JP6885096B2 - Polyphenylene sulfide resin composition and molded article - Google Patents

Description

The present invention provides a polyphenylene sulfide resin composition and a molded product thereof, which are excellent in fluidity, low-temperature toughness, and cold-heat impact resistance of a welded portion while maintaining high dimensional accuracy.

Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has a good balance of rigidity, heat resistance, heat resistance, water resistance, chemical resistance, electrical insulation, and molding processability. Widely used for parts.

On the other hand, PPS resin is inferior in toughness to other engineering plastics. Therefore, for the purpose of improving the cold impact resistance by repeating low temperature and high temperature, which is required in applications where a metal is inserted, a PPS resin composition obtained by blending an olefin copolymer with a PPS resin has been studied. It is done.

By the way, Patent Document 1 contains a reactive olefin copolymer, an unmodified olefin copolymer containing butyl acrylate, and an inorganic filler in a PPS resin for the purpose of exhibiting impact resistance. The composition is described.

On the other hand, Patent Documents 2 and 3 describe a composition obtained by blending a reactive olefin copolymer, an unmodified olefin copolymer, and an inorganic filler with a PPS resin for the purpose of exhibiting cold and thermal impact resistance. Is described.

Further, in Patent Documents 4 and 5, a reactive olefin copolymer, an unmodified olefin copolymer, and an inorganic filler are blended with a PPS resin for the purpose of adapting to a molded product containing a weld portion. The composition is described.

Further, Patent Document 6 describes a composition obtained by blending a reactive olefin-based copolymer and an unmodified olefin-based copolymer containing butyl acrylate with a PPS resin for the purpose of improving low-temperature toughness. ing.

Japanese Unexamined Patent Publication No. 1-30467 Japanese Unexamined Patent Publication No. 2008-75049 JP-A-2002-129014 Japanese Unexamined Patent Publication No. 2001-31867 JP-A-2002-3716 Japanese Unexamined Patent Publication No. 2008-75034

The present invention provides a polyphenylene sulfide resin composition having excellent fluidity, low temperature toughness, and cold thermal shock resistance of a welded portion.

In recent years, with the spread of hybrid cars and electric cars, the number of products with metal inserts mounted on automobiles such as bus bars has increased significantly, and the shape of the products is small and complicated due to the need for space saving. It has become. Along with this, the number of welds formed in the product is increasing, and there is a demand for a resin composition having excellent cold and thermal impact resistance, which does not cause cracks in the welds.

Further, cracks due to thermal impact occur as a result of the resin shrinking on the low temperature side to generate stress, which is repeatedly applied, resulting in the resin gradually deteriorating. As mentioned above, studies have been conducted to improve the toughness by blending an olefin copolymer with the PPS resin. However, in order to further improve the cold thermal shock resistance, the toughness in a low temperature environment is improved and shrinkage is performed. It is important to relieve the stress generated. On the other hand, increasing the toughness by reducing the amount of inorganic filler or increasing the amount of olefin copolymer may deteriorate the mechanical strength and dimensional accuracy of the product.

Further, in order to mold a thin-walled, complicated-shaped product, a resin composition having good fluidity is required, but the fluidity and the weld strength are in a contradictory relationship, and good fluidization of the resin composition is a weld strength. As a result, it may cause a decrease in the cold and thermal impact resistance of the weld portion.

Therefore, the PPS resin composition used for such applications in recent years is required to have a good flow, excellent low temperature toughness, and excellent thermal impact resistance of the welded portion while maintaining high dimensional accuracy.

However, the composition described in Patent Document 1 has a large amount of the olefin copolymer and a small amount of the inorganic filler, so that the dimensional accuracy is insufficient and the mold stain property is also insufficient. Is. On the other hand, although Patent Documents 2 to 5 describe a reactive olefin-based copolymer containing an acrylic acid ester and an unmodified olefin-based copolymer containing butyl acrylate, a specific study using these in combination is not possible. No composition has been found that has not been implemented and has improved low temperature toughness and cold thermal impact resistance of the weld portion. Further, the composition of Patent Document 6 does not contain an inorganic filler, and its mechanical strength and dimensional accuracy are insufficient.

The present inventors have reached the present invention as a result of repeated diligent studies in order to solve the above problems.

