JP2022010455A - Polyphenylene sulfide resin composition, and molding - Google Patents

Abstract

To provide a polyphenylene sulfide resin composition that achieves both of toughness and good flowability and has excellent injection moldability, and a molding obtained therefrom.SOLUTION: A polyphenylene sulfide resin composition contains (A) polyphenylene sulfide resin 99-60 pts.wt. and (B) polyether sulfone resin 1-40 pts.wt., and relative to 100 pts.wt of the total of (A) and (B), (C) tetracarboxylic acid dianhydride 0.01-10 pts.wt. is contained as well.SELECTED DRAWING: None

Description

The present invention relates to a polyphenylene sulfide resin composition having both toughness and good fluidity and excellent injection moldability, and a molded product using the same.

Polyphenylene sulfide (hereinafter abbreviated as PPS) resin has excellent heat resistance, barrier properties, chemical resistance, electrical insulation, moisture heat resistance, and other properties suitable for engineering plastics, and is injection molded and extruded. Molded products are manufactured by a molding method centered on, and are used for various electric / electronic parts, mechanical parts, automobile parts, and the like.

However, since PPS resin has lower toughness than other engineering plastics such as polyamide, its use is currently limited, and improvement thereof is strongly desired.

Therefore, the PPS resin contains an amorphous resin made of a polyetherimide resin or a polyethersulfone (hereinafter abbreviated as PES) resin, and an alkoxysilane having one or more groups selected from an epoxy group, an amino group, and an isocyanate group. It has been reported that the island phase made of an amorphous resin is finely dispersed and the toughness is dramatically improved by blending the above (for example, Patent Document 1).

International Publication No. 2007/108384

However, in the PPS resin composition described in Patent Document 1, the amorphous resin has a high viscosity at the processing temperature of PPS, and the alkoxy has one or more groups selected from an epoxy group, an amino group, and an isocyanate group. Since the viscosity tends to increase with the chemical reaction of silane, the injection moldability may be insufficient depending on the mold shape that requires high fluidity.

Therefore, as a result of diligent studies to solve the above problems, the present inventors have found that a composition composed of a polyphenylene sulfide resin, a PES resin, and a tetracarboxylic acid dianhydride can achieve both toughness and good fluidity.

That is, the present invention has the following configuration.
1. 1. 0.01 to 10 parts by weight of (C) tetracarboxylic acid dianhydride with respect to 99 to 60 parts by weight of (A) polyphenylene sulfide resin and 1 to 40 parts by weight of (B) polyether sulfone resin. A polyphenylene sulfide resin composition which is partially blended.
2. 2. The polyphenylene sulfide resin composition according to Item 1, wherein the (C) tetracarboxylic dianhydride is the (C) tetracarboxylic dianhydride represented by the general formula (1) or the general formula (2).

(R ¹ to R ⁸ may be the same or different, hydrogen atom, alkyl group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, halogen, hydroxyl group, carboxyl group, amino group, sulfone group, nitro. It is either a group or a cyano group. X is either a single bond, O, CO, S, SO, CH ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) _2. )
3. 3. Item 2. The polyphenylene sulfide resin composition according to Item 1 or 2, wherein the inorganic filler is blended in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the total of the polyphenylene sulfide resin (A) and the polyether sulfone resin (B). thing.
4.1 A molded product comprising the polyphenylene sulfide resin composition according to any one of Items 1 to 3.

According to the present invention, a polyphenylene sulfide resin composition having both excellent toughness, strength and good fluidity can be obtained. The polyphenylene sulfide resin composition having these characteristics is suitable for an injection-molded product that requires high fluidity.

Hereinafter, the present invention will be described in more detail.

(A) Polyphenylene sulfide resin The (A) polyphenylene sulfide 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, the PPS resin (A) may be composed of a repeating unit having the following structure or the like in an amount of less than 30 mol% of the repeating unit.

The melt viscosity of the (A) PPS resin used in the present invention is not particularly limited, but it is preferable that the melt viscosity is high in order to obtain better toughness. For example, a range exceeding 30 Pa · s is preferable, 50 Pa · s or more is more preferable, and 100 Pa · s or more is further preferable. The upper limit is preferably 600 Pa · s or less from the viewpoint of ensuring liquidity.

The melt viscosity in the present invention is a value measured using a capillograph manufactured by Toyo Seiki under the conditions of 310 ° C. and a shear rate of 1000 / 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 the (A) PPS resin having the above structure can be obtained.

First, the contents of the dihaloaromatic compound, the sulfidizing agent, the polymerization solvent, the molecular weight modifier, the polymerization aid and the polymerization stabilizer used in the production method will be described.

[Dihalo aromatic compounds]
The dihalo aromatic compound is 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. Dihaloaromatic compounds such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene However, p-dichlorobenzene is preferably used.

The amount of the dihalo aromatic compound added is 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, per mol of the sulfidizing agent from the viewpoint of obtaining the (A) PPS resin having a viscosity suitable for processing. More preferably, the range of 1.005 to 1.2 mol can be exemplified.

[Sulfidating agent]
Sulfides include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

Specific examples of the alkali metal sulfide include, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture of two or more thereof, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.

Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these, 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 a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Further, the alkali metal sulfide can be prepared from the alkali metal hydrosulfide and the alkali metal hydroxide, and the alkali metal sulfide can be transferred to a polymerization tank for use.

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

The amount of the charged sulfidating agent shall mean the residual amount obtained by subtracting the loss from the actual charging 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 is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfide agent. Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof as preferable ones. Specific examples of the alkaline earth 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 0.95 to 1. per 1 mol of alkali metal hydrosulfide. The range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.

[Polymerization solvent]
It is preferable to use an organic polar solvent 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 preferably in the range of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, and more preferably 2.5 to 5.5 mol per mol of the sulfidizing agent.

