JP6809291B2 - Polyphenylene sulfide resin composition for forcible injection molding - Google Patents

Description

The present invention relates to a polyphenylene sulfide resin composition used for a cylindrical pipe-shaped molded product having a bulging portion.

Polyphenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) belongs to super engineering plastics and has excellent mechanical strength, rigidity, flame retardancy, chemical resistance, electrical characteristics, dimensional stability, etc. , Mainly for injection molding, widely used in various electric / electronic parts, home appliances parts, automobile parts and mechanical parts.

Since PPS resin is a resin that has excellent mechanical strength, heat resistance, and water resistance and can withstand harsh usage conditions, it has not been used until now, such as parts for thermo-fluid transfer in which metal was used. It is spreading to other parts. For example, in automobiles, the needs for further weight reduction and space saving are increasing, and resin products are being widely used. In particular, cooling system parts are miniaturized, and multiple parts are combined instead of parts to form multiple parts. Development is shifting to parts with integrated functions. Along with this, the shape becomes more complicated, so that the number of parts increases and the manufacturing man-hours increase. Then, it is required that each part is integrally molded instead of being retrofitted. When performing integral molding, for example, for piping parts having a bulging portion at the end in order to improve airtightness, it is necessary to carry out by "mold split molding" or by "forced punching molding". .. However, in mold split molding, burrs are generated on the mold split surface of the molded product, which increases the number of deburring steps, which is not preferable. In order to omit this deburring step, it is necessary to perform integral molding and forcibly punch out the portion having a bulging portion, and a resin composition capable of forcibly punching is required. There is. Here, forcible punching means that the mold is pulled out in the axial direction over the bulging portion of the molded product. Since the bulging portion of the molded product gets over the undercut portion of the mold, it is necessary to elastically deform to the inside of the molded product at the time of die cutting.

While the PPS resin has excellent rigidity, it has poor toughness, so that when forcibly punching is performed, breakage and cracks occur, so that it is not possible to obtain a molded product with high accuracy and good appearance. Therefore, attempts have been made to forcibly remove the rigid resin by changing the product shape.

Further, in Patent Document 1, by making the inner peripheral surface of the bulging portion into a waveform in which the radial cross section repeats unevenness, the peripheral distance of the inner peripheral surface is lengthened, and the deflection generated during forcible punching is prevented. By absorbing it, the limit of elastic deformation of the inner peripheral surface is raised.

Further, in Patent Document 2, a technique of forming a thin-walled portion at a predetermined position on the circumference of the bulging portion is known. This resin injection-molded product relieves stress by causing deformation at the time of forcible removal centering on a thin-walled portion.

Further, in Patent Document 3, a technique of forming a D-cut portion in a radial cross section inside a portion considered to have weak strength is known.

In this resin injection molded product, the D-cut portion is formed at the portion where the weld is generated during molding of the bulge portion, so that the wall thickness of the D-cut portion is increased and the strength of the bulge portion is small. The strength can be increased. Therefore, it is possible to prevent the stress at the time of forcible pulling from concentrating on the portion having weak strength, and to prevent the deformation at the time of forcible pulling.

Japanese Unexamined Patent Publication No. 2012-183646 JP 2015-198036 JP-A-2007-0555057

The present invention solves the above-mentioned problem of conventional forcible molding, that is, using a highly rigid PPS resin composition, resin injection having a bulging portion while maintaining sufficient strength and without appearance defects. It provides a resin composition capable of forcibly removing a molded product. Cracks due to forcible punching occur when the strength of the resin is insufficient against the stress generated when the mold gets over the bulging portion at high speed when the resin has high rigidity. Therefore, it is important that the strength applied at the time of high-speed change at high temperature is improved and becomes higher than the generated stress. On the other hand, reducing the rigidity by reducing the fibrous filler in order to reduce the generated stress may deteriorate the mechanical strength and dimensional accuracy of the product.

In addition, it is possible to force punching by reducing the undercut rate. The undercut ratio referred to here is the ratio of the outer diameter of the bulging portion to the outer diameter of the cylindrical portion. However, when the undercut rate is smaller than 3.5, it is not preferable because the function as a retaining function at the time of plug-in joining with the pipe is insufficient.

Therefore, a resin composition capable of forcibly removing a resin injection-molded product having a cylindrical bulge having a high elastic modulus, high strength, no appearance defect, and a sufficient undercut ratio can be obtained. It is required to provide.

However, Patent Documents 1 and 2 have a problem that the strength of the molded product itself is lowered because a thin portion is intentionally formed in the thick portion and a portion having a weak strength is formed. Further, in Patent Document 3, since a D-cut portion is formed in the radial cross section inside the portion where the strength of the bulging portion is weak to increase the rigidity, a resin having a large rigidity such as PPS resin is used. When used, the rigidity becomes even higher. For this reason, there is a problem that the bulging portion is not elastically deformed and is damaged or wrinkled when forcibly pulled out.

In order to solve the above problems, the present invention provides the following.
(1) For forcible injection molding, which comprises 100 parts by weight of (A) polyphenylene sulfide resin and 30 to 120 parts by weight, preferably 50 to 105 parts by weight of (B) fibrous filler. It is a polyphenylene sulfide resin composition, has a bending elasticity E1 at 23 degrees Celsius of 7 to 20 GPa, a tensile strength σ1 at 120 degrees Celsius of 50 MPa or more, and α represented by (Equation 1) is 0.011 ≦ α ≦. A polyphenylene sulfide resin composition for forcible injection molding having a bulging portion shape on a cylindrical pipe, characterized by being 0.033, preferably 0.012 ≦ α ≦ 0.030.

(2) The polyphenylene sulfide resin composition for forcible injection molding according to claim 1, wherein the fibrous filler is 30 to 90 parts by weight.
(3) The bulging portion has a relationship in which the undercut ratio Ki represented by (Equation 2) is 3.5 ≦ Ki ≦ 14, preferably 4.0 ≦ Ki ≦ 10.0. The polyphenylene sulfide resin composition for forcible removal according to (1) to (3), which preferably has a relationship of 4.0 ≦ Ki ≦ 6.5.

