JP7151086B2 - Polyphenylene sulfide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition having excellent dielectric properties and mechanical strength.

Polyphenylene sulfide (hereinafter abbreviated as "PPS") resin is an engineering plastic excellent in heat resistance, flame retardancy, chemical resistance, electrical insulation, heat and humidity resistance, mechanical strength and dimensional stability. PPS resin can be molded into various molded products, fibers, films, etc. by various molding methods such as injection molding and extrusion molding, so it is practically used in a wide range of fields such as electrical and electronic parts, mechanical parts and automobile parts. ing. Further, the mechanical strength and dimensional stability can be improved by blending the PPS resin with a fibrous filler such as glass fiber or carbon fiber, or an inorganic filler such as calcium carbonate, talc or mica.

In recent years, there has been a demand to suppress transmission loss, which is caused by dielectric loss and conductor loss, in the housing applications of electronic devices such as personal computers, tablets, and mobile phones that use megahertz and gigahertz band radio waves for communication. A high-strength resin material having a low dielectric constant is required for the purpose of suppressing the

However, E-glass, which is most commonly used as glass fiber for resin reinforcement, has a high dielectric constant. Application to the above uses was difficult.

For the purpose of solving this problem, Patent Document 1 discloses that polyarylene sulfide resin is blended with an ethylene copolymer, glass fiber, a white colorant, a blue colorant and a purple colorant in a specific composition. , proposals have been made to obtain compositions with low dielectric constants.

Patent Document 2 discloses a glass composition with a low dielectric constant, which has a composition in which CaO is reduced and B ₂ O ₃ is increased as compared with the commonly used E glass. discloses a reinforced resin molded article using glass fibers made of glass having a low dielectric constant.

JP 2017-88690 A JP-A-63-2831 JP 2017-52974 A

However, the glass fiber used in Patent Document 1 is a glass fiber having an E-glass composition that is used for general purposes, and a sufficiently low dielectric constant cannot be obtained.

Moreover, Patent Document 2 does not describe a reinforced resin using glass fibers having a low dielectric constant.

On the other hand, although Patent Document 3 describes a reinforced resin molded product, there is no description about the modification of the resin when increasing the strength of the resin using glass fibers, and the strength improvement effect is limited.

Therefore, the present invention provides a PPS resin composition that has both excellent dielectric properties (low relative dielectric constant) and mechanical strength without impairing various physical properties such as excellent heat resistance and chemical resistance inherent in PPS resin. The task is to obtain

As a result of intensive studies aimed at solving such problems, the present invention has found that by blending a PPS resin, a glass fiber made of glass having a relative dielectric constant of 5.5 or less, and a silane coupling agent in a specific composition, an excellent To obtain a PPS resin composition having both excellent dielectric properties and mechanical strength.

That is, the present invention has been made to solve at least part of the above problems, and can be implemented as the following modes.
(1) (a) 100 parts by weight of polyphenylene sulfide resin, (b) 25 to 100 parts by weight of glass fiber made of glass having a dielectric constant of 5.5 or less, (c) 0.1 to 100 parts by weight of a silane coupling agent 10 parts by weight, and (d) a polyphenylene sulfide resin composition containing 5 to 80 parts by weight of any resin selected from thermoplastic elastomers and fluororesins, and a molded article made of the resin composition. In the resin phase separation structure observed with an electron microscope, the component (a) forms a continuous phase (sea phase) and the component (d) forms a primary dispersed phase (island phase) having a number average dispersion diameter of 1 μm or less. A polyphenylene sulfide resin composition characterized by:
(2) The polyphenylene sulfide resin composition according to (1), wherein the polyphenylene sulfide resin (a) has a carboxyl group content of 25 to 400 μmol/g.

According to the present invention, a PPS having both excellent dielectric properties and mechanical strength is obtained by blending a PPS resin, a glass fiber made of glass having a dielectric constant of 5.5 or less, and a silane coupling agent in a specific composition. A resin composition can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
(1) (a) polyphenylene sulfide resin (a) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula,

From the viewpoint of heat resistance, a polymer containing 70 mol % or more, more preferably 90 mol % or more of a polymer containing a repeating unit represented by the above structural formula is preferred. In the (a) PPS resin, about less than 30 mol % of the repeating units may be composed of repeating units having the following structure.

Since a PPS copolymer partially having such a structure has a low melting point, such a resin composition is advantageous in terms of moldability.

The weight-average molecular weight of the (a) PPS resin used in the present invention is not particularly limited, but the weight-average molecular weight is preferably 20,000 to 150,000, more preferably 25,000 to 130,000, and more preferably 30,000 to 90,000 in order to obtain better mechanical properties. is more preferred. When the weight-average molecular weight is small, the mechanical properties of the PPS resin itself deteriorate, so the weight-average molecular weight is preferably 20,000 or more. On the other hand, when the weight-average molecular weight exceeds 150,000, the melt viscosity is significantly increased, which tends to be unfavorable in molding.

In addition, the weight average molecular weight in the present invention is a value calculated in terms of polystyrene using gel permeation chromatography (GPC) manufactured by Senshu Kagaku.