[Molecular weight regulator]
The monohalogenated compound (not necessarily an aromatic compound) is used as the polyhalogenated fragrance in order to form a reactive end in the (A) PPS resin to be produced, or to adjust the polymerization reaction or the molecular weight. Can be used in combination with group compounds.

[Polymerization aid]
It is also one of the preferable embodiments to use a polymerization aid in order to obtain the (A) PPS resin having a relatively high degree of polymerization in a shorter time. Here, the polymerization aid means a substance having an action of increasing the viscosity of the obtained (A) 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 may be used alone or in combination of two or more at the same time. Of these, an organic carboxylate, water, and an alkali metal chloride are preferable, an alkali metal carboxylate is preferable as the organic carboxylate, and lithium chloride is preferable as the alkali metal chloride.

The alkali metal carboxylate is a general formula R (COMM) _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-tolurate, 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. 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. Seem. 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 a polymerization aid, the amount used is usually in the range of 0.01 mol to 2 mol with respect to 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization. The range of 0.1 mol to 0.6 mol is preferable, and the range of 0.2 mol to 0.5 mol is more preferable.

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 alkali metal sulfide, and 0.6 mol in the sense of obtaining a higher degree of polymerization. The range of ~ 10 mol is preferable, and the range of 1 mol ~ 5 mol is more preferable.

Of course, two or more of these polymerization aids can be used in combination, and 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-step, 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 dihalo aromatic compound in the middle of the polymerization reaction after charging it.

[Polymerization stabilizer]
Polymerization stabilizers can also be used to stabilize the polymerization reaction system and suppress side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses undesired side reactions. One guideline for side reactions is the production of thiophenols, and the addition of a polymerization stabilizer can suppress the production of thiophenols. 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. 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 is used. 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 mol to 0.2 mol, preferably 0.03 mol to 0.1 mol, more preferably 0.04 mol to 0.09 mol, per 1 mol of the charged alkali metal sulfide. It is preferably used in a molar ratio. If this ratio is small, the stabilizing effect is insufficient, and conversely, if it is too large, it is economically disadvantageous and 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 because it is easy to add at the same time at the start of the process or the start of polymerization.

Next, a preferable method for producing the (A) PPS resin used in the present invention will be specifically described step by step in the order of a pre-step, a polymerization reaction step, a recovery step, and a post-treatment step, but of course, it is limited to this method. It's not something.

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

Further, as described above, as the sulfidizing agent, a sulfidizing agent prepared from alkali metal hydrosulfide and alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank is also used. Can be done. Although this method is not particularly limited, it is desirable to use alkali metal hydrosulfide and alkali metal hydroxide as an organic polar solvent in a temperature range of normal temperature to 150 ° C., preferably normal 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 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 outside of 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]
The (A) PPS resin is produced by reacting a sulfidizing agent and a dihaloaromatic compound in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 290 ° C.

At the start of the polymerization reaction step, the organic polar solvent, the sulfidizing agent and the dihaloaromatic compound are mixed in a temperature range of preferably room temperature to 240 ° C., preferably 100 ° C. to 230 ° C. under 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.

The temperature of such a mixture is usually raised to a range of 200 ° C. or higher and lower than 290 ° C. The rate of temperature rise is not particularly limited, but usually a rate of 0.01 ° C./min to 5 ° C./min is selected, and a range of 0.1 ° C./min to 3 ° C./min is more preferable.

Generally, the temperature is finally raised to a temperature of 250 ° C. or higher and lower than 290 ° C., and the reaction is usually carried out at that temperature for 0.25 hours to 50 hours, preferably 0.5 hours 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 ° C. or higher and lower than 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 hours 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 dihaloaromatic compound in the system at 245 ° C. reaches 40 mol% or more, preferably 60 mol% or more.

The conversion rate of the dihaloaromatic compound (abbreviated as DHA here) is a value calculated by the following formula. The residual amount of DHA can usually be determined by gas chromatography.
(A) When the dihalo aromatic compound is excessively added to the alkali metal sulfide in a molar ratio, conversion rate = [DHA charge amount (mol) -DHA residual amount (mol)] / [DHA charge amount (mol) -DHA Excess amount (mol)]
(B) In cases other than the above (a) Conversion rate = [DHA charge amount (mol) -DHA residual amount (mol)] / [DHA charge amount (mol)].

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

For example, a method of slowly cooling after the 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 all the slow cooling steps, and the polymer particles are slowly cooled at a rate of 0.1 ° C./min to 1 ° C./min until the polymer particles crystallize and precipitate, and then at a rate of 1 ° C./min or higher. A method or the like may be adopted.

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

[Post-treatment process]
The (A) PPS resin may be produced through the above-mentioned polymerization reaction step and recovery step, and then subjected to acid treatment, hot water treatment, washing with an organic solvent, and alkali metal or alkaline earth metal treatment. ..

When performing acid treatment, it is as follows. The acid used for the acid treatment of the (A) PPS resin is not particularly limited as long as it does not have the action of decomposing the (A) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Of these, acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate the (A) PPS resin such as nitric acid are not preferable.

As a method of acid treatment, there is a method such as immersing the (A) PPS resin in an acid or an aqueous solution of an acid, and it is also possible to appropriately stir or heat as necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous solution of pH 4 heated to 80 ° C. to 200 ° C. and stirring for 30 minutes. The pH after the treatment may be 4 or more, for example, pH 4 to 8. The acid-treated (A) 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 the preferable chemical modification of the (A) PPS resin by the acid treatment is not impaired.