(4) A method for producing a forcibly punched injection-molded product having a bulging portion in a cylindrical pipe obtained by using the polyphenylene sulfide resin composition according to any one of (1) to (3).

According to the present invention, in an injection-molded article having an undercut ratio of 3.5 ≦ Ki ≦ 14, it is possible to release the mold by forcibly removing the PPS resin composition having high rigidity. As a result, it is possible to suppress the appearance defect of the bulging portion that occurs at the time of mold release while maintaining the strength of the molded product.

An embodiment of a resin injection molded product according to the present invention is shown, and is a perspective view of a main part of the resin molded product. It is a figure which looked at the cylindrical tip portion of the resin injection molded article in FIG. 1 in the cross section perpendicular to the cylindrical axis, and is the figure which shows the undercut rate. The shape at the time of measuring the strength of an injection-molded article in this invention is shown.

The present invention will be described in detail below. In the present invention, "weight" means "mass".

The (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 the polymer containing the repeating unit represented by the above structural formula is preferable. Further, less than 30 mol% of the repeating unit of the PPS resin may be composed of a repeating unit having the following structure or the like.

The melt viscosity of the (A) PPS resin used in the present invention ranges from 5 to 50 Pa · s (310 ° C., shear rate 1,216 / s) from the viewpoint of obtaining a resin composition having excellent melt fluidity. Preferably, the range of 10 to 45 Pa · s is more preferable, and the range of 10 to 40 Pa · s is further preferable. Further, two or more kinds of 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., Ltd. under the conditions of 310 ° C. and a shear rate of 1,216 / s.

The method for producing the (A) PPS resin used in the present invention will be described below, but the method is not limited to the following method as long as a PPS having the above structure and characteristics can be obtained. However, a method in which dichlorobenzene and a sulfur source are the main monomers (90 mol% or more) and polymerization is carried out in the presence of an aprotic polar solvent is most preferable in terms of production stability.

Next, the contents of the polyhalogen aromatic compound, the sulfidizing agent, the polymerization solvent, the molecular weight modifier, the polymerization aid and the 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, and hexa. Polyhalogenated fragrances such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Group compounds are mentioned, 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. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, but the p-dihalogenated aromatic compound typified by p-dichlorobenzene can be used as a main component. preferable.

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

[Sulfide agent]
Examples of the sulfidizing agent used in the present invention include alkali metal sulfide, alkali metal hydrosulfide, 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 sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these, among which sodium hydrosulfide is used. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.

Further, an alkali metal sulfide prepared in situ in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Further, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and this can be transferred to a polymerization tank for use.

Alternatively, alkali metal sulfides prepared in situ in the reaction system from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide can also be used. Further, an alkali metal sulfide can be prepared from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide, and the alkali metal sulfide can be transferred to a polymerization tank for use.

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

It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfide agent. Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and a mixture of two or more of these, and alkaline earth. Specific examples of the metal hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide and the like, and sodium hydroxide is preferably used.

When alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use alkali metal hydroxide at the same time, but the amount used is 0.90 to 1. per 1 mol of alkali metal hydrosulfide. The range of 50 mol, preferably 0.90 to 1.30 mol, more preferably 0.95 to 1.20 mol can be exemplified.

[Polymerization solvent]
In the present invention, an organic polar solvent is used as the 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-imidazolidi. Examples thereof include aprotic organic solvents typified by non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphate triamide, dimethylsulfone, tetramethylenesulfocide, and mixtures thereof, all of which are used. It is preferably used because of its high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) is particularly preferably used.

The amount of the organic protic 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 compound in order to form the terminal of the PPS resin to be produced, or to adjust the polymerization reaction or molecular weight. Can be used in combination with compounds. Examples of the monohalogenated compound include monohalogenated benzene, monohalogenated naphthalene, monohalogenated anthracene, a monohalogenated compound containing two or more benzene rings, and a monohalogenated heterocyclic compound. Of these, benzene monohalogenated is preferable from the viewpoint of economy. It is also possible to use two or more different monohalogenated compounds in combination.

[Polymerization aid]
In the present invention, it is also one of the preferable embodiments to use a polymerization aid for adjusting the degree of polymerization. Here, the polymerization aid 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 soils. Examples include metal phosphates. These can be used alone or in combination of two or more. Of these, organic carboxylates, water, and alkali metal chlorides are preferred, and sodium, lithium carboxylates and / or water are particularly preferred.

The alkali metal carboxylate is a general formula R (COOM) n (in the formula, R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group having 1 to 20 carbon atoms. M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium. 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 lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluic acid, and mixtures thereof. Can be mentioned.

The alkali metal carboxylate is a reaction in which an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates are added in approximately equal chemical equivalents and reacted. It may be formed by. Among the above alkali metal carboxylates, the lithium salt is highly soluble in the reaction system and has a large auxiliary effect, but is expensive, and the potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in a polymerization system, is most preferably used.

When these alkali metal carboxylates are used as polymerization aids, the amount used is usually 0.01 mol per 1 mol of the charged sulfidizing agent from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing and low oligomer elution. It is in the range of ~ 2 mol, and is preferably in the range of 0.010 to 0.088 mol from the viewpoint of achieving both the degree of polymerization useful for the present invention and low oligomerism. In the case of the above range, a PPS resin having the above-mentioned melt viscosity in a preferable range can be obtained.

When water is used as a polymerization aid, the amount added is usually in the range of 0.3 mol to 15 mol with respect to 1 mol of the charged sulfidizing agent, and is 0.6 to 10 in the sense of obtaining a higher degree of polymerization. The molar range is preferred, and the range of 1-5 moles is more preferred. Of course, two or more of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, it is possible to increase the molecular weight in a smaller amount of each.

The timing of addition of these polymerization aids is not particularly specified, and may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or may be added in a plurality of times. When an alkali metal carboxylate is used as the polymerization aid, it is more preferable to add it at the same time as the start of the previous step or the start of polymerization because it is easy to add. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound in the middle of the polymerization reaction after charging it.