The (a) PPS resin of the present invention is used from the viewpoint of (b) improving the adhesion with glass fibers made of glass having a relative dielectric constant of 5.5 or less, and (c) improving the toughness of the resin with a silane coupling agent. , containing 25 to 400 μmol/g of carboxyl groups is also mentioned as a preferred embodiment. More preferably, the lower limit of the carboxyl group content is 30 μmol/g or more. The upper limit of the carboxyl group content is more preferably 250 μmol/g or less, still more preferably 150 μmol/g or less, even more preferably 80 μmol/g or less, most preferably 60 μmol/g or less. If the amount of carboxyl groups in the PPS resin is less than 25 μmol/g, the interaction between the silane coupling agent and the glass fiber made of glass having a dielectric constant of 5.5 or less tends to decrease, which is not preferable. On the other hand, when the carboxyl group content of the PPS resin exceeds 400 μmol/g, the volatile content in the processing step increases, which is not preferable.

(a) A method for introducing a carboxyl group into a PPS resin includes a method of copolymerizing a polyhalogenated aromatic compound containing a carboxyl group, or adding a compound containing a carboxyl group, such as maleic anhydride or sorbic acid. Then, (a) a method of introducing by reacting with a PPS resin while being melt-kneaded can be exemplified.

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 polyhalogen aromatic compound, the sulfidating agent, the polymerization solvent, the molecular weight modifier, the polymerization aid and the polymerization stabilizer used in the production method will be explained.

[Polyhalogenated Aromatic Compound]
A polyhalogenated 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, hexa Polyhalogenated aromatics such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene group compounds, preferably p-dichlorobenzene is used. In addition, for the purpose of introducing a carboxyl group, carboxyl group-containing dihalogenated aromatics such as 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, and 3,5-dichlorobenzoic acid It is also one of preferred embodiments to use compounds and mixtures thereof as copolymerizable monomers. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, It is preferable to use p-dihalogenated aromatic compound as a main component.

The amount of the polyhalogenated aromatic compound used is 0.9 to 2.0 mol, preferably 0.95 to 1.0 mol, per mol of the sulfidating agent, from the viewpoint of obtaining the (a) PPS resin having a viscosity suitable for processing. A range of 5 mol, more preferably 1.005 to 1.2 mol can be exemplified.

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

Specific examples of alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, with sodium sulfide being preferred. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in anhydrous form.

Specific examples of alkali metal hydrosulfides include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in anhydrous form.

Alkali metal sulfides prepared in situ in the reaction system from alkali metal hydrosulfides and alkali metal hydroxides can also be used. Alternatively, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and transferred to a polymerization vessel for use.

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

The amount of the charged sulfidating agent means the remaining amount obtained by subtracting the loss from the actual charged amount when a part of the sulfiding agent is lost before the start of the polymerization reaction due to dehydration or the like.

An alkali metal hydroxide and/or an alkaline earth metal hydroxide can be used together with the sulfidating agent. Specific examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures of two or more thereof. Specific examples of metal hydroxides include calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Among them, sodium hydroxide is preferably used.

When an alkali metal hydrosulfide is used as the sulfidating agent, it is particularly preferable to use an alkali metal hydroxide at the same time. A range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.

[Polymerization solvent]
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, 1,3-dimethyl-2-imidazolidine non-, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric acid triamide, dimethylsulfone, aprotic organic solvents represented by tetramethylene sulfoxide, and mixtures thereof; It is preferably used because of its high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

The organic polar solvent is used in an amount of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, more preferably 2.5 to 5.5 mol per 1 mol of the sulfidating agent.

[Molecular weight modifier]
(a) A monohalogen compound (not necessarily an aromatic compound) is combined with the polyhalogenated aromatic compound in order to form a terminal of the PPS resin to be produced, or to adjust the polymerization reaction or molecular weight. Can be used together.

[Polymerization aid]
In order to obtain the (a) PPS resin with a relatively high degree of polymerization in a shorter time, it is also one of preferred embodiments to use a polymerization aid. The term "polymerization aid" as used herein means a substance that has the effect of increasing the viscosity of the resulting (a) PPS resin. Specific examples of such polymerization aids include organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earth metal salts. metal phosphates and the like. These may be used alone or in combination of two or more. Among them, organic carboxylates, water, and alkali metal chlorides are preferable, and more preferable organic carboxylates are alkali metal carboxylates, and alkali metal chlorides are lithium chloride.

The alkali metal carboxylate has the general formula R(COOM) _n (wherein R is an alkyl group, cycloalkyl group, aryl group, alkylaryl group or 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, anhydrous or aqueous solutions. Specific examples of alkali metal carboxylates include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. can be mentioned.

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

When these alkali metal carboxylates are used as polymerization aids, the amount used is usually in the range of 0.01 mol to 2 mol per 1 mol of the charged alkali metal sulfide. A range of 0.1 to 0.6 mol is preferred, and a range of 0.2 to 0.5 mol is more preferred.