When performing hot water treatment, it is as follows. When the PPS resin is treated with hot water, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If the temperature is lower than 100 ° C., the effect of preferable chemical modification of the (A) 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 (A) PPS resin by hot water washing. There is no particular limitation on the operation of hot water treatment, and it is carried out by a method of putting a predetermined amount of (A) PPS resin in a predetermined amount of water, heating and stirring in a pressure vessel, a method of continuously performing hot water treatment, and the like. Will be. The ratio of (A) PPS resin to water is preferably more than that of water, but usually, a bath ratio of 200 g or less of (A) PPS resin is selected with respect to 1 liter of water.

Further, the atmosphere of the treatment is preferably an inert atmosphere in order to avoid the decomposition of the terminal group, which is not preferable. Further, the (A) 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 (A) PPS resin is not particularly limited as long as it does not have the action of decomposing the (A) PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, etc. Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphorasamide, and piperazinones, sulfoxide-sulfone solvents such as dimethylsulfoxide, dimethylsulfone, and sulfolane, and ketones such as acetone, methylethylketone, diethylketone, and acetophenone. Solvents, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, chlorbenzene, etc. Alcohol-phenolic solvents such as halogen-based solvents, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and aromatic hydrocarbons such as benzene, toluene and xylene. Examples include solvents. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. In addition, these organic solvents are used in one kind or a mixture of two or more kinds.

As a method of washing with an organic solvent, there is a method of immersing the (A) PPS resin in the organic solvent, and if necessary, stirring or heating can be performed as appropriate. The cleaning temperature when cleaning the (A) 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 above 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 washing for 5 minutes or more. It is also possible to wash continuously.

As a method of alkali metal treatment and alkaline earth metal treatment, a method of adding an alkali metal salt and an alkaline earth metal salt before, during, or after the above-mentioned pre-step, before the polymerization step, during the polymerization step, Alternatively, a method of adding an alkali metal salt or an alkaline earth metal salt into the polymerization kettle after the polymerization step, or a method of adding an alkali metal salt or an alkaline earth metal salt at the first, middle, or last stage of the above cleaning step, etc. Can be mentioned. Among them, the simplest method includes organic solvent washing and a method of adding an alkali metal salt and an alkaline earth metal salt after removing residual oligomers and salts by washing with warm water or hot water. The alkali metal and alkaline earth metal are preferably introduced into the PPS resin in the form of alkali metal ions such as acetate, hydroxide and carbonate, and alkaline earth metal ions. Further, it is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water or the like. The alkali metal ion concentration and the alkaline earth metal ion concentration at the time of introducing the alkali metal and the alkaline earth metal are preferably 0.001 mmol or more, more preferably 0.01 mmol or more with respect to 1 g of PPS. The temperature is preferably 50 ° C. or higher, more preferably 75 ° C. or higher, and particularly preferably 90 ° C. or higher. Although there is no particular upper limit temperature, it is usually preferably 280 ° C. or lower from the viewpoint of operability. The bath ratio (weight of the washing liquid with respect to the weight of the dried PPS) is preferably 0.5 or more, more preferably 3 or more, still more preferably 5 or more.

In the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition having excellent toughness, after removing residual oligomers and salts by repeating organic solvent washing and washing with warm water at about 80 ° C. or the above-mentioned hot water washing several times, A method of treating with an acid or an alkali metal salt or an alkaline earth metal salt is preferable, and a method of treating with an alkali metal salt or an alkaline earth metal salt is particularly preferable.

In addition, the PPS resin (A) can be used by increasing the molecular weight by heating in an oxygen atmosphere after the completion of polymerization and by thermal oxidative cross-linking treatment by adding a cross-linking agent such as a peroxide.

In the case of dry heat treatment for the purpose of increasing the molecular weight by thermal oxidative crosslinking, the temperature is preferably 160 ° C. to 260 ° C., more preferably 170 ° C. 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 hours to 100 hours, more preferably 1 hour to 50 hours, still more preferably 2 hours to 25 hours. The heat treatment device may be a normal hot air dryer or a heating device with a rotary or stirring blade, but for efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. It is more preferable to use it.

It is also possible to perform dry heat treatment for the purpose of suppressing thermal oxidative cross-linking and removing volatile components. The temperature is preferably 130 ° C to 250 ° C, more preferably 160 ° C 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 hours to 50 hours, more preferably 1 hour to 20 hours, still more preferably 1 hour to 10 hours. The heat treatment device may be a normal hot air dryer, a rotary type or a heating device with a stirring blade, but for efficient and more uniform processing, a rotary type or a heating device with a stirring blade may be used. It is more preferable to use it.

However, from the viewpoint of exhibiting excellent toughness, the (A) PPS resin of the present invention is a substantially linear PPS resin that is not polymerized by thermal oxidative cross-linking treatment, or is lightly oxidatively cross-linked. It is preferably a semi-crosslinked PPS resin. On the other hand, the PPS resin subjected to the thermal oxidative cross-linking treatment is suitable from the viewpoint of suppressing creep strain to a small extent, and can be appropriately mixed with a linear PPS resin and used. Further, in the present invention, a plurality of (A) PPS resins having different melt viscosities may be mixed and used.

(B) Polyether sulfone resin The (B) polyether sulfone resin used in the present invention is a general term for those having a skeleton in which an aromatic group is bonded by a sulfone group and an ether group. For example, a polyether sulfone composed of at least one repeating unit selected from the group consisting of the following general formulas (3) to (5) can be mentioned.

In formula (3), Ar ¹ and Ar ² are aromatic hydrocarbon groups having the same or different carbon atoms of 6 to 12. In the formula (4), Ar ³ to Ar ⁶ are aromatic hydrocarbon groups having the same or different carbon atoms 6 to 12, and X is a divalent hydrocarbon group having 1 to 15 carbon atoms. In formula (5), Ar ⁷ to Ar ⁹ are aromatic hydrocarbon groups having the same or different carbon atoms of 6 to 12.