[Polymerization stabilizer]
In the present invention, a polymerization stabilizer can also be used in order to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses unwanted side reactions. One guideline for the side reaction is the production of thiophenol, and the production of thiophenol can be suppressed by adding a polymerization stabilizer. 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 them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, it is one of the polymerization stabilizers used in the present invention. Further, when an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but here, the alkali metal water which is excessive with respect to the sulfidizing agent. 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, based on 1 mol of the charged sulfidizing agent. It is preferable to use it. If this ratio is small, the stabilizing effect is insufficient, and if it is too large, it tends to be economically disadvantageous or the polymer yield tends to decrease.

The timing of addition of the polymerization stabilizer is not particularly specified, and it may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or it may be added in a plurality of times. It is more preferable to add them at the same time as the start of the process or the start of polymerization because the addition is easy.

Next, the method for producing the (A) PPS resin used in the present invention will be specifically described step by step in the pre-step, polymerization reaction step, recovery step, and post-treatment step.

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

Further, as described above, as the sulfidizing agent, a sulfidizing agent prepared from alkali metal hydrosulfide and alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank is also used. Can be done. Although this method is not particularly limited, it is desirable to use alkali metal hydrosulfide and alkali metal hydroxide as an organic polar solvent in a temperature range of room temperature to 150 ° C., preferably room temperature to 100 ° C. in an inert gas atmosphere. In addition, there is a method in which the temperature is raised to at least 150 ° C. or higher, preferably 180 to 260 ° C. under normal pressure or reduced pressure to distill off water. A polymerization aid may be added at this stage. Further, in order to promote the distilling of water, toluene or the like may be added to carry out the reaction.

The amount of water in the polymerization system in the polymerization reaction is preferably 0.3 to 10.0 mol per 1 mol of the charged sulfidizing agent. Here, the amount of water in the polymerization system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. Further, the water to be charged may be in any form such as water, an aqueous solution, and water of crystallization.

[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 mixed in a temperature range of preferably room temperature to 240 ° C., preferably 100 to 230 ° C. in an inert gas atmosphere. .. A polymerization aid may be added at this stage. The order in which these raw materials are charged may be random or simultaneous.

Such a mixture is usually heated to the range of 200 ° C to 290 ° C. The rate of temperature rise is not particularly limited, but a rate of 0.01 to 5 ° C./min is usually selected, and a range of 0.1 to 3 ° C./min is more preferable. In general, the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is carried out at that temperature for usually 0.25 to 50 hours, preferably 0.5 to 20 hours. A method of reacting at 200 ° C. to 260 ° C. for a certain period of time before reaching the final temperature and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200 ° C. to 260 ° C. is usually selected in the range of 0.25 hours to 20 hours, preferably in the range of 0.25 to 10 hours.

In addition, in order to obtain a polymer having a higher degree of polymerization, it may be effective to carry out the polymerization in a plurality of steps. When the polymerization is carried out in a plurality of steps, it is effective that the conversion rate 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 (abbreviated as PHA here) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.

(A) When a polyhalogenated aromatic compound is excessively added to an alkali metal sulfide in a molar ratio. Conversion rate = [PHA charge amount (mol) -PHA residual amount (mol)] / [PHA charge amount (mol)) -PHA excess (mol)]

(B) In cases other than the above (a) Conversion rate = [PHA charge amount (mol) -PHA residual amount (mol)] / [PHA charge amount (mol)]

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

For example, a method of slowly cooling after completion of the polymerization reaction to recover the particulate polymer may be used. The slow cooling rate at this time is not particularly limited, but is usually about 0.1 ° C./min to 3 ° C./min. It is not necessary to slowly cool at the same rate in the entire process of the slow cooling process, and a method of slowly cooling at a rate of 0.1 to 1 ° C./min until the polymer particles crystallize and precipitate, and then at a rate of 1 ° C./min or more is used. It may be adopted. When the above recovery method is used, a PPS resin in which the above-mentioned chloroform extraction amount is in a preferable range can be obtained.

Further, it is also preferable to carry out the above recovery under quenching conditions, and a flash method is mentioned as a preferable method of this recovery method. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (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. It is a method, and the term “flash” as used herein means that a polymerization reaction product is ejected from a nozzle. Specific examples of the flashing atmosphere include nitrogen or water vapor under normal pressure, and the temperature is usually selected in the range of 150 ° C. to 250 ° C.

Among them, in order to exhibit more excellent low oligomeric properties, a method of slowly cooling after completion of the polymerization reaction to recover the particulate polymer is preferably used in order to enhance the cleaning effect with an organic solvent described later.

[Post-treatment process]
The PPS resin (A) 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 performing acid treatment, 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 PPS resins such as nitric acid are not preferable.

The acid treatment method includes a method of immersing the PPS resin in an acid or an aqueous solution of an acid, and it is also 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 solution of pH 4 heated to 80 to 200 ° C. and stirring for 30 minutes. The pH after the treatment may be 4 or more, for example, pH 4 to 8. The acid-treated PPS resin is preferably washed with water or warm water several times 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 preferable chemical modification of the PPS resin by acid treatment is not impaired.

When hot water treatment is performed, it is as follows. When treating the PPS resin used in the present invention with hot water, 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 the temperature is lower 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 exhibit the preferable chemical modification effect of the PPS resin by the hot water washing of the present invention. The operation of the hot water treatment is not particularly limited, and is carried out by a method of putting a predetermined amount of PPS resin into a predetermined amount of water, heating and stirring in a pressure vessel, a method of continuously performing hot water treatment, and the like. The ratio of the PPS resin to water is preferably more than that of water, but usually, a bath ratio of 200 g or less of PPS resin is selected with respect to 1 liter of water.

In addition, the treatment atmosphere is preferably an inert atmosphere in order to avoid decomposition of the terminal groups. Further, the PPS resin that has been subjected to this hot water treatment operation is preferably washed with warm water several times in order to remove residual components.