When water is used as a polymerization aid, the amount added is usually in the range of 0.3 mol to 15 mol per 1 mol of the charged alkali metal sulfide. A range of 10 moles is preferred, and a range of 1 to 5 moles is more preferred.

Of course, it is possible to use two or more kinds of these polymerization aids in combination. For example, if an alkali metal carboxylate and water are used in combination, it is possible to increase the molecular weight with a smaller amount of each.

The timing of addition of these polymerization auxiliaries is not particularly specified, and they may be added at any time during the pre-process described later, at the start of polymerization, or during polymerization, or may be added in multiple portions. When an alkali metal carboxylate is used as a polymerization aid, it is more preferable to add it at the start of the preceding step or at the same time as the start of polymerization from the viewpoint of ease of addition. Further, when water is used as a polymerization aid, it is effective to add it during the polymerization reaction after charging the polyhalogenated aromatic compound.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One indication of side reactions is the formation of thiophenol, and the addition of a polymerization stabilizer can suppress the formation of thiophenol. Specific examples of polymerization stabilizers 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 preferred. The above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, and is included in one of the polymerization stabilizers. In addition, when an alkali metal hydrosulfide is used as the sulfidation agent, it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also serve as polymerization stabilizers.

These polymerization stabilizers may be used alone or in combination of two or more. The amount of the polymerization stabilizer is usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, per 1 mol of the charged alkali metal sulfide. It is preferred to use in If this ratio is too small, the stabilizing effect will be insufficient.

The timing of addition of the polymerization stabilizer is not particularly specified. It is more preferable from the point that it is easy to add at the time of starting the process or at the time of starting the polymerization.

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

[pre-process]
(a) In the method for producing the PPS resin, the sulfidation agent is usually used in the form of a hydrate. It is preferable to warm and remove excess water out of the system.

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

In the polymerization reaction, the amount of water in the polymerization system is preferably 0.3 to 10.0 mol per 1 mol of the charged sulfidating 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 fed into the polymerization system. Moreover, the water to be charged may be in any form such as water, an aqueous solution, or water of crystallization.

[Polymerization reaction step]
(a) PPS resin is produced by reacting a sulfidating 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 sulfidating agent and the polyhalogenated aromatic compound are preferably mixed in an inert gas atmosphere at a temperature range of room temperature to 240° C., preferably 100 to 230° C. . A polymerization aid may be added at this stage. These raw materials may be added in any order, or may be added at the same time.

Such a mixture is usually heated to a temperature in the range of 200°C to 290°C. There is no particular limitation on the heating rate, 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.

Generally, the temperature is finally raised to 250-290° C., and the reaction is carried out at that temperature for usually 0.25-50 hours, preferably 0.5-20 hours.

A method of raising the temperature to 270 to 290° C. after reacting at 200 to 260° C. for a certain period of time before reaching the final temperature is effective in obtaining a higher degree of polymerization. In this case, 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 order to obtain a polymer with a higher degree of polymerization, it may be effective to carry out polymerization in multiple stages. When the polymerization is carried out in multiple stages, 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 (hereinafter abbreviated as PHA) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When the polyhalogenated aromatic compound is added in excess molar ratio to the alkali metal sulfide Conversion rate = [PHA charge amount (mol) - PHA residual amount (mol)] / [PHA charge amount (mol) -PHA excess amount (mol)]
(B) In cases other than the above (A) Conversion rate = [PHA charged amount (mol) - PHA residual amount (mol)]/[PHA charged amount (mol)].

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

For example, after completion of the polymerization reaction, a method of recovering the particulate polymer by slow cooling may be used. The slow cooling rate at this time is not particularly limited, but it is usually about 0.1° C./min to 3° C./min. It is not necessary to anneal at the same rate throughout the slow cooling process, and a method of slow 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 may be used. May be adopted.

It is also one of the preferred methods to perform the above-mentioned recovery under rapid cooling conditions, and one preferred method of this recovery method is the flash method. In the flash method, the polymerization reaction product is flashed from a high temperature and high pressure state (usually 250° C. or higher, 8 kg/cm ² or higher) into an atmosphere of normal pressure or reduced pressure, and the polymer is powdered and recovered at the same time as the solvent is recovered. The term "flash" as used herein means ejecting the polymerization reactant from a nozzle. The flashing atmosphere is, for example, 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]
(a) The PPS resin may be subjected to acid treatment, hot water treatment, washing with an organic solvent, alkali metal or alkaline earth metal treatment after being produced through the above polymerization and recovery steps.

When acid treatment is performed, it is as follows. (a) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not decompose the (a) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid are more preferably used, but those such as nitric acid that decompose and deteriorate the (a) PPS resin are not preferable.

The acid treatment may be carried out by immersing the (a) PPS resin in an acid or an acid aqueous solution, and if necessary, stirring or heating may be used. For example, when using acetic acid, 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 higher, eg, about pH 4-8. The acid-treated (a) PPS resin is preferably washed several times with water or hot water in order to remove residual acids or salts. The water used for washing is preferably distilled water or deionized water in the sense that the preferable chemical modification effect of the (a) PPS resin by acid treatment is not impaired.