Here, Ar ¹ and Ar ² suitable in the formula (3) are an arylene group having 6 to 12 carbon atoms, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples thereof include m-phenylene group, p-phenylene group, dimethyl-p-phenylene group, tetramethyl-p-phenylene group, naphthylene group and biphenylylene group. When both Ar ¹ and Ar ² are p-phenylene groups, it is advantageous in terms of production and is particularly preferably used.

In the formula (4), the preferred Ar ³ to Ar ⁶ are an arylene group having 6 to 12 carbon atoms, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples thereof include m-phenylene group, p-phenylene group, dimethyl-p-phenylene group, tetramethyl-p-phenylene group, naphthylene group and biphenylylene group. As a particularly suitable example, Ar ³ to Ar ⁶ all have a p-phenylene group. Further, X is a divalent hydrocarbon group having 1 to 15 carbon atoms, and a group selected from a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group and an alkylene group is preferable. .. A group selected from a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group and an alkylene group is preferable. Specifically, aliphatic hydrocarbon groups such as methylene group, 1,1-ethylene group, 2,2-propylene group, 2,2-butylene group, 4-methyl-2,2-pentylene group, 1,1- Examples thereof include an alicyclic hydrocarbon group such as a cyclohexylene group, a 3,3,5-trimethyl-1,1-cyclohexylene group, and an alkylene group such as a 1-phenyl-1,1-ethylene group and a diphenylmethylene group. Of these, the 2,2-propylene group is more preferably used. In the formula (2), Ar ³ to Ar 6 are all p-phenylene groups, and X is a 2,2-propylene group.

In the formula (5), the preferred Ar ⁷ and Ar ⁸ are an arylene group having 6 to 12 carbon atoms, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples thereof include m-phenylene group, p-phenylene group, dimethyl-p-phenylene group, tetramethyl-p-phenylene group, naphthylene group and biphenylylene group. Of these, p-phenylene groups are more preferably used for both Ar ⁷ and Ar ⁸ . Further, a suitable Ar ⁹ is an arylene group having 6 to 12 carbon atoms, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples thereof include an m-phenylene group, a p-phenylene group, a naphthylene group and a biphenylylene group. Of these, the p-phenylene group or biphenylylene group is even more suitable. In the formula (5), Ar ⁷ , Ar ⁸ and Ar ⁹ are all p-phenylene groups, which are particularly preferable.

The above-mentioned (B) PES resin can be polymerized by a known method. For example, it can be obtained by polycondensing a monomer having a hydroxyl group and a halogen group at the ends in an aprotic polar solvent in the presence of an alkali metal carbonate. Due to this polymerization mode, since the polyether sulfone has a hydroxyl group at the end of the polymer, the compatibility with PPS is improved and excellent toughness can be easily obtained, and (C) the effect of improving the characteristics by adding tetracarboxylic acid dianhydride is effective. Easy to get. Therefore, it is preferable that the (B) PES resin contains a large amount of hydroxyl groups. The (B) PES resin used in the present invention has a reduced viscosity of 0.3 dL / measured at 25 ° C. in an N, N-dimethylformamide (DMF) solution. It is preferably g or more and 0.6 dL / g or less. If it is less than 0.3, the toughness imparted to PPS is insufficient, and if it exceeds 0.6, the fluidity is lowered, which is not preferable.

The (B) PES resin used in the present invention is a trademark of "Radel (registered trademark)" from Solvay Advanced Polymers, a trademark of "Ultrazone (registered trademark)" from BSF, and "Sumika Excel (registered trademark)". ) ”, Which is commercially available from Sumitomo Chemical Co., Ltd., can be used.

The blending amount of the (B) PES resin used in the present invention is 1 to 60 parts by weight with respect to 99 to 60 parts by weight of the (A) PPS resin, with the total of (A) PPS resin and (B) PES resin being 100 parts by weight. It is 40 parts by weight, preferably 5 parts by weight or more, and more preferably 10 parts by weight or more. The upper limit of the blending amount is preferably 50 parts by weight or less. When it is 1 part by weight or more, a sufficient toughness improving effect can be obtained, and when it is 40 parts by weight or less, the original chemical resistance of PPS can be exhibited.

(C) Tetracarboxylic acid dianhydride In order to impart features suitable for injection molding such as high toughness, high temperature rigidity retention, and good fluidity in the PPS resin composition of the present invention, (C) tetracarboxylic acid dianhydride. It is essential to mix things.

The present inventors show good fluidity when the PPS resin composition is melted by adding (C) tetracarboxylic acid sulfide to the resin composition composed of (A) PPS resin and (B) PES resin, and PPS. It has been newly found that when the resin composition is solidified, it promotes improvement of toughness and high temperature rigidity. Therefore, it is possible to achieve both good fluidity required for injection molding, an effect of improving releasability at 130 to 150 ° C., which is a general mold temperature when injection molding a PPS resin composition, and toughness of a molded product. I found it. These effects are not limited to other structures as long as they are tetracarboxylic dianhydrides, but they are aromatic compounds as represented by the general formulas (1) and (2) (A) PPS resin. (B) It is preferable from the viewpoint of compatibility with the PES resin and suppression of gas generation during melting.

(R ¹ to R ⁸ may be the same or different, hydrogen atom, alkyl group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, halogen, hydroxyl group, carboxyl group, amino group, sulfone group, nitro. It is either a group or a cyano group. X is either a single bond, O, CO, S, SO, CH ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) _2. )

Specific examples of the tetracarboxylic acid dianhydride represented by the general formula (1) include pyromellitic acid anhydride, dimethylpyromellitic acid anhydride, dibromopyromellitic acid anhydride and the like.