That is, the present invention provides the following.
(1) A total of (B) a reactive olefin-based copolymer containing an acrylic acid ester and (C) an unmodified olefin-based copolymer containing butyl acrylate with respect to 100 parts by weight of (A) polyphenylene sulfide resin. A polyphenylene sulfide resin composition comprising 10 to 20 parts by weight and 100 to 200 parts by weight of (D) an inorganic filler.
(2) The weight ratio of the reactive olefin copolymer containing (B) acrylate ester / the unmodified olefin copolymer containing butyl acrylate (C) is 1/4 to 4/1 (1/4 to 4/1). 1) The polyphenylene sulfide resin composition according to the above.
(3) The reactive olefin-based copolymer containing (B) acrylic acid ester is an olefin copolymer containing ethylene, a glycidyl ester of α, β-unsaturated acid, and an acrylic acid ester (1). ), Or the polyphenylene sulfide resin composition according to (2).
(4) The polyphenylene sulfide resin composition according to any one of (1) to (3), wherein the unmodified olefin copolymer containing butyl acrylate (C) is an olefin copolymer containing ethylene and butyl acrylate. Stuff.
(5) The (D) inorganic filler is at least one selected from (D-1) glass fiber, (D-2) calcium carbonate and (D-3) metal hydroxide. 4) The polyphenylene sulfide resin composition according to any one.
(6) The polyphenylene sulfide resin composition according to any one of (1) to (5), wherein the (A) polyphenylene sulfide resin is a crosslinked polyphenylene sulfide resin.
(7) The amount of gas generated when the (A) 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) 250 ° C. for 5 minutes, 20. A polyphenylene sulfide resin having a residual amount of 4.0% by weight or less when melted in double the weight of 1-chloronaphthalene and subjected to hot pressure filtration with a PTFE membrane filter having a pore size of 1 μm (1) to (6). The polyphenylene sulfide resin composition according to the above.
(8) An alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureido group, and the above-mentioned (A) polyphenylene sulfide resin by 100 weight. The polyphenylene sulfide resin composition according to any one of (1) to (7), which is obtained by blending 0.1 to 3 parts by weight with respect to parts.
(9) A molded product comprising the polyphenylene sulfide resin composition according to any one of (1) to (8).
(10) The molded product according to (9), wherein the molded product includes two or more weld portions.
(11) The molded product according to (9) or (10), wherein the molded product includes a metal insert.

The present invention has an unknown property that a PPS resin composition having a specific composition has both excellent fluidity and low-temperature toughness while maintaining high dimensional accuracy, and also has high thermal impact resistance in a welded portion. We have found that the composition containing a metal hydroxide is also excellent in tracking resistance. The PPS resin composition of the present invention is useful for a molded product having a complicated shape, and particularly useful for a molded product containing two or more weld portions and a molded product containing a metal insert.

It is the schematic of the molded article used for the evaluation of cold thermal shock resistance -1. It is the schematic of the molded product used for the evaluation of cold thermal shock resistance-2. It is the schematic of the molded article used for the evaluation of the dimensional accuracy. It is the schematic of the molded product used for the evaluation of the mold stain property.

Hereinafter, embodiments of the present invention will be described. In the present invention, "weight" means "mass".

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

(1) PPS resin 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 even more 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 oligomeric properties 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.

[Sulfidating 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, an alkali metal sulfide prepared in situ in the reaction system from an alkali metal hydroxide such as lithium hydroxide or 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. It shall be.

It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfidizing 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, tetramethylenesulfoxide, 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 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 sulfide agent. ..

[Molecular weight regulator]
In the present invention, a monohalogen compound (not necessarily an aromatic compound) is used as the polyhalogenated aromatic 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 hydroxide, alkali metal carbonate and alkali metal bicarbonate are added in approximately equal chemical equivalents and reacted. May be formed by. Among the above alkali metal carboxylates, the lithium salt has high solubility in the reaction system and has a large auxiliary effect, but is expensive, and the potassium, rubidium and cesium salts have insufficient solubility 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. The range is from 0.01 to 0.088 mol, which 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 oligomeric properties. 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 sulfide 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 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 side reactions is the production of thiophenol, and the addition of a polymerization stabilizer can suppress the production 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 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 sulfide 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 at the start of the process or at 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 with a pre-step, a polymerization reaction step, a recovery step, and a 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. This method is not particularly limited, but preferably, an alkali metal hydrosulfide and an alkali metal hydroxide are used 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, a method of distilling off water by raising the temperature to at least 150 ° C. or higher, preferably 180 to 260 ° C. under normal pressure or reduced pressure can be mentioned. A polymerization aid may be added at this stage. Further, in order to promote the distillation 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 of charging these raw materials 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 (A) 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 step, 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 one of the preferable methods to carry out the above-mentioned recovery under quenching conditions, and a flash method is mentioned as one of the preferable methods 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 is recovered. 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 if necessary, stirring or heating can be performed as appropriate. 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, about 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. Below 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 effect of preferable chemical modification of the PPS resin by hot water washing of the present invention. The operation of 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 aromatic hydrocarbon solvents such as benzene, toluene and xylene. 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 of 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 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. As a specific method for washing the PPS resin with water containing an alkaline earth metal salt, the following method can be exemplified. 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, and it is more 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 used in the present invention can also be used as a crosslinked PPS by heating in an oxygen atmosphere after completion of polymerization or by adding a crosslinking agent such as a peroxide.

When a dry heat treatment is performed for the purpose of cross-linking by thermal oxidation treatment, 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 suppress cross-linking due to thermal oxidation treatment and perform dry heat treatment for the purpose of 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.

Among them, in the present invention, the PPS resin having the following characteristics (1) and (2) is particularly preferably used in terms of high weld strength and high antifreeze resistance.

(1) The amount of gas generated 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, and more preferably 0.22% by weight or less. It is desirable to have. A PPS resin having such properties can be obtained by appropriately applying the above-mentioned cleaning and thermal oxidation treatment. It is preferable to reduce the amount of gas generated to 0.3% by weight or less because the volatile components are reduced and the weld strength and antifreeze resistance are improved. The lower limit of the amount of gas generated after the thermal oxidation treatment is preferably small, but the preferable lower limit is 0.01% by weight. By setting the content to 0.01% by weight or more, it is possible to prevent the thermal oxidation treatment time from becoming too long and to prevent economic disadvantage. Further, it is also preferable in the sense of preventing the gelled product from being easily formed due to the prolongation of the thermal oxidation treatment time, which is one of the causes of molding defects.