The case of performing hot water treatment is as follows. (a) 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 less than 100°C, the desired chemical modification effect of (a) the PPS resin is small, which is not preferable.

The water to be used is preferably distilled water or deionized water in order to exhibit the desired chemical modification effect of the (a) PPS resin by washing with hot water. There are no particular restrictions on the operation of the hot water treatment, and a predetermined amount of (a) PPS resin is added to a predetermined amount of water, heated and stirred in a pressure vessel, or continuously subjected to hot water treatment. will be The proportion of (a) PPS resin and water is preferably as high as possible, but usually a bath ratio of 200 g or less of (a) PPS resin per 1 liter of water is selected.

In addition, since decomposition of terminal groups is undesirable, the atmosphere for the treatment is desirably an inert atmosphere in order to avoid this. Furthermore, the (a) PPS resin that has undergone this hot water treatment operation is preferably washed several times with warm water to remove residual components.

In the case of washing with an organic solvent, it is as follows. (a) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not decompose the (a) PPS resin. Examples include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphorasamide, and piperazinones, sulfoxide/sulfone solvents such as dimethylsulfoxide, dimethylsulfone, and sulfolane, ketones such as acetone, methylethylketone, diethylketone, and acetophenone Ether solvents such as dimethyl ether, dipropyl ether, dioxane and tetrahydrofuran, chloroform, methylene chloride, trichlorethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, chlorobenzene Alcohol/phenol 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 Solvents and the like are included. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferred. These organic solvents are used singly or in combination of two or more.

As a method for washing with an organic solvent, there is a method such as immersing (a) the PPS resin in an organic solvent, and if necessary, it is possible to appropriately stir or heat the resin. The washing temperature for washing the (a) PPS resin with an organic solvent is not particularly limited, and any temperature in the range of normal temperature to about 300° C. can be selected. There is a tendency that the higher the washing temperature, the higher the washing efficiency. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Also, the cleaning time is not particularly limited. Although it depends on the cleaning conditions, in the case of batch cleaning, a sufficient effect can be obtained by cleaning for 5 minutes or more. It is also possible to wash continuously.

Examples of the method of treating with an alkali metal or alkaline earth metal include a method of adding an alkali metal salt or an alkaline earth metal salt before, during, or after the pre-process, a method of adding an alkali metal salt or an alkaline earth metal salt before, during, or after the pre-process, before, during, or during the polymerization process. Examples include a method of adding an alkali metal salt or alkaline earth metal salt to the polymerization reactor afterward, or a method of adding an alkali metal salt or alkaline earth metal salt at the beginning, middle or end of the washing process. Among them, the easiest method includes a method of adding an alkali metal salt or an alkaline earth metal salt after removing residual oligomers and residual salts by washing with an organic solvent or washing with warm or hot water. Alkali metals and alkaline earth metals are preferably introduced into the PPS in the form of alkali metal ions and alkaline earth metal ions such as acetates, hydroxides and carbonates. Further, it is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water or the like. When the alkali metal or alkaline earth metal is introduced, the concentration of the alkali metal ion or alkaline earth metal ion is preferably 0.001 mmol or more, more preferably 0.01 mmol or more, relative 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, 280° C. or less is usually preferable from the viewpoint of operability. The bath ratio (the weight of the washing liquid to the weight of the dry PPS) is preferably 0.5 or more, more preferably 3 or more, and even more preferably 5 or more.

In the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition excellent in retention stability, residual oligomers and residual salts are removed by repeating organic solvent washing and hot water washing at about 80° C. or the above hot water washing several times. After that, acid treatment or treatment with an alkali metal salt or alkaline earth metal salt is preferred, and a method of treatment with an alkali metal salt or alkaline earth metal salt is more preferred.

In addition, the (a) PPS resin can be used after being polymerized by thermal oxidation cross-linking treatment by heating in an oxygen atmosphere and heating with addition of a cross-linking agent such as a peroxide after completion of polymerization.

When dry heat treatment is performed for the purpose of increasing the molecular weight by thermal oxidation crosslinking, the temperature is preferably 160 to 260°C, more preferably 170 to 250°C. Also, the oxygen concentration is desirably 5% by volume or more, more preferably 8% by volume or more. Although there is no particular upper limit for the oxygen concentration, the upper limit is about 50% by volume. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, even more preferably 2 to 25 hours. The heat treatment device may be a normal hot air dryer or a heating device with a rotating or stirring blade. For efficient and more uniform processing, a rotary or heating device with a stirring blade may be used. It is more preferable to use

It is also possible to perform dry heat treatment for the purpose of suppressing thermal oxidation cross-linking and removing volatile matter. The temperature is preferably 130-250°C, more preferably 160-250°C. In this case, the oxygen concentration is desirably 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, even more preferably 1 to 10 hours. The heat treatment device may be a normal hot air dryer or a heating device with a rotating or stirring blade. For efficient and more uniform processing, a rotary or heating device with a stirring blade may be used. It is more preferable to use

However, from the viewpoint of exhibiting excellent toughness, the (a) PPS resin of the present invention is a substantially straight-chain PPS resin that is not subjected to high molecular weight by thermal oxidative cross-linking, or is lightly oxidative cross-linked. It is preferably a semi-crosslinked PPS resin. Moreover, in the present invention, a plurality of (a) PPS resins having different melt viscosities may be mixed and used.