Specific examples of the tetracarboxylic dianhydride represented by the general formula (2) include 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 2,2-dimethyl3,3'-4. , 4'-biphenyltetracarboxylic dianhydride, 5,5-dimethyl3,3'-4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride Anhydroide, 2,3', 3,4'-diphenyl ether tetracarboxylic dianhydride, 2,2', 3,3'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone Tetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3', 3,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4, 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethylenetetracarboxylic dianhydride, Examples include 3,3', 4,4'-diphenylethylenetetracarboxylic dianhydride, 4,4'-isopropyridenediphthalic acid dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride, etc. Will be. Among these, pyromellitic acid anhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride from the viewpoint of reactivity and cost. , 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride is preferred. Further, these acid anhydrides may be those in which some acid anhydride groups are hydrolyzed to carboxyl groups by absorption of moisture. Even if a part of the acid anhydride group becomes a carboxyl group by hydrolysis, there is no problem because the ring is closed by dehydration during melt kneading. Further, these (C) tetracarboxylic dianhydrides can be used alone or in the form of a mixture of two or more kinds, respectively.

The blending amount of the (C) tetracarboxylic acid dianhydride is 0.01 to 60 parts by weight with respect to 99 to 60 parts by weight of the (A) PPS resin and 1 to 40 parts by weight of the (B) PES resin in total. It is essential that the amount is 10 parts by weight, preferably 0.1 part by weight or more. The upper limit of the blending amount is preferably 5 parts by weight or less, and more preferably 1 part by weight or less. (C) If the blending amount of the tetracarboxylic dianhydride exceeds 10 parts by weight, it causes gas generation, and if it is less than 0.01 parts by weight, a sufficient effect of improving the characteristics cannot be obtained.

Although the PPS resin composition of the present invention is not an essential component, it is also possible to blend and use the (D) inorganic filler as long as the effects of the present invention are not impaired. Specific examples of the (D) inorganic filler include glass fibers, carbon fibers, carbon nanotubes, carbon nanohorns, potassium titanate whiskers, zinc oxide whiskers, calcium carbonate whiskers, warasterite whiskers, aluminum borate whiskers, aramid fibers, and alumina fibers. Fibrous fillers such as silicon carbide fiber, ceramic fiber, asbestos fiber, stone saw fiber, metal fiber, or fullerene, talc, wallastenite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, Silicas such as asbestos and alumina silicate, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfuric acid such as calcium sulfate and barium sulfate. Hydroxide such as salt, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, non-fibrous fillers such as graphite Is used, and among them, a fibrous filler is preferable from the viewpoint of improving the releasability at the time of injection molding by improving the mechanical strength and the high temperature rigidity, and glass fiber is particularly preferable from the viewpoint of cost balance. Further, these (D) inorganic fillers may be hollow, and two or more kinds thereof can be used in combination. Pretreatment of these (D) inorganic fillers with a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound, and an epoxy compound can also improve dispersibility during resin compounding and resin. It is preferable from the viewpoint of improving the adhesion between the two.

The shape of the fibrous filler varies depending on the type of fiber used and cannot be unconditionally defined, but the fiber diameter is preferably 1 to 50 μm, more preferably 3 to 30 μm, and even more preferably 5 to 20 μm. The length is preferably 30 μm to 10 mm, more preferably 50 μm to 5 mm. By setting the fiber cross-sectional diameter and the fiber length within the above ranges, the effect of improving the mechanical strength of the resin composition can be obtained, which is preferable.

From the viewpoint of obtaining the strength improving effect, the blending amount of the (D) inorganic filler is 100 parts by weight in total with respect to 99 to 60 parts by weight of (A) PPS resin and 1 to 40 parts by weight of (B) PES resin. The range is preferably 1 to 50 parts by weight, preferably 10 parts by weight or more, and more preferably 30 parts by weight or more. The upper limit of the blending amount is preferably 50 parts by weight or less, more preferably 40 parts by weight or less. (D) If the blending amount of the inorganic filler is less than 1 part by weight, the mechanical strength and high temperature rigidity are insufficient, and if it exceeds 50 parts by weight, the melt viscosity is remarkably increased and the injection moldability is deteriorated, which is not preferable. .. In the present invention, additives, other thermoplastic resins, fillers and the like may be blended, if necessary, as long as the characteristics are not impaired.

Additives include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, plasticizers such as organic phosphorus compounds, organic phosphorus compounds, crystal nucleating agents such as polyether ether ketones, and montanic acid wax. Kind, metal soap such as lithium stearate, aluminum stearate, mold release agent such as ethylenediamine / stearic acid / sebacic acid polycondensate, silicone compound, etc., water, lubricant, UV inhibitor, colorant, foaming agent, etc. Can be formulated with the usual additives of.

The blending amount of the above additive may be 0.1 to 10 parts by weight with respect to 99 to 60 parts by weight of (A) PPS resin and 1 to 40 parts by weight of (B) PES resin in total of 100 parts by weight. It is preferable to add 0.2 to 5 parts by weight, more preferably.

Other thermoplastic resins include polyolefin resins, polyketone resins, polyarylate resins, liquid crystal polymers, polyether ketone resins, polythioether ketone resins, polyether ether ketone resins, tetrafluoropolyethylene resins, and ethylene tetrafluoroethylene copolymers. And so on.

If the amount of the above-mentioned other components added exceeds 20% by weight of the entire resin composition, the original characteristics are impaired, so that it is not preferable, and it is preferable to add 10% by weight or less, preferably 5% by weight or less.