When cleaning with an organic solvent, it is as follows. The organic solvent used for cleaning 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, hexamethylphosphorasamide and piperazinones, sulfoxide-sulfone solvents such as dimethylsulfoxide, dimethylsulfone and sulfolane, ketone solvents such as acetone, methylethylketone, diethylketone and acetophenone, Ether-based solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, halogen-based solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, and chlorobenzene. , Methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and other alcohol / phenol solvents and benzene, toluene, xylene and other aromatic hydrocarbon solvents. Can be mentioned. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is preferable, and the use of N-methyl-2-pyrrolidone is particularly preferable in the sense of obtaining a particularly excellent oligomer removing effect. preferable. Moreover, these organic solvents are used in one kind or a mixture of two or more kinds.

As a method of cleaning with an organic solvent, there is a method such as immersing the PPS resin in the organic solvent, and it is also possible to appropriately stir or heat as necessary. The cleaning temperature when cleaning the PPS resin with an organic solvent is not particularly limited, and any temperature of about room temperature to 300 ° C. can be selected. The higher the cleaning temperature, the higher the cleaning efficiency tends to be, but usually, a sufficient effect can be 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 higher than the boiling point of the organic solvent. In addition, there is no particular limitation on the cleaning time. Although it depends on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect is usually obtained by cleaning for 5 minutes or more. It is also possible to wash continuously. Cleaning with such an organic solvent is a process suitable for producing the (A) PPS resin used in the present invention because a high oligomer removing effect can be 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 methods can be exemplified as specific methods for washing the PPS resin with water containing an alkaline earth metal salt. The type of alkaline earth metal salt is not particularly limited, 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. Is mentioned as a preferable example, and an alkaline earth metal salt of a water-soluble organic carboxylic acid such as calcium acetate or magnesium acetate is 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, based on 1 kg of the dried PPS resin. The washing time is preferably 0.5 hours or more, more preferably 1.0 hours or more. The preferable washing bath ratio (weight of hot 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 hot water containing the above alkaline earth metal is used per 1 kg of dry PPS. It is preferable to wash with 10 kg or more. The upper limit is not particularly limited and may be high, but it is preferably 100 kg or less from the viewpoint of the amount used and the effect obtained. Such hot water washing may be performed a plurality of times.

The PPS resin (A) used in the present invention can also be used after the polymerization is completed by heating in an oxygen atmosphere and by performing thermal oxidative cross-linking treatment by adding a cross-linking agent such as a peroxide to increase the molecular weight. ..

In the case of dry heat treatment for the purpose of increasing the molecular weight by thermal oxidative crosslinking, the temperature is preferably 160 to 260 ° C, more preferably 170 to 250 ° C. Further, it is desirable that the oxygen concentration is 5% by volume or more, more preferably 8% by volume or more. The upper limit of the oxygen concentration is not particularly limited, but is limited to about 50% by volume. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, still more preferably 2 to 25 hours. The heat treatment device may be a normal hot air dryer or a rotary type or a heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary type or a stirring blade is used. It is more preferable to use it.

In addition, it is possible to perform a dry heat treatment for the purpose of suppressing thermal oxidation cross-linking and removing volatile components. The temperature is preferably 130 to 250 ° C, more preferably 160 to 250 ° C. Further, the oxygen concentration in this case is preferably less than 5% by volume, more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, still more preferably 1 to 10 hours. The heat treatment device may be a normal hot air dryer or a rotary type or a heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary type or a stirring blade is used. It is more preferable to use it.

In the present invention, it is essential to mix 30 to 120 parts by weight of (B) fibrous filler with 100 parts by weight of (A) polyphenylene sulfide resin, and excellent mechanical strength, toughness, and dimensional accuracy are made parallel. Necessary in the sense.

Specific examples of the (B) fibrous filler include glass fibers, glass milled fibers, glass flat fibers, irregular cross-section glass fibers, glass cut fibers, flat glass fibers, stainless fibers, aluminum fibers, brass fibers, and locks. Wool, PAN-based and pitch-based carbon fibers, carbon nanotubes, carbon nanofibers, calcium carbonate whisker, wallastenite whisker, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, aramid fiber, alumina fiber, Examples thereof include silicon carbide fiber, asbestos fiber, gypsum fiber, ceramic fiber, zirconia fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, and the like, and two or more of these can be used in combination. Further, it is more excellent mechanical strength to use these fibrous fillers by 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 sense of obtaining. Glass fibers and carbon fibers are preferred, and glass fibers are particularly preferable.

The blending amount of the (B) fibrous filler used in the present invention is 30 to 120 parts by weight, preferably 30 to 120 parts by weight, based on 100 parts by weight of the (A) PPS resin, in view of the balance of heat resistance, mechanical properties and the like. It is 30 to 90 parts by weight, more preferably 40 to 80 parts by weight. (B) If the blending amount of the fibrous filler is too small, heat resistance, mechanical properties, dimensional accuracy, etc. due to blending the fibrous filler cannot be obtained, which is not preferable. Too much tends to reduce toughness and fluidity.

Further, the PPS resin composition of the present invention may contain (C) a non-fibrous filler as long as the effects of the present invention are not impaired. Specific examples of the non-fibrous filler (C) include silicates such as talc, wallastenite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, and hydrotalcite, and oxidation. Silicon, glass powder, magnesium oxide, aluminum oxide (alumina), silica (crushed / spherical), quartz, glass beads, glass flakes, crushed / amorphous glass, glass microballoons, molybdenum disulfide, aluminum oxide (crushed / spherical) ), Translucent alumina (fibrous / plate / scaly / granular / amorphous / crushed), titanium oxide (crushed), zinc oxide (fibrous / plate / scaly / granular / amorphous / crushed) Oxides such as (product), carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, sulfates such as calcium sulfate 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 / plate / scale / granular / amorphous / crushed), calcium polyphosphate, graphite, metal powder, metal flakes, metal ribbon, metal oxidation Examples thereof include metal powders, metal flakes, and metal species of metal ribbons, and examples thereof include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Further, carbon powder, graphite, carbon flakes, reptile carbon, fullerene, graphene and the like may be mentioned, and these may be hollow, and two or more kinds of these fillers can be used in combination. Further, these non-fibrous fillers may be 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 before use. Preferred are calcium carbonate, carbon black and graphite.