(2) (b) Glass fiber made of glass having a dielectric constant of 5.5 or less Adding glass fiber made of glass having a dielectric constant of 5.5 or less to the PPS resin composition of the embodiment of the present invention is a PPS. It is essential for controlling the dielectric constant of the resin composition to be low and improving the mechanical strength. The dielectric constant of the glass constituting the glass fiber can be indicated as a preferable range of 3.7 to 5.5. The lower the lower limit of the relative dielectric constant, the better. However, in glass composed of SiO ₂ , the lower limit is 3.7, which is substantially the relative dielectric constant of SiO ₂ alone.

The glass fiber used in the present invention is a glass fiber made of glass having a dielectric constant of 5.5 or less, and is not particularly limited, but includes SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , CaO, The glass contains MgO, LiO ₂ , Na ₂ O, K ₂ O, and TiO ₂ , and the composition of each component is 50-70% by weight of SiO ₂ , 1-20% by weight of Al ₂ O ₃ , and B ₂ O ₃ . 15-30% by weight, 0.1-5% by weight of CaO, 0.1-5% by weight of MgO, _0-1 % by weight of _LiO2 , 0-1.5% by weight of _NaO2 , K2O preferably has a range of 0-1.5 wt% and TiO ₂ of 0-5 wt%.

A glass having a relative dielectric constant of 5.5 or less can be characterized by a large amount of B ₂ O ₃ and a small amount of CaO compared to the composition of E-glass, which is generally used.

The dielectric constant of the glass was determined by placing the glass in a platinum crucible and melting it in an electric furnace at about 1580° C. for 4 to 15 hours. After molding, the strain is removed by annealing, and the capacitance can be determined by evaluating the capacitance of the plate-shaped glass molding using an LCR meter or the like.

In the embodiment of the present invention, the amount of glass fiber (b) made of glass having a relative dielectric constant of 5.5 or less is made of (b) glass having a relative dielectric constant of 5.5 or less with respect to 100 parts by weight of the PPS resin. The glass fiber is selected in the range of 0.1 to 150 parts by weight, more preferably 1 to 135 parts by weight, more preferably 5 to 120 parts by weight, even more preferably 10 to 100 parts by weight. (b) If the amount of glass fiber made of glass having a relative dielectric constant of 5.5 or less exceeds 150 parts by weight, the melt viscosity of the PPS resin composition is significantly increased, resulting in deterioration of moldability, which is not preferable. Also, if (b) the glass fiber made of glass having a dielectric constant of 5.5 or less is less than 0.1 parts by weight, it is difficult to achieve both desired mechanical properties and dielectric properties.

(b) pretreating the surface of glass fibers made of glass having a relative dielectric constant of 5.5 or less 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 also preferable from the viewpoint of improving the bundling property of the glass fibers, the dispersibility when blending with the resin, and the adhesion between the glass fibers and the resin.

The shape of the glass fiber used in the present invention is not particularly limited, but the fiber diameter is preferably 1 to 50 μm, more preferably 3 to 30 μm, even more preferably 5 to 20 μm.

On the other hand, the length of the glass fiber is preferably 30 μm to 10 mm, more preferably 50 μm to 5 mm. If the fiber diameter and fiber length are outside the above ranges, the effect of improving the mechanical strength of the resin composition cannot be obtained, which is not preferred.

(3) (c) Silane coupling agent By adding a silane coupling agent to the PPS resin composition of the embodiment of the present invention, the PPS resin and (b) glass fibers made of glass having a dielectric constant of 5.5 or less In addition to improving the adhesion of the interface, it is essential for manifesting the modifying effect of improving the toughness and mechanical strength of the PPS resin itself.

Specific examples of such silane coupling agents include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. mercapto group-containing alkoxysilane compounds such as alkoxysilane compounds containing γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-(2 Ureido group-containing alkoxysilane compounds such as ureidoethyl)aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane , γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and other isocyanate group-containing alkoxysilane compounds, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-( Silane coupling agents such as amino group-containing alkoxysilane compounds such as 2-aminoethyl)aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane can be mentioned, among which amino group- and isocyanate group-containing alkoxysilane compounds are PPS. It is particularly preferred from the viewpoint of reactivity with the resin.

The amount of the silane coupling agent added is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight, and particularly preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of the PPS resin. . If the amount of the silane coupling agent added is less than 0.1 parts by weight, the effect of modifying the PPS resin is poor and the effect of improving mechanical properties is not exhibited. On the other hand, when the amount of the silane coupling agent added exceeds 10 parts by weight, a large amount of volatile gas is generated during the production of the composition, which is not preferable from the viewpoint of productivity.