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

(2) The amount of residue when dissolved in 20 times by weight of 1-chloronaphthalene at 250 ° C. for 5 minutes and subjected to hot pressure filtration with a PTFE membrane filter having a pore size of 1 μm is 4.0% by weight or less, preferably 3. It is preferably 5.5% by weight or less, more preferably 3.0% by weight or less. When the amount of the residue is 4.0% by weight or less, the volatile components are reduced and the weld strength and antifreeze resistance are improved, which is preferable. The lower limit of the residual amount is not particularly limited, but is preferably 1.5% by weight or more, preferably 1.7% by weight or more. By setting the amount of the residue to 1.5% by weight or more, it is possible to obtain the effect of advancing the cross-linking by the thermal oxidation treatment and reducing the volatile components at the time of melting. A PPS resin having such properties can be obtained by appropriately applying the above thermal oxidation treatment.

The amount of the residue is measured by using a PPS resin pressed film having a thickness of about 80 μm as a sample and using a SUS test tube equipped with a high-temperature filtration device, a pneumatic cap and a collection funnel. Specifically, first, a membrane filter having a pore size of 1 μm is set in a SUS test tube, and then a press film-formed PPS resin having 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 filtration device at 250 ° C. and heated and shaken for 5 minutes. Next, a syringe containing air is connected to the pneumatic cap, and then the piston of the syringe is pushed out to perform thermal filtration by pneumatic pressure. As a specific method for quantifying 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 adopting the above-mentioned production method, it is possible to obtain a PPS resin suitable for a PPS resin composition having excellent high weld strength and high antifreeze resistance, and the PPS resin according to the present invention. Is preferably used. It is preferable to blend such a PPS resin as a PPS resin to be blended in the PPS resin composition of the present invention, but by using at least 10% by weight of the PPS resin as such a PPS resin, the PPS resin composition It can be provided with excellent heat resistance, high weld strength, and high antifreeze resistance. It is preferable that at least 30% by weight of the PPS resin blended in the PPS resin composition is such a PPS resin, and more preferably 50% by weight or more.

In the PPS resin composition of the present invention, the total blending amount of the reactive olefin copolymer containing (B) acrylate ester and the unmodified olefin copolymer containing butyl acrylate (C) is (A). ) 10 to 20 parts by weight with respect to 100 parts by weight of PPS resin. These are necessary in the sense of providing excellent fluidity, low temperature toughness, and cold and thermal impact resistance of the weld portion in parallel, and in the sense of imparting appropriate strength and dimensional accuracy.

In the present invention, the reactive olefin-based copolymer is an olefin-based copolymer in which at least one or more kinds of reactive functional groups such as epoxy group, carboxylic acid, and acid anhydride are introduced. On the other hand, the unmodified olefin-based copolymer is an olefin-based copolymer in which the reactive functional group has not been introduced.

The total of the reactive olefin copolymer containing (B) acrylate and the unmodified olefin copolymer containing butyl acrylate is 10 parts by weight with respect to 100 parts by weight of the (A) PPS resin. If it is less than, it is not preferable because appropriate cold and thermal impact resistance as a composition cannot be obtained. Further, when the total of the reactive olefin copolymer containing (B) acrylic acid ester and the unmodified olefin copolymer containing butyl acrylate (C) exceeds 20 parts by weight, the fluidity deteriorates. , It is not preferable because the moldability is impaired. Further, it is not preferable because appropriate dimensional accuracy cannot be obtained. Further, it is not preferable because the stainability of the mold during continuous molding deteriorates. In particular, with respect to 100 parts by weight of (A) PPS resin, the total amount of the reactive olefin-based copolymer containing (B) acrylate ester and the unmodified olefin-based copolymer containing butyl acrylate (C) is 10 to 10. It should be in the range of 20 parts by weight, with a range of 12-18 parts by weight being particularly preferred. The total of the reactive olefin-based copolymer containing (B) acrylate ester and the unmodified olefin-based copolymer containing butyl acrylate (C) is 13 to 17 with respect to 100 parts by weight of (A) PPS resin. In the range of parts by weight, it is particularly preferable because it has excellent heat resistance, appropriate mechanical strength as a composition, and dimensional accuracy.

Further, it is excellent to use a reactive olefin copolymer containing (B) acrylic acid ester and an unmodified olefin copolymer containing butyl acrylate in combination to provide excellent low temperature toughness and a welded portion. It is preferable to obtain the cold thermal impact resistance of the above. These ratios are preferably (B) / (C) = 1/4 weight ratio to 4/1 weight ratio, and the range of (B) / (C) = 1/2 weight ratio to 2/1 weight ratio. It is more preferable because it has an excellent balance between fluidity during molding, low temperature toughness, and cold and thermal impact resistance of the weld portion.