The blending amount of the (C) non-fibrous filler used in the present invention is 0.5 to 50 parts by weight with respect to 100 parts by weight of the (A) PPS resin from the balance of heat resistance, mechanical properties and the like. It is preferably 0.5 to 40 parts by weight.

The PPS resin composition of the present invention may be further blended with (D) other resins as long as the effects of the present invention are not impaired. The blendable resin is not particularly limited, and specific examples thereof include polyamides such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, and aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, and poly. Polyester resins such as cyclohexyldimethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, polyolefin-based elastomers, polyether ester elastomers, polyetheramide elastomers, polyamideimide, polyacetal, polyimide, polyetherimide, polyethersulfone , Polysulfone resin, polyallyl sulfone resin, polyketone resin, polyallylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, polyamideimide resin, tetrafluoride polyethylene resin, epoxy group-containing polyolefin Examples thereof include copolymers and olefin-based copolymers.

Further, the PPS resin composition of the present invention contains 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 without impairing the effects of the present invention. A silane compound having at least one functional group selected from the above 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. , Γ-Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and other mercapto group-containing alkoxysilane compounds, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) amino Ureid group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropyl Isocyanate group-containing alkoxysilane compounds such as ethyldimethoxysilane, γ-isocyanatepropylethyldiethoxysilane, γ-isocyanatepropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) Contains amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and hydroxyl groups such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. Examples thereof include alkoxysilane compounds. Of these, an alkoxysilane having an epoxy group, an amino group, an isocyanate group, and a hydroxyl group is particularly suitable for obtaining excellent weld strength.

The PPS resin composition of the present invention contains other components such as antioxidants and heat-stabilizing agents (hindered phenol-based, hydroquinone-based, phosphorus-based, phosphite) other than the above, as long as the effects of the present invention are not impaired. System, amine system, sulfur system and their substitutes, etc.), weather resistant agents (resorcinol system, salicylate system, benzotriazole system, benzophenol system, hindered amine system, etc.), mold release agents and lubricants (montanoic acid and its metal salts, etc.) Esters, their half esters, stearyl alcohol, stearamide, stealth, bisurea, polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (niglosin, etc.), plasticizers (p-oxybenzoic acid, etc.) Octyl, N-butylbenzenesulfonamide, etc.), Antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium salt-type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate Agents, betaine-based amphoteric antioxidants, etc.), flame retardants (eg, red phosphorus, phosphoric acid ester, melamine cyanurate, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or these Combination of bromine-based flame retardant and antimony trioxide, etc.), heat stabilizer, lubricant such as calcium stearate, aluminum stearate, lithium stearate, bisphenol epoxy resin such as bisphenol A type, novolak phenol type epoxy resin, cresol novolak type Strength-enhancing materials such as epoxy resins, UV inhibitors, colorants, flame retardants and foaming agents can be added, and antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphorus) can be added. It is preferable to use a system, a phosphite system, an amine system, a sulfur system and a substitute thereof).

More preferably, a phosphorus-based antioxidant and a hindered phenol-based antioxidant are used. Specific examples thereof include tetrax (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite and bis (2,6-di) as the phosphorus-based and phosphite-based antioxidants. -T-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, triphenylphosphite, tris (2,4-) Di-t-butylphenyl) phosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, cyclic neo Pentantetraylbis (octadecylphosphite), cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphos Fight, 9,10-dihydro-9-oxa-10-phosphenylanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa -10-Phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, etc. or a mixture thereof can be exemplified.

Examples of the hindered phenolic antioxidant include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate and 4,4'-butylidenebis (3-methyl-6-). t-Butylphenol), 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4) -Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2 , 2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate , 2,2-thiobis (4-methyl-6-t-butylphenol), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5 -Di-t-Butyl-4-hydroxy-benzylphosphasphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-butyl-4-hydroxybenzyl) benzene , Bis (3,5-di-t-butyl-4-hydroxybenzyl sulfonate, ethyl calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di -T-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate , 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol), 4,4'-thiobis- (3 -Methyl-6-t-butylphenol), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -O-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 4,4'-butylidenebis (3-methyl-6-t-butylphenol, 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methyl) Phenyl) propionyloxy] ethyl] 2,4,8,10-tetraoki Saspiro [5,5] undecane, benzenepropanoic acid, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl-, 2,4,8,10-tetraoxapyro [5.5] undecane- 3,9-Diylbis (2,2-dimethyl-2,1-ethanediyl) ester, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) ) Butyric acid] glycol ester, 1,3,5-tris (3', 5'-di-t-butyl-4'-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) Trion, d-α-tocopherol, 3,9-bis (2- (3- (3-terriary butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl)- Examples include 2,4,8,10-tetraoxaspiro [5.5] undecane and / or mixtures thereof.

Examples of the amine-based antioxidant include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and poly [{6- (1,1). , 3,3,-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6, -tetramethyl-4-piperidyl) imino} hexamethylene {( 2,2,6,6,-tetramethyl-4-piperidyl) imino}], 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalate bis (1, 2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis-2,2 , 6,6-Tetramethyl-4-piperidyl-sevacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-) Piperidine) sebacate, 1- [2- [3- (3.5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-t-butyl-hydroxyphenyl) ) Propionyloxy] 2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, etc. or a mixture thereof can be exemplified.

Examples of sulfur-based antioxidants include 4,4'-thiobis (6-t-butyl-3-methylphenol), dialkyl (C12-18) 3,3'-thiodipropionate, and pentaerythrityl tetrakis (3). − Laurylthiopropionate) etc. or a mixture thereof can be exemplified.

The method for preparing the PPS resin composition of the present invention is not particularly limited, but each raw material is supplied to a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll, and 280. A typical example is a method of kneading at a temperature of about 380 ° C. The mixing order of the raw materials is not particularly limited, 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 some of the raw materials and then mixing the remaining raw materials with a side feeder during melt-kneading with a single-screw or twin-screw extruder. Further, as for the small amount additive component, it is of course possible to knead other components by the above method or the like to pelletize them, and then add them before molding and use them for molding.

The PPS resin composition of the present invention thus obtained can be used for forcible injection molding.