(4) (d) Alloy component In the embodiment of the present invention, although it is not an essential component, adding (d) an alloy component as a resin other than the PPS resin to the PPS resin composition can improve the mechanical properties of the PPS resin composition. and effective in enhancing dielectric properties.

The (d) alloy component used in the present invention includes polyamide resins, polyester resins, polyetherimide resins, polyethersulfone resins, polyphenylene ether resins, thermoplastic elastomers (olefin-based, polyamide-based, polyester-based), fluororesins, Any resin selected from silicone resins and epoxy resins, both of which are effective in improving mechanical properties. On the other hand, polyphenylene ether resins, thermoplastic elastomers, and fluororesins are preferred from the viewpoint of improving dielectric properties. These may be used in combination of multiple types.

The amount of the (d) alloy component in the embodiment of the present invention is preferably selected in the range of 0.1 to 150 parts by weight, and 1 to 125 parts by weight, relative to 100 parts by weight of the PPS resin. is more preferred, 3 to 100 parts by weight is more preferred, and 5 to 80 parts by weight is even more preferred. If the (d) alloy component exceeds 150 parts by weight, the dispersed state of the (d) alloy component in the PPS resin composition tends to become coarse, resulting in a decrease in mechanical properties. Also, if the (d) alloy component is less than 0.1 parts by weight, the desired mechanical properties and dielectric properties tend to be reduced. Using two or more alloy components in combination is also effective in achieving both excellent mechanical properties and dielectric properties.

The (d) alloy component used in the present invention may preferably contain a reactive functional group from the viewpoint of forming an intermolecular bond with a PPS resin or a silane coupling agent.

The reactive functional group is not particularly limited, and specifically includes a vinyl group, an epoxy group, a carboxyl group, an acid anhydride group, an ester group, an aldehyde group, a carbonyldioxy group, a haloformyl group, an alkoxycarbonyl group, an amino group, hydroxyl group, styryl group, methacryl group, acryl group, ureido group, mercapto group, sulfide group, isocyanate group, hydrolyzable silyl group, among others, epoxy group, carboxyl group, acid anhydride group, amino group , and hydroxyl groups are preferred, and two or more of these reactive functional groups may be contained.

As a method of introducing a reactive functional group into the alloy component, a method of blending a compound or resin containing the functional group which is compatible with the alloy component, or a method of adding the functional group when polymerizing the alloy component. A method of polymerizing with a polymerizable monomer containing or containing a functional group convertible to the functional group, and a functional group containing the functional group or convertible to the functional group when polymerizing the alloy component a method of using an initiator contained therein, a method of reacting the alloy component with a polymerizable monomer containing the functional group or a functional group convertible to the functional group in the presence of a radical generator, the alloy component Among them, among others, a method of introducing a functional group into the main chain or side chain of the alloy component by polymerization, and a polymerizable monomer containing the alloy component and a functional group and in the presence of a radical generator is preferable from the viewpoint of quality, cost, and control of the introduction amount.

The polymerizable monomer containing the functional group is not particularly limited, but for example acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, hymic acid, acid anhydrides thereof, acrylic acid glycidyl, glycidyl methacrylate, glycidyl ethylacrylate, glycidyl itaconate, vinyl acetate, vinyl propionate, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like.

(d) The amount of functional groups contained in the alloy component is 0 per 1 g of the alloy component (d) from the viewpoint of sufficient progress of the reaction with the (a) PPS resin and (c) the silane coupling agent. 01 wt% or more is preferable, 0.05 wt% or more is more preferable, and 0.1 wt% or more is even more preferable. The upper limit of the amount of functional groups is not particularly limited as long as the original properties of the (d) alloy component are not impaired, and a preferable range is 15 wt % or less in consideration of the deterioration of fluidity and the like.

(5) (e) Inorganic Filler Although it is not an essential component in the PPS resin composition of the present invention, (e) an inorganic filler may be blended and used as long as the effects of the present invention are not impaired. Specific examples of the (e) inorganic filler include glass fiber, carbon fiber, carbon nanotube, carbon nanohorn, and potassium titanate whisker made of glass that does not correspond to the component (b) of the present invention and has a dielectric constant exceeding 5.5. , zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, fullerene, talc , wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, silicates such as alumina silicate, silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, iron oxide, etc. Metal compounds, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide, glass beads, glass flakes, and glass powder , ceramic beads, boron nitride, silicon carbide, carbon black, silica, and non-fibrous fillers such as graphite are used. Among them, glass fibers made of glass having a relative dielectric constant exceeding 5.5, silica, and calcium carbonate are preferable. Furthermore, calcium carbonate and silica are particularly preferable from the viewpoint of anti-corrosion and lubricant effects. These (e) inorganic fillers may be hollow, and two or more of them may be used in combination. These (e) inorganic fillers may be pretreated 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 before use.