Examples of the reactive olefin copolymer containing the (B) acrylic acid ester include α-olefin and α such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. , Copolymers with alkyl esters of β-unsaturated acids, such as ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / butyl acrylate copolymers, ethylene / methyl methacrylate copolymers It can be obtained by introducing a monomer component (functional group-containing component) having an epoxy group into a polymer, an ethylene / ethyl methacrylate copolymer, an ethylene / butyl methacrylate copolymer, etc., and the functional group-containing component thereof. Examples of the above include monomers containing an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl etacrilate, glycidyl itaconate, and glycidyl citracone. The method for introducing these functional group-containing components is not particularly limited, and the olefin-based (co) polymer may be copolymerized when (co-) polymerized, or the olefin-based (co) polymer may be graft-introduced using a radical initiator. You can use a method such as making it. The amount of the functional group-containing component introduced is preferably in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on all the monomers constituting the modified olefin-based (co) polymer. Appropriate. Specific examples of the olefin-based copolymer having a glycidyl group obtained by introducing a monomer component having an epoxy group into a particularly useful olefin polymer include an ethylene / propylene-g-glycidyl methacrylate copolymer ("". "G" represents a graft, the same applies hereinafter), ethylene / 1-butene-g-glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / In addition to glycidyl methacrylate copolymers, ethylene / methyl methacrylate / glycidyl methacrylate copolymers, or glycidyl esters of α-olefins such as ethylene and propylene and α, β-unsaturated acids, and other monomers. An epoxy group-containing olefin-based copolymer containing the above as an essential component is also preferably used.

Preferred examples include ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer and the like. Particularly preferred are ethylene / methyl acrylate / glycidyl methacrylate copolymers.

On the other hand, as the unmodified olefin copolymer containing (C) butyl acrylate, α-olefin and α, β-unsaturated acid such as n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, etc. Examples of copolymers with alkyl esters include ethylene / n-butyl acrylate copolymer, t-butyl ethylene / acrylate copolymer, and isobutyl acrylate copolymer.

Particularly preferred are ethylene / n-butyl acrylate copolymers.

The blending amount of the (D) inorganic filler in the PPS resin composition of the present invention is 100 to 200 parts by weight of the (D) inorganic filler with respect to 100 parts by weight of the (A) PPS resin. It is necessary in the sense that excellent mechanical strength, toughness, and dimensional accuracy are parallel. Here, when a plurality of (D) inorganic fillers are used, the total blending amount is taken as the blending amount of (D) the inorganic filler.

If the amount of the (D) inorganic filler is less than 100 parts by weight with respect to 100 parts by weight of the (A) PPS resin, appropriate dimensional accuracy as a composition cannot be obtained, which is not preferable. Further, when the amount of the inorganic filler (D) exceeds 200 parts by weight, the melt fluidity of the composition is lowered, appropriate molding processability cannot be obtained, and toughness cannot be obtained, which is not preferable. Further, in particular, the amount of the (D) inorganic filler needs to be in the range of 100 to 200 parts by weight with respect to 100 parts by weight of the (A) PPS resin, and the range of 100 to 190 parts by weight is particularly preferable. The range of 100 to 190 parts by weight of the (D) inorganic filler with respect to 100 parts by weight of the (A) PPS resin 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 (D) inorganic filler include glass fiber, glass milled fiber, glass flat fiber, irregular cross-section glass fiber, glass cut fiber, flat glass fiber, stainless fiber, and aluminum fiber. And brass fiber, rock wool, PAN-based and pitch-based carbon fiber, carbon nanotube, carbon nanofiber, calcium carbonate whisker, wallastenite whisker, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, aramid Examples thereof include fibers, alumina fibers, silicon carbide fibers, asbestos fibers, gypsum fibers, ceramic fibers, zirconia fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, 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 pretreating them 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.

(D) Specific examples of the non-fibrous filler as the inorganic filler include talc, wallastenite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, and hydrotalcite. Sirates such as silicate, silicon oxide, 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), translucent alumina (fibrous / plate / scale / granular / amorphous / crushed), titanium oxide (crushed), zinc oxide (fibrous / plate / scale / Oxides such as granular, amorphous, and crushed products), carbonates such as calcium carbonate, magnesium carbonate, and zinc carbonate, sulfates such as calcium sulfate and barium sulfate, and metals such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. Hydroxide, silicon carbide, carbon black and silica, graphite, aluminum oxide, translucent aluminum oxide (fibrous, plate-like, scaly, granular, amorphous, crushed product), calcium polyphosphate, graphite, metal powder, metal Examples include flakes, metal ribbons, and metal oxides, wherein specific examples of metal powders, metal flakes, and metal species of metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Etc. can be exemplified. Further, carbon powder, graphite, carbon flakes, scaly 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, graphite and metal hydroxides. Among them, metal hydroxides are suitable for obtaining excellent tracking resistance.

Here, the tracking failure means that when a voltage is applied to the surface of a soiled insulator, a short-circuit current flows along with the formation of a carbonized conductive path.

Examples of the metal hydroxide used in the present invention include magnesium hydroxide, aluminum hydroxide, and calcium hydroxide, but magnesium hydroxide is preferably used in consideration of the effect of improving tracking resistance.

Examples of magnesium hydroxide used in the present invention include magnesium hydroxide having a relatively high purity containing 80% by weight or more of an inorganic substance _{represented by the chemical formula Mg (OH) 2, and has tracking resistance, mechanical strength, and melt viscosity.} From the point of view, it preferably contains _{80% by weight or more of the inorganic substance represented by Mg (OH) 2} , 5% by weight or less of CaO content, 1% by weight or less of chlorine content, and more preferably 95% by weight or more _{of Mg (OH) 2.} CaO content of 1 wt% or less, a chlorine content 0.5 wt% or less, more preferably Mg _(OH) and comprises 2 98 wt% or more, CaO content 0.1 wt% or less, a chlorine content of 0.1 wt% or less of the high Purity magnesium hydroxide is suitable.