In the present invention, forcible punching is a molding method in which a mold is pulled out in the axial direction over a bulging portion of a molded product, and a molded product having a relatively small bulging portion on the outside or inside of a pipe shape is formed. Forcible punching is possible by taking out with a two-way punching die. The resin composition of the present invention is particularly effective in obtaining a molded product having a bulging portion on the outside of the pipe shape.

The PPS resin composition of the present invention needs to have a flexural modulus E1 of 7 to 20 GPa at 23 degrees Celsius when it is made into a molded product. This is because when E1 is low, it does not have rigidity as a product, so that the product strength and dimensional accuracy are deteriorated. On the other hand, if E1 is too high, it cannot be deformed because the rigidity is too high, and it cannot be forcibly removed.

The PPS resin composition of the present invention needs to have a tensile strength σ1 at 120 degrees Celsius or more of 50 MPa or more. If the tensile strength at 120 degrees is less than this, it cannot be forcibly removed due to breakage during molding.

In the PPS resin composition of the present invention, it is important that α represented by (Formula 1) satisfies 0.011 ≦ α ≦ 0.033, preferably 0.012 ≦ α ≦ 0.030. More preferably, 0.012 ≦ α ≦ 0.022. Here, α is a parameter representing the balance between the tensile strength and the flexural modulus during forcible punching, and the tensile speed of 50 mm / representing the speed of removal from the mold at 120 degrees Celsius, which is the temperature at which the product is removed from the mold. It is obtained by dividing the tensile strength [Pa] at min by the flexural modulus [Pa] at 120 degrees. If the tensile strength at 120 degrees is too small with respect to the flexural modulus, the molded product will break. If it is too strong, the molded product may have a poor appearance such as wrinkles. If α is too small, it means that the strength is low or the elastic modulus is high. In the former case, it cannot withstand the stress applied to the deformation that occurs when forcibly pulling out, and “tear” occurs at the base of the bulge. However, in the latter case, it cannot be forcibly pulled out because it cannot be deformed due to its high rigidity. On the other hand, if α is too high, it means that the elastic modulus is low, and since it does not have rigidity as a product, it leads to deterioration of product strength and dimensional accuracy.

In the molding method for forcibly punching using the resin composition of the present invention, the resin temperature is 300 to 330 degrees Celsius, preferably 300 to 320 degrees Celsius. If the resin temperature is too low, the resin cannot obtain the melt viscosity required for injection molding, and if it is too high, the resin is soft when forcibly removed, causing "tear". Further, the mold is molded at a mold temperature of 100 to 140 degrees Celsius, preferably 100 to 120 degrees Celsius. If the mold temperature is too low, crystallization will proceed faster and more stress will be generated during forcible removal, causing cracks. If the mold temperature is too high, the rigidity of the resin will be insufficient during forcible removal, resulting in "tear". ..

In the mold release after molding, the mold (core mold) for molding the inner peripheral surface of the cylindrical portion is removed, and then the molded product is forcibly removed from the mold (cavity mold) for molding the outer surface including the bulging portion 1.

An example of a molded product obtained by forcible punching using the PPS resin composition of the present invention will be described with reference to the drawings. FIG. 1 is a resin injection-molded product targeted by the present invention, and is a perspective view showing a main part thereof. It has a cylindrical portion 1, and a bulging portion 2 having a larger outer diameter than other portions of the cylindrical portion is provided at the tip of the cylinder. In the embodiment of the present invention, the shape of the bulging portion is not particularly limited, but it is preferable that the general bulging portion has a mountain shape from the viewpoint of insertion and prevention of disconnection. Further, it is suitable for obtaining a molded product having an undercut ratio Ki represented by (Equation 2) of 3.5 ≦ Ki ≦ 14 with respect to the bulging portion. It is preferably 4.0 ≦ Ki ≦ 10.0, and more preferably 4.0 ≦ Ki ≦ 6.0. A molded product having a small undercut rate is not preferable because it has an insufficient function as a stopper for preventing it from coming off when it is used for insertion joining with a pipe. On the other hand, if the undercut rate is too large, forcible punching becomes difficult.

Examples will be shown below and the present invention will be described in more detail, but the present invention is not limited to the description of these examples.

Reference Example Polymerization of PPS resin The MFR values of PPS-1, 2 obtained by the following methods were measured according to JIS K7210 (2014).
[Reference Example 1] Preparation of PPS-1 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.94 kg (70) of 96% sodium hydroxide in a 70-liter autoclave with a stirrer and a bottom plug valve. .63 mol), 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), 0.513 kg (6.25 mol) of sodium acetate, and 3.82 kg of ion-exchanged water were charged at normal pressure. The reaction vessel was cooled to 200 ° C. after distilling 8.09 kg of water and 0.28 kg of NMP by gradually heating to 245 ° C. over about 3 hours while passing through nitrogen. The amount of residual water in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

After that, the mixture was cooled to 200 ° C., 10.34 kg (70.32 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the reaction vessel was stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min, and the reaction was carried out at 270 ° C. for 140 minutes. Then, 2.67 kg (148.4 mol) of water was press-fitted while cooling from 270 ° C. to 250 ° C. over 15 minutes. Then, after gradually cooling from 250 ° C. to 220 ° C. over 75 minutes, the contents were rapidly cooled to near room temperature and the contents were taken out.

The contents were diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (opening 0.175 mm) to obtain a solid substance. The obtained solid was similarly washed and filtered with about 35 liters of NMP. The operation of diluting the obtained solid matter with 70 liters of ion-exchanged water, stirring at 70 ° C. for 30 minutes, and then filtering with an 80-mesh wire mesh to collect the solid matter was repeated a total of 3 times. The obtained solid matter and 32 g of acetic acid are diluted with 70 liters of ion-exchanged water, stirred at 70 ° C. for 30 minutes, filtered through an 80 mesh wire net, and the obtained solid matter is further diluted with 70 liters of ion-exchanged water. After stirring at 70 ° C. for 30 minutes, the solid matter was collected by filtration through an 80 mesh wire net. The solid matter thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS.