The melt viscosity of the PPS resin composition of the present invention is preferably 400 Pa · s or less, more preferably 350 Pa · s or less, from the viewpoint of improving injection moldability. Further, considering application to thin-walled molded products, 300 Pa · s or less is particularly preferable, and 250 Pa · s or less is particularly preferable. The lower limit of the melt viscosity is preferably 100 Pa · s or more from the viewpoint of ensuring toughness. By setting the melt viscosity to 400 Pa · s or less, it is possible to suppress the occurrence of molding defects such as short shots.

The melt viscosity of the PPS resin composition of the present invention can be determined by, for example, selecting a low molecular weight (A) PPS resin or (B) PES resin, or increasing the blending amount of (C) tetracarboxylic acid dianhydride. It is possible to reduce it. The melt viscosity of the resin composition in the present invention is a value measured using a capillograph manufactured by Toyo Seiki under the conditions of 300 ° C. and a shear rate of 1216 / s.

The PPS resin composition of the present invention is a resin composition having excellent toughness, and although it cannot be said unconditionally because it depends on the blending amount of the (D) inorganic filler, it cannot be said unconditionally, but an ISO (1A) dumbbell test piece obtained by injection molding. The tensile elongation at break measured in accordance with ISO527-1 and -2 is preferably 3.0% or more, more preferably 5.0% or more.

The PPS resin composition of the present invention is a resin composition having excellent high-temperature rigidity, and the glass transition temperature derived from the PES resin in the PPS resin composition is preferably 215 ° C. or higher, more preferably 220 ° C. or higher, and more excellent. In order to obtain high temperature rigidity, 225 ° C. or higher is particularly preferable, and 230 ° C. or higher is particularly preferable. The glass transition temperature derived from the PES resin in the PPS resin composition can be increased, for example, by increasing the entanglement by increasing the molecular weight of the PES resin (B) or introducing a crosslinked structure. Therefore, it is also preferable to perform a dry heat treatment if necessary.

The flexural modulus at 150 ° C. depends on the amount of the inorganic filler (D) and cannot be unequivocally determined, but is preferably 0.5 GPa or more, more preferably 1.0 GPa or more, and improves releasability during injection molding. From the viewpoint, 3.0 GPa or more is particularly preferable, and 5.0 GPa or more is particularly preferable. The glass transition temperature derived from the PES resin in the PPS resin composition of the present invention rises to 50 to 250 ° C. in the dynamic viscoelasticity measurement in a three-point bending mode, a frequency of 1 Hz, and a temperature rise rate of 2 ° C./min. The temperature was set so that the loss tangent (tan δ) was maximized at 200 ° C. or higher when heated. The elastic modulus (E) at 150 ° C. was defined as the bending elastic modulus at 150 ° C.

The method for producing the PPS resin composition of the present invention is not particularly limited, and the raw material is supplied to a commonly known melt-kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll, and the resin temperature is reached. (A) A method of melt-kneading so that the melting peak temperature of the PPS resin becomes + 5 ° C. to 100 ° C. can be mentioned as a typical example, but melt-kneading by a twin-screw extruder is particularly preferable.

The ratio (L / D) of the screw length L (mm) to the screw diameter D (mm) of the twin-screw extruder is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more. The upper limit of L / D of a twin-screw extruder is usually 60. When the L / D is less than 10, kneading is insufficient and it tends to be difficult to obtain sufficient melt viscosity and toughness.

At this time, 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, and some raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are further mixed. Any method may be used, such as a method of blending and melt-kneading, or a method of blending some raw materials and then mixing the remaining raw materials using a side feeder from the middle of melt-kneading with an extruder. From the viewpoint of obtaining sufficient material strength, it is preferable to mix the (D) inorganic filler using a side feeder.

Further, it is preferable to suppress the gelation of the extruded gut due to (A) PPS resin, (B) PES resin, and (C) tetracarboxylic acid dianhydride and the accompanying decrease in toughness, and the screw configuration for achieving this is preferable. It is preferable to use a stirring screw having a notch. Here, the "notch" is a part of the screw flight that has been cut off. A stirring screw having a notch can increase the resin filling rate. The molten resin is susceptible to the extruder cylinder temperature as it passes through the kneading section to which the stirring screw is connected. By using a stirring screw having a notch, the molten resin generated by shearing during kneading is efficiently cooled, so that the resin temperature during kneading can be lowered. Further, unlike the conventional method of grinding the resin, the stirring screw having the notched portion can perform kneading mainly by stirring and stirring, so that the thermal deterioration of the resin due to heat generation can be further suppressed.

As a stirring screw having a notch, the screw pitch length is 0.1D to 0.3D when the screw diameter is D (mm) from the viewpoint of improving the cooling efficiency of the molten resin and improving the kneading property by filling the resin. It is preferable that the stirring screw has a notch portion which is in the range and has 10 to 15 notches per pitch. Here, the "screw pitch length" means the screw length between the screw ridges when the screw is rotated 360 degrees.

The stirring type screw having a notch is preferably introduced so as to be 3% or more of the total length L (mm) of the screw, and more preferably 5% or more. The upper limit is preferably 20% or less, more preferably 15% or less.

The cylinder temperature of the extruder cannot be unequivocally determined because it depends on the melting point of the (A) PPS resin used, but 280 ° C. or higher and 320 ° C. or lower can be exemplified as a preferable range.

The PPS resin composition of the present invention can be applied to various molding methods, and examples thereof include extrusion molding, injection molding, hollow molding, calender molding, compression molding, vacuum molding, foam molding, blow molding, and rotation molding. .. In particular, the PPS resin composition of the present invention is useful for injection molding because it has excellent good fluidity, toughness, and high-temperature rigidity.