The shape of magnesium hydroxide used in the present invention may be particle-like, flake-like, or fibrous, but the particle-like or flake-like shape is most preferable from the viewpoint of dispersibility and the like. Further, the specific surface area is preferably 15 m ² / g or less, ^{more preferably 10 m 2} / g or less, and if the specific surface area ^{exceeds 15 m 2} / g, the dispersibility of magnesium hydroxide may be affected, and the tracking resistance improving effect. It is not preferable because it adversely affects the mechanical strength and the like. In the case of particles and flakes, the average primary particle size in the range of 0.3 to 5 μm, preferably 0.3 to 3 μm is suitable for the balance of tracking resistance improving effect, mechanical strength, and melt viscosity. There is. When a fibrous material is used, one having an average fiber diameter of 0.1 to 2 μm and an aspect ratio of 20 to 60, preferably an average fiber diameter of 0.3 to 2 μm and an aspect ratio of 30 to 50 is suitable.

Further, this magnesium hydroxide is used as a vinylsilane compound such as vinyltriethoxysilane or vinyltrichlorosilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysisilane, β- (3,4-epoxy). Epoxysilane compounds such as cyclohexyl) ethyltrimethoxysilane, aminosilanes such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane Compounds, γ-Isocyanatopropyltriethoxysilane, γ-Isocyanatopropyltrimethoxysilane, γ-Isocyanatopropylmethyldimethoxysilane, γ-Isocyanatopropylmethyldiethoxysilane, γ-Isocyanatopropylethyldimethoxysilane, γ- Isocyanato group-containing alkoxysilane compounds such as isocyanatopropyl ethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy. It is preferable to surface-treat with a methacrylosilane compound such as silane, 3-methacryloxypropyltriethoxysilane, a long-chain fatty acid such as stearic acid, oleic acid, montanic acid, or stearyl alcohol, or a long-chain aliphatic alcohol. In particular, the application of magnesium hydroxide surface-treated with an epoxysilane compound, an aminosilane compound, or an isocyanatosilane compound is effective in suppressing aggregation in the composition or molded product, and thus in terms of tracking resistance and mechanical strength. Is suitable.

The preferred amount of the metal hydroxide added is selected in the range of 20 to 100 parts by weight, more preferably in the range of 40 to 90 parts by weight, based on 100 parts by weight of the PPS resin. If the amount of the metal hydroxide is less than 20 parts by weight, the effect of improving the tracking resistance cannot be obtained, which is not preferable. Further, when the amount of metal hydroxide exceeds 100 parts by weight, the mechanical strength is lowered, which is not preferable.

Further, the PPS resin composition of the present invention has at least one selected from 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. It is preferable to add an alkoxysilane compound having a functional group. 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 hydroxylates 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 suitable amount of the silane compound added is selected in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the (A) PPS resin.

The PPS resin composition of the present invention may be further blended with 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 include copolymers.

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. Systems, amines, sulfurs and their substitutions, etc.), weather resistant agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, 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-stabilizing agents (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-phosphaphenanthrene-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)- 2,4,8,10-Tetraoxaspiro [5.5] undecane and the like or mixtures thereof can be exemplified.

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 a part of the raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading by 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 various moldings such as injection molding, extrusion molding, blow molding, and transfer molding, and is particularly suitable for injection molding applications.

As described above, the PPS resin composition of the present invention is not only excellent in fluidity, but also excellent in low temperature toughness and cold thermal shock resistance of the weld portion in a balanced manner. That is, since the PPS resin composition of the present invention has the characteristics of excellent fluidity, low temperature toughness, and cold and thermal impact resistance of the weld portion, it is useful for molded articles having a complicated shape, and in particular, two or more. It is useful for molded products including welded parts and molded products containing metal inserts.

Other applicable uses 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 condenser cases, oscillators, various terminal boards, and the like. Transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc. Electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademarks) / compact discs, lighting parts, refrigerator parts, air conditioner parts It can also be applied to household and office electrical product parts such as typewriter parts and word processor parts. Other machine-related parts such as office computer-related parts, telephone equipment-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, writers, typewriters, etc .: microscopes, binoculars, cameras, watches, etc. Optical equipment represented by, precision machinery related parts; 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 and other water-related parts; valves Alternator terminal, alternator connector, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, 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, oil temperature 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 impeller, Water pump housing, Engine cooling module, Turbine vane, Wiper motor related parts, Dustributor, 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, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, vehicle speed sensor, Various applications such as automobile / vehicle-related parts such as cable liners can be exemplified.

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.

[Evaluation method of PPS resin manufactured in the reference example]
(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, and then vacuum-sealed. Only the body of this glass ampoule was inserted into a ceramic electric tube furnace ARF-30K manufactured by Asahi Rika Seisakusho and heated at 320 ° C. for 2 hours. After removing the ampoule, the neck of the ampoule, which was not heated by the tube furnace and had volatile gas attached, was cut out with a file and weighed. Then, the adhering gas was dissolved in 5 g of chloroform to remove it, dried in a glass dryer at 60 ° C. for 1 hour, and then weighed again. The difference in weight of the ampoule neck before and after removing the gas was defined as the amount of gas generated (% by weight).