[Reference Example 2] Preparation of PPS-2 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.92 kg (70) of 96% sodium hydroxide in a 70-liter autoclave with a stirrer and a bottom plug valve. .20 mol), 13.86 kg (140.00 mol) of N-methyl-2-pyrrolidone (NMP), 2.19 kg (26.67 mol) of sodium acetate, and 10.50 kg of ion-exchanged water were charged at normal pressure. The reaction vessel was cooled to 160 ° C. after distilling 14.74 kg of water and 0.28 kg of NMP by gradually heating to 240 ° C. over about 3 hours while passing through nitrogen. The amount of residual water 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 charged alkali metal sulfide.

Next, 10.25 kg (69.76 mol) of p-dichlorobenzene and 6.45 kg (65.17 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and 0.8 ° C./min with stirring at 240 rpm. The temperature was raised from 200 ° C. to 250 ° C. at the same rate as above, and the temperature was maintained at 250 ° C. for 70 minutes. Then, the temperature was raised from 250 ° C. to 278 ° C. at a rate of 0.8 ° C./min, and the temperature was maintained at 278 ° C. for 78 minutes. The bottom valve of the autoclave was opened, the contents were flushed into a container with a stirrer for 15 minutes while pressurizing with nitrogen, and the mixture was stirred at 250 ° C. for a while to remove most of NMP.

The obtained solid matter 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 with a glass filter. Then, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter and suction filtered to obtain a cake.

90 liters of the obtained cake and ion-exchanged water 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 the temperature was maintained for 30 minutes. The autoclave was then cooled and the contents were removed.

After suction-filtering the contents with a glass filter, 76 liters of ion-exchanged water at 70 ° C. was poured into the contents and suction-filtered to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS.

The obtained PPS had an MFR of 200 g / 10 minutes.

[Method for producing compounding material and PPS resin composition used in Examples and Comparative Examples]
PPS obtained in Reference Examples 1 to 5 using a twin-screw extruder (TEX-44 manufactured by Japan Steel Works, Ltd.) having a 44 mm diameter intermediate addition port with a cylinder set temperature of 310 ° C. and a screw rotation speed of 200 rpm. 100 parts by weight of resin (A), (B) fibrous inorganic material, and (C) non-fiber filler are supplied from the intermediate addition port at the ratios shown in Table 1 and melt-kneaded at a discharge rate of 40 kg / hour to obtain pellets. It was. Each of the following characteristics was evaluated using this pellet. The measurement and test of the physical properties in the examples were carried out by the following methods. The results are shown in Table 1.

(B) Fibrous filler: Glass chopped strand "ECS T-760H" manufactured by Nippon Electric Glass Co., Ltd.
(C) Non-fiber filler: Calfine, heavy calcium carbonate "KSS-1000"
(D) Other resin: Ethylene, glycidyl methacrylate, methyl acrylate copolymer "Bond First E manufactured by Sumitomo Chemical Co., Ltd."

[Resin pellet adjustment method]
Each of the above raw materials (A), (C) and (D) is dry-blended in advance at the ratio shown in Table 1, the raw material (B) is charged from the side feeder, and the cylinder temperature is 280 ° C. (lower side of the hopper) to 310 ° C. ( A pellet-shaped resin composition was prepared by melt-kneading and pelletizing using a screw-type twin-screw extruder (TEX-44 manufactured by Japan Steel Works, Ltd.) set on the discharge port side. Using these pellets, bending strength, water absorption rate, and epoxy adhesiveness were measured by each of the means shown below. It should be noted that, which is common to all measurements, the pellets were pre-dried for 3 hours in a hot air dryer whose temperature was adjusted to 130 ° C. before molding.

[Measuring method]
(1) Flexural modulus (E1)
The measurement was performed according to the ISO 178 (2010) method. Specifically, the measurement was performed as follows. The PPS resin composition pellet of the present invention was dried at 130 ° C. for 3 hours using a hot air dryer, and then an injection molding machine (SE-50D) manufactured by Sumitomo Heavy Industries was set at a cylinder temperature of 310 ° C. and a mold temperature of 145 ° C. ), And the average velocity of the molten resin passing through the cross-sectional area of the central parallel part is 400 ± 50 mm / s using a mold of type A1 test piece shape specified in ISO 20753 (2008). Injection molding was performed to obtain a test piece. A central parallel portion of this test piece was cut out to obtain a type B2 test piece. This test piece was adjusted for 16 hours under the conditions of 23 ° C. and 50% relative humidity, and then the flexural modulus was adjusted under the conditions of 23 ° C. and 50% relative humidity, a span of 64 mm, and a test speed of 2 mm / s. Measurements were made.

(2) Flexural modulus (E2)
The measurement was performed according to the ISO 178 (2010) method. Specifically, the measurement was performed as follows. The PPS resin composition pellet of the present invention was dried at 130 ° C. for 3 hours using a hot air dryer, and then an injection molding machine (SE-50D) manufactured by Sumitomo Heavy Industries was set at a cylinder temperature of 310 ° C. and a mold temperature of 145 ° C. ), And the average velocity of the molten resin passing through the cross-sectional area of the central parallel part is 400 ± 50 mm / s using a mold of type A1 test piece shape specified in ISO 20753 (2008). Injection molding was performed to obtain a test piece. A central parallel portion of this test piece was cut out to obtain a type B2 test piece. This test piece was adjusted for 16 hours under the conditions of 23 ° C. and 50% relative humidity, and then the flexural modulus was measured under the conditions of an atmosphere of 120 ° C., a span of 64 mm, and a test speed of 2 mm / s.

(3) Tensile strength (σ1)
The measurement was performed according to the ISO 527-1, 2 (2012) method. However, the tensile speed was changed from 5 mm / s, which is a normal condition, to 50 mm / s. Specifically, the measurement was performed as follows. The PPS resin composition pellet of the present invention was dried at 130 ° C. for 3 hours using a hot air dryer, and then an injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. was set to a cylinder temperature of 310 ° C. and a mold temperature of 145 ° C. The average velocity of the molten resin supplied to (SE-50D) and passed through the cross-sectional area of the central parallel portion is 400 ± 50 mm / s using a mold of type A1 test piece shape specified in ISO 20753 (2008). Injection molding was performed under the conditions to obtain a test piece. After adjusting the state of this test piece for 16 hours under the conditions of 23 ° C. and 50% relative humidity, the tensile strength and the test speed under the conditions of 120 ° C., distance between grippers: 114 mm, and test speed: 50 mm / s, and Tensile elongation measurement was performed.