Applications of molded products obtained by injection molding include generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, machine breakers, knife switches, and multi-poles. Electrical equipment parts such as rods and electrical parts cabinets, sensors, LED lamps, connectors, sockets, resistors, relay cases, small switches, coil bobbins, condensers, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs. , Printed boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other 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 trademark) / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriters. Home and office electrical parts such as parts and word processor parts; office computer related parts, telephone equipment related parts, facsimile related parts, copying machine related parts, cleaning jigs, motor parts, writers, typewriters, etc. Machine-related parts; Optical equipment / precision machine-related parts such as microscopes, binoculars, cameras, watches, etc .; Alternator terminals, alternator connectors, IC regulators, potential meter bases for light dimmers, various valves such as exhaust gas valves, etc. Automotive cooling piping, fuel-related / exhaust / intake system pipes and ducts, turbo ducts, 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, Brake pad wear sensor, Throttle position sensor, Crank shaft position sensor, Air flow meter, Brake pad wear sensor, Thermostat base for air conditioner, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, wiper motor related parts, dustributor, starter switch, starter relay, transmission wire Harness, 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 Examples thereof include automobile / vehicle-related parts such as an oil filter and an ignition device case, a gasket for a primary battery or a secondary battery such as a mobile phone, a notebook computer, a video camera, a hybrid vehicle, and an electric vehicle.

Applications of molded products obtained by extrusion molding and blow molding include round bars, square bars, sheets, films, tubes, pipes, etc., and more specific applications include water heater motors, air conditioner motors, and drive motors. Electrical insulation materials for, film condensers, speaker vibration plates, magnetic tapes for recording, printed board materials, printed board peripheral parts, semiconductor packages, semiconductor transport trays, process / release films, protective films, automobile film sensors, etc. Insulation tape for wire cables, insulation washer in lithium ion batteries, hot water and cooling water, tubes for chemicals, fuel tubes for automobiles, hot water pipes, chemical pipes for chemical plants, ultra-pure water and ultra-high purity Examples thereof include pipes for solvents, automobile pipes, automobile cooling pipes, pipes for freon and supercritical carbon dioxide refrigerants, and workpiece holding rings for polishing devices. In addition, wire harnesses and control wires such as hybrid automobiles, electric automobiles, railways, coating molded bodies for windings for motor coils of power generation equipment, heat-resistant electric wire cables for home appliances, flat cables used for wiring in automobiles, communication, etc. Examples thereof include a wire coating for transmission, high frequency, audio, measurement, etc., or a wound coating molded body of an in-vehicle transformer.

Hereinafter, the effects of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The basic evaluation in each example and comparative example was performed by the following method.

(1) Evaluation of melt viscosity For the resin composition pellets obtained in each Example and Comparative Example, a capillary graph manufactured by Toyo Seiki Co., Ltd. was used under the conditions of a test temperature of 300 ° C., a shear rate of 1216 / s, a capillary length of 10 mm, and a capillary diameter of 1 mm. Was measured.

(2) Injection Molding For the resin composition pellets obtained in each Example and Comparative Example, an injection molding machine SE75-DUZ manufactured by Sumitomo Heavy Industries was used, and the cylinder temperature was 310 ° C. and the mold temperature was 140 ° C., ISO (1A). The dumbbell test piece was injection molded.

(3) Mechanical characteristic evaluation For the ISO (1A) dumbbell test piece obtained in (2), a fulcrum distance of 114 mm and tension were obtained according to ISO527-1, -2 using an Autograph AG-Xplus20kN tester under 23 ° C. conditions. The tensile properties were evaluated under the condition of a speed of 5 mm / min. Then, according to ISO178, the bending characteristics were evaluated under the conditions of a distance between fulcrums of 64 mm and a speed of 2 mm / min.

(4) Dynamic viscoelasticity evaluation The ISO (1A) dumbbell test piece obtained in (2) was cut to prepare a Charpy impact test piece (without notch) having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm.

Then, using DMA + 1000 (manufactured by Metarivib), the dynamic viscoelasticity was measured under the following conditions.
Test mode: 3-point bending test frequency: 1Hz
Distortion: 0.1%
Measurement temperature range: 50-250 ° C
Temperature rise rate: 2 ° C / min

Based on the data measured under the above conditions, create a graph with the obtained loss tangent (tan δ) as the horizontal axis, read the temperature at which tan δ is maximum at 200 ° C or higher, and read the temperature in the PPS resin composition. The glass transition temperature derived from the PES resin was used. Further, the elastic modulus (E) at 150 ° C. was read and used as the flexural modulus at 150 ° C.

The raw materials used in each example and comparative example are shown below.

[Reference Example 1] (A) Polyphenylene sulfide resin (A-1)
4.75% sodium hydroxide 8.27 kg (70.00 mol), 96% sodium hydroxide 2.94 kg (70.63 mol), N-methyl-2 in a 70 liter autoclave with stirrer and bottom plug valve. -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 2.24 kg (27.3 mol), and ion-exchanged water 5.50 kg were charged, and it took about 3 hours to reach 245 ° C while passing nitrogen under normal pressure. After gradually heating and distilling 9.77 kg of water and 0.28 kg of NMP, 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., 10.32 kg (70.20 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 to 0. The temperature was raised from 200 ° C. to 235 ° C. at a rate of 8 ° C./min, and the reaction was carried out at 235 ° C. for 40 minutes. After that, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min, the reaction was carried out at 270 ° C. for 70 minutes, and then 2.40 kg (133 mol) of water was press-fitted while cooling from 270 ° C. to 250 ° C. over 15 minutes. .. Then, after gradually cooling from 250 ° C. to 220 ° C. over 75 minutes, the mixture was rapidly cooled to near room temperature and the contents were taken out.