(2) Residue amount A pre-weighed 1 μm PTFE membrane filter was set in a SUS test tube manufactured by Senshu Kagaku equipped with a pneumatic cap and a collection funnel, and 100 mg of PPS resin was press-filmed to a thickness of about 80 μm. And 1-chloronaphthalene (2 g) was weighed 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 the weight of the membrane filter before and after filtration was defined as the residual amount (% by weight).

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

[Reference Example 1] Polymerization of PPS (PPS-1)
In a stirrer and an autoclave with a valve on the bottom, 8267.4 g (70.0 mol) of 47.5% sodium hydroxide, 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 it took about 3 hours to reach 240 ° C. through nitrogen at normal pressure. After gradual heating to distill out 14772.1 g of water and 280.0 g of NMP, the reaction vessel was cooled to 160 ° C. 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, 10646.7 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 the mixture was stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 0.6 ° C./min and maintained at 270 ° C. for 70 minutes. The extraction valve at the bottom 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 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 with 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 filtration was performed to obtain 18,000 g of PPS resin cake (including 7550 g of PPS resin).

18,000 g of the PPS resin cake, 40 liters of ion-exchanged water, and 43 g of acetic acid 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 for acid treatment. The pH at the time of acid treatment was 7. After autoclave cooling, the contents were filtered through a glass filter with a pore size of 10-16 μm. Then, 60 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 was dried at 120 ° C. for 4 hours under a nitrogen stream to obtain an acid-treated PPS resin powder. Next, this PPS resin powder was placed in a heating device equipped 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 carried out in an air atmosphere of 1.96 liters / minute to obtain a crosslinked PPS-1. The gas generation amount of the obtained polymer was 0.16% by weight, the residue amount was 1.9% by weight, and the MFR was 554 g / 10 minutes.

[Reference Example 2] Polymerization of PPS (PPS-2)
8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 in a 70 liter autoclave with a stirrer and bottom plug valve. -Pyrrolidone (NMP) 11.45 kg (115.50 mol) and ion-exchanged water 10.5 kg were charged and gradually heated to 245 ° C. over about 3 hours while passing nitrogen under normal pressure to 14.78 kg of water and NMP0. After distilling .28 kg, the reaction vessel was cooled to 200 ° C. 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., 10.48 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 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. After reacting at 270 ° C. for 100 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 contents were 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.

The obtained cake and 90 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, and acetic acid was added so that the pH became 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. After that, the autoclave was cooled and the contents were taken out.

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.
This was heat-treated at 200 ° C. under an oxygen stream until the MFR value reached 500 g / 10 minutes to obtain a crosslinked PPS-2. The amount of gas generated by the obtained polymer was 0.39% by weight, and the amount of residue was 4.3% by weight.

[Compounding materials used in Examples and Comparative Examples]
The formulations used in this example and comparative examples are as follows.
(A) PPS resin PPS-1: PPS resin polymerized by the method described in Reference Example 1 PPS-2: Reactive olefin-based copolymer containing PPS resin (B) acrylic acid ester polymerized by the method described in Reference Example 2. Polymer B-1: Ethylene, glycidyl methacrylate, methyl acrylate copolymer (Bond First 7M manufactured by Sumitomo Chemical Co., Ltd.)
B-2 (Comparative example): Ethylene-glycidyl methacrylate copolymer (Bond First E manufactured by Sumitomo Chemical Co., Ltd.)
(C) Unmodified olefin-based copolymer containing butyl acrylate C-1: n-butyl copolymer of ethylene / acrylate (Rotril 35BA40 manufactured by Alchema Co., Ltd.)
C-2 (Comparative example): Methyl ethylene / methyl acrylate (Rotril 29MA03 manufactured by Arkema Co., Ltd.)
C-3 (Comparative example): Ethylene 1-octene copolymer pair (Dow Chemical Japan Co., Ltd. Engage 8842)
(D) Inorganic filler D-1: Chopped strand (T-760H manufactured by Nippon Electric Glass Co., Ltd., 3 mm long, average fiber diameter 10.5 μm)
D-2: Heavy calcium carbonate (KSS-1000 50% average particle size 4.2 μm manufactured by Calfine Co., Ltd.)
D-3: Magnesium hydroxide (Kyowa Chemical Industry Co., Ltd. Kisuma 5P 50% average particle size 0.8 μm)
(E) Alkoxysilane compound E-1: Epoxy group-containing alkoxysilane (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.)

[Measurement and evaluation method for molded products made of resin composition]
The measurement and evaluation methods in this example and the comparative example are as follows.

(1) Tensile strength, tensile elongation (23 ° C, -40 ° C)
The measurement was performed in accordance with ISO 527-1 and 2 methods. 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. Using a mold of type A1 test piece shape supplied to (SE-50D) and specified in ISO20753, the average velocity of the molten resin passing through the cross-sectional area of the central parallel portion is 400 ± 50 mm / s. Injection molding was performed 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 distance between the grippers: 114 mm under the atmosphere of 23 ° C. and 50% relative humidity and -40 ° C. Test speed: Tensile strength and tensile elongation were measured under the condition of 5 mm / s.

(2) Liquidity
Using a spiral flow mold with a thickness of 1 mm, molding is performed under the conditions of cylinder temperature 320 ° C., mold temperature 140 ° C., injection speed 230 mm / sec, injection pressure 98 MPa, injection time 5 sec, and cooling time 15 sec, and the flow length is measured. (Injection molding machine used: "SE-30D" manufactured by Sumitomo Heavy Industries). The larger this value, the better the fluidity.

