined as dimensional stability-1. The measurement was performed according to JIS B0621 using a Mitutoyo three-dimensional dimension measuring machine. If it is 80 μm or less, it can be said that the product level has no practical problem, but the smaller this value, the better the dimensional stability and the better.

(5-2) Dimensional stability-2
The above-described measurement of dimensional stability-1 was performed on 10 samples, and the difference between the maximum value and the minimum value of the measured values was defined as dimensional stability-2. This value shows the variation in molding when molding under the same molding conditions. If it is 10 μm or less, it can be said that the product level has no practical problem, but the smaller this value, the better the dimensional stability and the better.

(6-1) Antifreeze resistance-1
As the antifreeze, Volkswagen LLC “G13” was diluted with distilled water to a 40 volume% aqueous solution. A molded product of ISO 3167 A-shaped dumbbell test piece (4 mm thickness) is immersed in a 40% by volume aqueous solution of LLC at a temperature of 135 ° C. for 168 hours, and the molded product is pulled in accordance with ISO 527-1, 2 method. The strength was measured. The strength retention at that time was defined as antifreeze-related-1. If it is 90% or more, it can be said that the product level has no problem in practical use, but the higher this value, the better the antifreeze resistance, which is preferable.

(6-2) Antifreeze resistance-2
The molded article having the cylindrical portion shown in FIG. 1 is immersed in a 40% by volume LLC aqueous solution at a temperature of 135 ° C. for 168 hours, and the inner diameter roundness of the molded article is measured in the same manner as in (5-1). I did it. If the difference from the dimensional stability-1 is 5 μm or less, it can be said that there is no practical problem, but the smaller this value, the better the antifreeze resistance and the better.

(7) Cold and thermal shock resistance The metal insert molded product shown in FIG. 2 in which a metal block was insert-molded under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. was used. This was treated at 130 ° C. for 1 hour and then treated at −40 ° C. for 1 hour as a single thermal shock treatment, and the presence or absence of cracks was visually confirmed every 5 times. The number of cold shock treatments where cracks were observed was defined as cold shock resistance. If cracks do not occur 30 times or more, it can be said that the product level has no practical problem. However, the greater the number of treatments until the cracks are generated, the better the thermal shock resistance.

[Production of PPS resin composition]
Obtained in Reference Examples 1 and 2 using a twin-screw extruder (TEM-26 manufactured by Toshiba Machine Co., Ltd.) having an intermediate addition port with a diameter of 26 mm, in which the cylinder temperature was set to 320 ° C. and the screw rotation speed was set to 400 rpm. 100 parts by weight of PPS resin (A) and (C) additive are added from the raw material supply port at a weight ratio shown in Tables 1 and 2 to be in a molten state, and (B) inorganic fillers are shown in Tables 1 and 2. Pellets were obtained by feeding from the intermediate addition port at a weight ratio and melt-kneading at a discharge rate of 30 kg / hour. The following properties were evaluated using this pellet. The results are shown in Tables 1 and 2.

  The molded product obtained by injection molding of the PPS resin composition thus obtained is excellent in dimensional stability, thermal shock resistance and antifreeze resistance, and is therefore useful for automobile cooling modules.

1. Sprue 2. Runner 3. Gate 4. 4. Molded product for roundness evaluation 5. Roundness measurement site 6. Insert metal Gate 8. Metal insert molding

Claims (5)

(A) 1 to 4 parts by weight of an olefin copolymer having a glycidyl group, and (B-2) an olefin copolymer 1 having no polar functional group to 100 parts by weight of a polyphenylene sulfide resin. An automotive cooling module formed by injection-molding a polyphenylene sulfide resin composition containing 4 parts by weight and (C) 150 to 250 parts by weight of an inorganic filler. The automotive cooling module according to claim 1, wherein the amount of (C-3) mica contained in the polyphenylene sulfide resin composition is less than 5 parts by weight relative to 100 parts by weight of the polyphenylene sulfide resin. When the polyphenylene sulfide resin is (a) heated and melted under vacuum at 320 ° C. for 2 hours, the gas generation amount volatilized is 0.3% by weight or less, and (b) the amount of ash when incinerated at 550 ° C. is 0.00. 3% by weight or less, (c) Residue amount is 4% by weight or less when melted in 20-fold weight 1-chloronaphthalene at 250 ° C. for 5 minutes and filtered under pressure with a PTFE membrane filter having a pore size of 1 μm. The automotive cooling module according to claim 1 or 2, which is a polyphenylene sulfide resin. The automobile cooling module according to claim 1, wherein the automobile cooling module includes a housing, a valve, and at least three pipes. The automobile cooling module according to claim 4, wherein the flow rate and flow path of the antifreeze liquid flowing inside the housing of the automobile cooling module are controlled by opening and closing a valve included in the housing.

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