(4) Superiority or Inferiority of Forcible Punching Moldability A molded product having a cylindrical portion 2 having a bulging portion 1 on the end face as shown in FIG. 1 was injection-molded, and forcibly punching molding was performed. If cracks were present, they were rated as "inferior" (x), and if they were not present, they were rated as "excellent" (○).

(5) Appearance When wrinkles were not confirmed, it was rated as "excellent" (◎), when it was confirmed a little, it was rated as "normal" (○), and when it was confirmed in large quantities, it was rated as "inferior" (x).

(6) Strength of Forced Injection Molded Product The strength starts from the point where the forceless injection molded product obtained by using the PPS resin composition of the present invention is rotated 90 degrees from the gate portion as shown in FIG. It was cut so as to be a semicircle, and further, it was carried out with a test piece cut out with a width of 10 mm including a bulging portion. The test piece including the gate portion was defined as a non-welded portion. After adjusting the state of this test piece for 16 hours under the conditions of 23 degrees Celsius and 50% relative humidity, bending measurement is performed under the conditions of 23 degrees Celsius and 50% relative humidity and a test speed of 1 mm / s. Therefore, the intensity [MPa] was measured.

[Examples 1 to 5]
[Comparative Examples 1 to 3]
In Examples 1 to 5 and Comparative Examples 1 and 2, a molded product having a cylindrical portion 2 having a bulging portion 1 on the end face as shown in FIG. 1 was injection-molded, and forcibly punched molding was performed. In Comparative Example 3, a molded product having a cylindrical portion 2 having a bulging portion 1 on the end surface as shown in FIG. 1 was injection-molded, and the molded product was obtained by mold splitting without forcibly punching. These molded products have an outer diameter of Φ40.4 mm and an inner diameter of Φ35.0 mm of the bulging portion 1, and an outer diameter of Φ38.0 mm and an inner diameter of Φ33.0 mm of the other portion of the cylindrical portion 2 (the portion other than the bulging portion 1). Is. The undercut rate Ki of this molded product is 5.9. The results are shown in Table 1.

As can be seen from the comparison between Examples 1 to 5 and Comparative Example 1, even if the tensile strength at 120 degrees Celsius is the same, if α is low, forcible punching cannot be performed.

As can be seen from the comparison between Examples 1 to 5 and Comparative Example 2, in the case where the fibrous filler is not contained, forcible punching is possible, but the strength of the product is low.

As can be seen from the comparison between Examples 1 to 5 and Comparative Example 3, Examples 1 to 5 have sufficient strength as a product when the strength with the molded product obtained by mold split molding is compared. It turns out that there is.

The molded product made of the polyphenylene sulfide resin composition of the present invention is excellent in heat resistance, chemical resistance, heat resistance and water resistance, and mechanical properties originally exhibited by the PPS resin. Therefore, for example, it is used for electric / electronic use, automobile use, and water supply use. It is useful for general miscellaneous goods applications, building materials, etc., specifically, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminals. For boards, metamorphic devices, plugs, printed boards, tuners, speakers, microphones, headphones, small motors, porcelain head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc. Typical electrical and electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio / laser discs (registered trademarks), compact discs and other audio equipment parts, lighting parts, etc. Household and office electrical parts such as refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc .; office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning jigs, motor parts, Machine-related parts such as lighters and typewriters, optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machine-related parts; water faucet tops, mixing faucets, pump parts, pipe joints, valves, cheese , Joints, sockets, water volume control valves, pressure reducing valves, relief valves, electromagnetic valves, hot water temperature sensors, water volume sensors, water meter housings, and other water-related parts; valve alternator terminals, alternator connectors, IC regulators, light dial potentials Various valves such as meter base and exhaust gas valve, various pipes related to fuel, exhaust system and intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water Sensor, hot water temperature sensor, brake pad wear sensor, throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor -, Water pump, water pump impeller, water inlet, water outlet, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve Coil, fuse connector, horn terminal, electrical component insulation plate, ECU case, condenser case, power module component, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device Examples include automobile / vehicle-related parts such as cases, vehicle speed sensors, cable liners, gasoline tanks, and various other uses. In particular, water-related parts not only have a poor appearance when a large amount of gas is generated during molding, but also deteriorate the sealing property of water and cannot be formed as a part. However, when the PPS resin composition of the present invention is used, molding is performed. Since the amount of gas generated at the time is small, it can be preferably used.

1 bulge 2 Cylindrical part D bulge outer diameter H Cylindrical outer diameter

Claims (5)

With respect to 100 parts by weight of (A) polyphenylene sulfide resin, (B) a polyphenylene sulfide resin composition for forcible injection molding containing 30 to 120 parts by weight of a fibrous filler has a bulging portion on the outside of a cylindrical pipe. It is an injection molded product
The polyphenylene sulfide resin composition has a flexural modulus E1 at 23 degrees Celsius of 7 to 20 GPa and a tensile strength σ1 at a tensile speed of 50 mm / min at 120 degrees Celsius of 50 MPa or more.
The α represented by (Formula 1) of the polyphenylene sulfide resin composition is 0.011 ≦ α ≦ 0.033.
An injection-molded article having an undercut ratio Ki represented by (Equation 2) of the bulging portion of 3.5 ≦ Ki ≦ 14.

The injection-molded article according to claim 1, wherein the polyphenylene sulfide resin composition contains 30 to 90 parts by weight of (B) a fibrous filler with respect to 100 parts by weight of (A) polyphenylene sulfide resin. The injection-molded article according to claim 1 or 2, wherein the α is 0.012 ≦ α ≦ 0.030. The injection-molded article according to any one of claims 1 to 3, wherein the undercut ratio Ki of the bulging portion is 4.0 ≦ Ki ≦ 10.0. A method for producing an injection-molded article, which comprises producing the injection-molded article according to any one of claims 1 to 4 by forcible punching .