(3) Weld strength
An ATM4 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 under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 135 ° C. After molding 100 molded pieces and forcibly contaminating the mold, 10 samples for measurement were obtained, and the tensile strength was measured under the conditions of a test speed of 10 mm / min and a distance between grippers: 64 mm. ..

(4-1) Cold and thermal impact resistance-1
A metal insert-molded product shown in FIG. 1 in which a metal block was insert-molded under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. was used. After treating this at 130 ° C. for 1 hour, the treatment was performed once at −40 ° C. for 1 hour, and the cold shock treatment was performed, and the presence or absence of cracks was visually confirmed every 5 times. The number of thermal shock treatments in which cracks were observed was defined as cold thermal impact resistance. If cracks do not occur 30 times or more, it can be said that there is no problem in practical use, but the more the number of treatments until cracks occur, the better the cold and thermal impact resistance, which is preferable.

(4-2) Cold and thermal impact resistance-2
A metal insert-molded product shown in FIG. 2 was used in which a cassette-shaped metal having two holes in the center was insert-molded under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. After treating this at 130 ° C. for 1 hour, the treatment was performed once at −40 ° C. for 1 hour, and the cold shock treatment was performed, and the presence or absence of cracks was visually confirmed every 5 times. This molded product is a molded product in which a weld portion is intentionally generated by providing a hole in the central portion, and the cold and thermal impact resistance of the weld portion is assumed. The number of thermal shock treatments in which cracks were observed was defined as cold thermal impact resistance. If cracks do not occur 30 times or more, it can be said that there is no problem in practical use, but the more the number of treatments until cracks occur, the better the cold and thermal impact resistance, which is preferable.

(5) Dimensional accuracy The molded product shown in FIG. 3 was molded using an injection molding machine (SE-100DU) manufactured by Sumitomo Heavy Industries. The molding conditions were a cylinder temperature of 320 ° C., a mold temperature of 130 ° C., and other conditions were general molding conditions. The dimensions of the molded product in the MD direction were measured at three points, and the average value was calculated. The average value measured from the actual size of the mold was subtracted, and the value divided by the actual size of the mold was used as the dimensional accuracy. The measurement was carried out in accordance with JIS B0621 using a three-dimensional dimension measuring machine manufactured by Mitutoyo. If it is smaller than 0.15%, it can be said that there is no problem in practical use, but the smaller this value is, the more excellent the dimensional accuracy is, which is preferable. Those smaller than 0.15% were evaluated as ◯, those smaller than 0.11% were evaluated as ⊚, and those smaller than 0.15% were evaluated as ×.

(6) Mold stain property Molded product shown in FIG. 4 (molded product size; length 55 mm, width 20 mm, thickness 2 mm, gate size; width 1.5 mm, thickness 1 mm, maximum gas vent portion length 20 mm, width 10 mm, depth With a gas evaluation mold of 5 μm), the cylinder temperature is 325 ° C, the mold temperature is 130 ° C, the injection speed is 100 mm / s, and the injection pressure is 50 to 80 MPa so that the filling time for each resin composition is 0.4 seconds. The mold was continuously molded by setting the inside, and the mold contamination status of the mold gas vent portion was visually observed every 10 shots (molding machine used: "SE-30D" manufactured by Sumitomo Heavy Industries). If the number of shots until adhesion is 100 or more, it can be said that it is practically usable, but the larger the number of shots, the better the mold deposit property, which is preferable. FIG. 4A is a top view of the molded product for evaluating the mold deposit, and FIG. 4B is a side view thereof. Those with 100 shots or more were marked with ◯, those with 50 shots or more were marked with Δ, and those with 30 shots or more were marked with x.

(7) Antifreeze-resistant Antifreeze was used by diluting Toyota genuine S-LLC with distilled water into a 50% by weight aqueous solution. A molded product of ISO 3167 A type dumbbell test piece (4 mm thickness) was immersed in a 50 wt% LLC aqueous solution at a temperature of 130 ° C. for 1,000 hours, and the molded product conformed to the ISO 527-1 and 2 methods. The tensile strength was measured. The strength retention rate at that time was set to antifreeze resistance. If it is 80% or more, it can be said that there is no problem in practical use, but the higher this value is, the more excellent the antifreeze resistance is, which is preferable.

(8) Tracking resistance The molded product shown in FIG. 3 was molded using an injection molding machine (SE-100DU) manufactured by Sumitomo Heavy Industries. The molding conditions were a cylinder temperature of 320 ° C., a mold temperature of 130 ° C., and other conditions were general molding conditions. Using this molded product, the maximum voltage at which tracking failure does not occur was determined in accordance with IEC60112 4th edition. A 0.1% ammonium chloride aqueous solution was used as the electrolytic solution.

[Examples 1 to 6 and Comparative Examples 1 to 7]
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 having a diameter of 26 mm, in which the cylinder temperature was set to 320 ° C. and the screw rotation speed was set to 250 rpm. Weights of (A) 100 parts by weight of PPS resin, (B) reactive olefin copolymer containing acrylate ester, and (C) unmodified olefin copolymer containing butyl acrylate are shown in Tables 1 and 2. The mixture is added from the raw material supply port to make it in a molten state, and the inorganic filler (D) is supplied from the intermediate addition port at the weight ratios shown in Tables 1 and 2, and melt-kneaded at a discharge rate of 35 kg / hour to obtain pellets. It was. Each of the above characteristics was evaluated using this pellet. The results are shown in Tables 1 and 2.