The amount of the inorganic filler compounded is selected from a range of 40 parts by weight or less, preferably less than 10 parts by weight, more preferably less than 1 part by weight, based on 100 parts by weight of the (a) polyphenylene sulfide resin. A range of 0.8 parts by weight or less is more preferred. Although there is no particular lower limit, 0.0001 parts by weight or more is preferable. Although the addition of inorganic fillers is effective in improving the mechanical strength of the material, addition of a large amount exceeding 40 parts by weight is not preferable because the balance between mechanical strength and dielectric properties is lowered. The content of the inorganic filler can be appropriately changed depending on the application from the balance between mechanical strength and dielectric properties.

(6) (f) Other Additives Further, the PPS resin composition of the present invention may contain a resin other than the alloy component (d) as long as the effects of the present invention are not impaired. Specific examples thereof include polysulfone resins, polyarylsulfone resins, polyketone resins, polyarylate resins, liquid crystal polymers, polyetherketone resins, polythioetherketone resins, polyetheretherketone resins, polyimide resins, and polyamideimide resins. be done.

Moreover, the following compounds can be added for the purpose of modification. Polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, plasticizers such as organic phosphorus compounds, crystal nucleating agents such as organic phosphorus compounds, polyether ether ketones, montanic acid waxes, lithium stearate, aluminum stearate metal soaps such as ethylenediamine/stearic acid/sebacic acid polycondensate, release agents such as silicone compounds, coloring inhibitors such as hypophosphite, water, lubricants, UV inhibitors, coloring agents, foaming Usual additives such as agents can be incorporated. If any of the above compounds exceeds 20% by weight of the total composition, the original properties of the PPS resin composition of the present invention are impaired, so it is preferable to add 10% by weight or less, more preferably 1% by weight or less.

(7) Method for producing a resin composition As a method for producing the PPS resin composition of the present invention, production in a molten state, production in a solution state, or the like can be used. Manufacturing is preferably used. For production in a molten state, melt-kneading by an extruder, melt-kneading by a kneader, or the like can be used, but from the viewpoint of productivity, melt-kneading by an extruder, which enables continuous production, is preferably used.

For melt-kneading by an extruder, one or more extruders such as a single-screw extruder, a twin-screw extruder, a multi-screw extruder such as a four-screw extruder, and a twin-screw single-screw composite extruder can be used. From the viewpoint of improving properties, reactivity and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and melt-kneading by a twin-screw extruder is most preferable.

A more specific method of melt-kneading is not necessarily limited to this, but L/D (L: screw length, D: screw diameter) is 10 or more, preferably 20 or more, and kneading It is preferable to use a twin-screw extruder having two or more, preferably three or more, sections. Although the upper limit of L/D is not particularly limited, 60 or less is preferable from the viewpoint of economy. Also, the upper limit of the number of kneading portions is not particularly limited, but from the viewpoint of productivity, it is preferably 10 or less.

The number of screw revolutions is 150 to 1000 revolutions/minute, preferably 300 to 1000 revolutions/minute, and a typical example is a method of kneading at a processing temperature of +5 to 100°C of the melting point of (a) the PPS resin and (d) the alloy component. can be mentioned.

The order of mixing raw materials during melt-kneading is not particularly limited, but a method of melt-kneading by the above method after blending all the raw materials, a method of melt-kneading by the above method after blending some of the raw materials, A method of blending this and the remaining raw materials and melt-kneading, or a method of blending a part of the raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading with a twin-screw extruder. may be used.

As for (f) other additive components, it is of course possible to knead and pelletize the other components by the above-described method, and then add the pellets before molding and subject them to molding.

(8) PPS resin composition The PPS resin composition of the embodiment of the present invention has a tensile strength (ISO (1A) dumbbell test piece, tensile speed 5 mm / min, 23 ° C., ISO527) is preferably 115 MPa or higher, more preferably 140 MPa or higher, more preferably 155 MPa or higher, and even more preferably 170 MPa or higher. If it is less than 115 MPa, for example, the practical strength of the housing of electronic equipment is inferior and cannot be applied. There is no particular limitation on the upper limit of tensile strength.

The dielectric constant of the PPS resin composition of the embodiment of the invention is preferably 3.50 or less, more preferably 3.40 or less.

The term "relative dielectric constant" refers to a value measured on a 3 mm-thick square plate made of a PPS resin composition in accordance with ASTM D-150 transformer bridge method at a measurement frequency of 1 MHz. If the dielectric constant exceeds 3.50, the electrical properties are poor, and it is not possible to obtain a PPS resin composition that is excellent in the balance between mechanical strength and dielectric properties desired by the present invention. A lower dielectric constant is more preferable, but the lower limit can be exemplified by a vacuum dielectric constant of 1 or more.

As for the phase structure of the (d) alloy component in the PPS resin composition of the embodiment of the present invention, the PPS resin forms a sea phase (continuous phase or matrix), and the (d) alloy component forms an island phase (dispersed phase). It is desirable to form Furthermore, the number average dispersion diameter of the primary dispersed phase of the alloy component (d) is preferably 1 μm or less, more preferably 800 nm or less, and even more preferably 500 nm or less. The lower limit is preferably 1 nm or more from the viewpoint of productivity. The PPS resin phase forms a continuous phase, and the (d) alloy component is present with good dispersibility. Dielectric properties can be expressed.