The contents were diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (opening 0.175 mm) to obtain a solid substance. The obtained solid was similarly washed and filtered with about 35 liters of NMP. The operation of diluting the obtained solid matter with 70 liters of ion-exchanged water, stirring at 70 ° C. for 30 minutes, and then filtering with an 80-mesh wire mesh to recover the solid matter was repeated a total of 3 times. The obtained solid matter and 32 g of acetic acid are diluted with 70 liters of ion-exchanged water, stirred at 70 ° C. for 30 minutes, filtered through an 80-mesh wire mesh, and the obtained solid matter is further diluted with 70 liters of ion-exchanged water. After stirring at 70 ° C. for 30 minutes, the solid material was recovered by filtering with an 80 mesh wire mesh. The solid matter thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS. The obtained (A) polyphenylene sulfide resin had a melt viscosity of 200 Pa · s (310 ° C., shear rate: 1000 / s). The (A) polyphenylene sulfide resin thus obtained was designated as A-1.

[Reference Example 2] (A) Polyphenylene sulfide resin (A-2)
4.75% sodium hydroxide 8.27 kg (70.00 mol), 96% sodium hydroxide 2.91 kg (69.80 mol), N-methyl-2 in a 70 liter autoclave with stirrer and bottom plug valve. -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 1.89 kg (23.10 mol), and ion-exchanged water 10.5 kg were charged, and it took about 3 hours to reach 245 ° C while passing nitrogen under normal pressure. After gradually heating and distilling 14.78 kg of water and 0.28 kg of NMP, 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., 10.45 kg (71.07 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 to 0. 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, open the bottom valve of the autoclave, flush the contents into a container with a stirrer for 15 minutes while pressurizing with nitrogen, and stir for a while at 250 ° C to remove most NMP. did.

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

90 liters of the obtained cake and ion-exchanged water were 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. The obtained (A) polyphenylene sulfide resin had a melt viscosity of 40 Pa · s (310 ° C., shear rate: 1000 / s). The (A) polyphenylene sulfide resin thus obtained was designated as A-2.

[Other raw materials]
(B-1) PES resin: "Sumika Excel" 4800G manufactured by Sumitomo Chemical Co., Ltd., reducing viscosity: 0.48
(B-2) PES resin: "Sumika Excel" 5003P manufactured by Sumitomo Chemical Co., Ltd., reduction viscosity: 0.50, 100 (C-1) tetracarboxylic acid having a terminal hydroxyl group per unit of polymerization repeat. Dianhydride 1: Pyromeric anhydride (C-2) tetracarboxylic acid dianhydride 2: 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (C-3) Tetracarboxylic acid dianhydride 3: 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (C-4) tetracarboxylic acid dianhydride 4: 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (D-1) Inorganic filler: glass fiber (T-747H manufactured by Nippon Denki Glass Co., Ltd.), 3 mm long, average fiber diameter 10.5 μm
Organic silane compound (alkoxysilane): 3-isocyanatepropyltriethoxysilane (KBE9007N manufactured by Shinetsu Silicone Co., Ltd.)

[Examples 1 to 7, Comparative Examples 1 to 4]
After dry blending each raw material at the ratios shown in Tables 1 and 2, a cylinder temperature was used using a TEX30α twin-screw extruder (L / D = 45, kneading section 2 locations) manufactured by Japan Steel Works, which was equipped with a vacuum vent. It was melt-kneaded at 280 ° C. and a screw rotation speed of 300 rpm, and pelletized by a strand cutter. Next, various physical property evaluations were performed on the test pieces obtained by injection molding the pellets dried at 130 ° C. overnight.

The results of the examples and comparative examples in Tables 1 and 2 will be described.

By comparing Examples 1 and 2 with Comparative Examples 1 to 3, a resin composition composed of (A) polyphenylene sulfide resin and (B) PES resin was blended with alkoxysilane to achieve tensile modulus at break and bending at 150 ° C. It can be seen that while the elastic modulus increased, the melt viscosity increased, that is, the fluidity decreased. On the other hand, by blending (C) tetracarboxylic acid dianhydride instead of alkoxysilane, the tensile elongation at break and the flexural modulus at 150 ° C. are increased, while the melt viscosity is lowered, and the toughness, high-temperature rigidity, and fluidity are increased. It can be seen that the excellent characteristics suitable for injection molding are exhibited. In addition, Table 1 is a PPS resin composition containing no inorganic filler (D), and since the load in the high temperature range in the dynamic viscoelasticity measurement is small, the glass transition temperature derived from the PES resin in the PPS resin composition is measured. Can not do it.

Table 2 shows Examples and Comparative Examples in the case of blending (D) an inorganic filler, but by comparing Examples 3 to 7 with Comparative Example 4, the PPS resin composition containing (D) an inorganic filler was used. Even so, it can be seen that the blending of (C) tetracarboxylic acid dianhydride increases the tensile elongation at break and the flexural modulus at 150 ° C., while lowering the melt viscosity.

Claims (4)

0.01 to 10 parts by weight of (C) tetracarboxylic acid dianhydride with respect to 99 to 60 parts by weight of (A) polyphenylene sulfide resin and 1 to 40 parts by weight of (B) polyether sulfone resin. A polyphenylene sulfide resin composition which is partially blended. The polyphenylene sulfide resin composition according to claim 1, wherein the (C) tetracarboxylic acid dianhydride is the (C) tetracarboxylic acid dianhydride represented by the general formula (1) or the general formula (2). ..

(R ¹ to R ⁸ may be the same or different, hydrogen atom, alkyl group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, halogen, hydroxyl group, carboxyl group, amino group, sulfone group, nitro. It is either a group or a cyano group. X is either a single bond, O, CO, S, SO, CH ₂ , C (CH ₃ ) ₂ , or C (CF ₃ ) _2. ) The polyphenylene sulfide resin composition according to claim 1 or 2, wherein the inorganic filler is blended in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total of the polyphenylene sulfide resin (A) and the polyether sulfone resin (B). thing. A molded product comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 3.