As can be seen from the comparison between Example 1 and Comparative Examples 1 to 3, a reactive olefin copolymer containing (B) acrylic acid ester and an unmodified olefin copolymer containing butyl acrylate (C) are used in combination. By doing so, it can be seen that the fluidity, tensile elongation at −40 ° C., and cold thermal impact resistance are well-balanced.

As can be seen from the comparison between Example 1 and Comparative Example 4, (B) a reactive olefin-based copolymer containing an acrylic acid ester and (C) an unmodified olefin-based copolymer containing butyl acrylate are excessively blended. It can be seen that the fluidity deteriorates, and the mold stainability and dimensional accuracy also deteriorate. Further, as can be seen from the comparison between Example 1 and Comparative Example 5, a combination of (B) a reactive olefin-based copolymer containing an acrylic acid ester and (C) an unmodified olefin-based copolymer containing butyl acrylate. It can be seen that if the amount is too small, the tensile elongation at −40 ° C. decreases and the cold thermal impact resistance-2 deteriorates.

As can be seen from the comparison between Example 1 and Comparative Example 6, if the blending amount of the (D) inorganic filler is too large, not only the tensile elongation at −40 ° C. is lowered, but also the mold stain property is deteriorated. There is a tendency. The reason why the mold stainability deteriorates despite the low resin content is that (D) the excessive blending of the inorganic filler increases the shear calorific value of the resin during injection molding, and the heat of the PPS resin and additives. It is presumed that the decomposition progresses excessively.

As can be seen from the comparison between Example 1 and Comparative Example 7, (B) if the blending amount of the inorganic filler is too small, not only the dimensional accuracy becomes insufficient, but also the mold stain property due to the high resin ratio. It tends to get worse.

As can be seen from the comparison between Example 1 and Example 3, it can be seen that the use of PPS-1 is excellent in antifreeze resistance.

As can be seen from the comparison between Examples 1 and 4 and 5, it can be seen that by setting the elastomer ratio to 1/4 to 4/1, the fluidity and the cold and thermal impact resistance are superior.

As can be seen from the comparison between Example 1 and Example 6, it can be seen that the addition of magnesium hydroxide is superior in tracking resistance.

The PPS resin composition of the present invention is excellent in fluidity, low-temperature toughness, and cold-heat impact resistance of welds while maintaining high dimensional accuracy, and is therefore useful for molded articles having complicated shapes, and particularly two or more welds. It is used for molded products containing parts and molded products containing metal inserts.

1. 1. Insert metal 2. Gate 3. Metal insert molded product 4. Insert metal 5. Gate 6. Metal insert molded product 7. Molded product for dimensional accuracy and tracking resistance evaluation 8. Gate 9. Molded product for mold stainability evaluation 10. Gate

Claims (11)

A total of 10 to 20 of (B) a reactive olefin-based copolymer containing acrylate ester and (C) an unmodified olefin-based copolymer containing butyl acrylate with respect to 100 parts by weight of (A) polyphenylene sulfide resin. A polyphenylene sulfide resin composition comprising 100 to 200 parts by weight of (D) an inorganic filler. The first aspect of claim 1, wherein the weight ratio of the reactive olefin-based copolymer containing (B) acrylate ester / the unmodified olefin-based copolymer containing butyl acrylate (C) is 1/4 to 4/1. Polyphenylene sulfide resin composition. Claim 1 or claim 1, wherein the reactive olefin-based copolymer containing the (B) acrylic acid ester is an olefin copolymer containing ethylene, an α, β-unsaturated acid glycidyl ester, and an acrylic acid ester. 2. The polyphenylene sulfide resin composition according to 2. (C) The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the unmodified olefin copolymer containing butyl acrylate is an olefin copolymer containing ethylene and butyl acrylate. The invention according to any one of claims 1 to 4, wherein the (D) inorganic filler is at least one selected from (D-1) glass fiber, (D-2) calcium carbonate and (D-3) metal hydroxide. Polyphenylene sulfide resin composition. The polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein the polyphenylene sulfide resin (A) is a crosslinked polyphenylene sulfide resin. When the (A) polyphenylene sulfide resin is (a) heated and melted under vacuum at 320 ° C. for 2 hours, the amount of gas generated volatilizes is 0.3% by weight or less, and (b) at 250 ° C. for 5 minutes, 20 times the weight. The polyphenylene sulfide according to any one of claims 1 to 6, which is a polyphenylene sulfide resin having a residual amount of 4.0% by weight or less when melted in 1-chloronaphthalene and subjected to hot pressure filtration with a PTFE membrane filter having a pore size of 1 μm. Resin composition. An alkoxysilane compound (E) having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureido group was added to 100 parts by weight of the (A) polyphenylene sulfide resin. , 0.1 to 3 parts by weight of the polyphenylene sulfide resin composition according to any one of claims 1 to 7. A molded product comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 8. The molded product according to claim 9, wherein the molded product includes two or more weld portions. The molded product according to claim 9 or 10, wherein the molded product includes a metal insert.

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