The "number average dispersion diameter of the primary dispersed phase of component (d)" is the higher melting peak temperature of the melting peak temperatures of the PPS resin and (d) alloy component + the molding temperature of 20 to 40 ° C. An ISO (1A) dumbbell test piece was molded with, a thin piece of 0.1 μm or less was cut from the center in the cross-sectional area direction of the dumbbell piece, and observed at a magnification of about 1000 to 10000 times with a transmission electron microscope. For 100 island phases of the (d) alloy component, first, the maximum diameter and minimum diameter of each island phase are measured to obtain an average value, and then the numerical average value obtained from them.

(9) Applications The polyphenylene sulfide resin composition of the present invention can be molded by various molding techniques such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding, etc. Among them, it is useful for injection molding and extrusion molding. is.

In addition, the polyphenylene sulfide resin composition of the present invention has excellent chemical resistance and heat resistance, as well as excellent mechanical strength and dielectric properties. It is suitable to use for such as.

Molded products obtained by extrusion molding include round bars, square bars, sheets, films, tubes, pipes, etc. More specific uses include electric insulation for water heater motors, air conditioner motors, drive motors, etc. Materials, film capacitors, speaker diaphragms, magnetic tapes for recording, printed circuit board materials, printed circuit board peripheral parts, semiconductor packages, semiconductor transport trays, process/release films, protective films, film sensors for automobiles, insulating tapes for wire cables , insulating washers in lithium-ion batteries, hot water and cooling water, tubes for chemicals, fuel tubes for automobiles, hot water piping, chemical piping in chemical plants, piping for ultrapure water and ultrapure solvents, Examples include piping for automobiles, piping for freon and supercritical carbon dioxide refrigerants, and workpiece retaining rings for polishing equipment. In addition, hybrid vehicles, electric vehicles, railways, coated moldings for motor coil windings for power generation equipment, heat-resistant electric wires and cables for home appliances, wire harnesses and control wires such as flat cables used for wiring in automobiles, communication, For example, it may be a signal transformer for transmission, high frequency, audio, measurement, or the like, or a coated molding of windings of a vehicle-mounted transformer.

Applications of molded products obtained by injection molding include generators, electric motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, and other poles. Electric equipment parts such as rods, electric parts cabinets, sensors, LED lamps, connectors, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs , printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc.; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio equipment, laser discs (registered trademark) and compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriters Household/office electrical product parts represented by parts, word processor parts, etc. Representatives are office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, writers, typewriters, etc. Machine-related parts used: Microscopes, binoculars, cameras, clocks and other optical equipment and precision machinery-related parts; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light gear, various valves such as exhaust gas valves , fuel related / exhaust system / intake system various pipes and ducts, turbo duct, 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, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating warm air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, Wiper motor related parts, dust tributors, starter switches, starter relays, wire harnesses for transmissions, windshields 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 , automobile/vehicle-related parts such as ignition device cases, gaskets for primary or secondary batteries of mobile phones, laptop computers, video cameras, hybrid vehicles, electric vehicles, and the like.

Among others, it is useful as housings for electronic devices such as personal computers, tablets, and mobile phones that use the megahertz band or gigahertz band for communication, and interior and exterior members for gasoline-powered vehicles, hybrid vehicles, and electric vehicles.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Examples 1 to 4 are reference examples.

In the examples and comparative examples, (a) PPS resin, (b) glass fiber made of glass having a dielectric constant of 5.5 or less, (c) silane coupling agent, (d) alloy component, (e) inorganic filler The following were used.
[(a) PPS resin (a-1 to 3)]
a-1: Linear type PPS resin weight average molecular weight: 50000, carboxyl group content: 42 μmol/g
a-2: Linear type PPS resin weight average molecular weight: 70000, carboxyl group content: 26 µmol/g
a-3: Crosslinked PPS resin Weight average molecular weight: 40000, carboxyl group content: 17 μmol/g
[(b) Glass fiber (b-1) made of glass having a dielectric constant of 5.5 or less]
b-1: Glass fiber (chopped strand CS (HL)-E303N-3 manufactured by CPIC) Fiber diameter: 13 μm, relative dielectric constant 4.8
[(c) silane coupling agent (c-1)]
c-1: γ-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.)
[(d) alloy components (d-1 to 2)]
d-1: Olefin-based thermoplastic elastomer (Bondfast E manufactured by Sumitomo Chemical Co., Ltd.), ethylene-glycidyl dimethacrylate copolymer, glycidyl methacrylate: 12 wt%
d-2: olefinic thermoplastic elastomer (TX-650 manufactured by Mitsui Chemicals), ethylene-butene copolymer d-3: fluororesin (AH2000 manufactured by Asahi Glass Co., Ltd.), ethylene-tetrafluoroethylene copolymer [(e) Inorganic filler (e-1)]
e-1: Glass fiber (chopped strand ECS-T747 manufactured by Nippon Electric Glass Co., Ltd.) fiber diameter 13 μm, relative dielectric constant 6.2
In the following examples, material properties were evaluated by the following methods.

[Tensile test]
An ISO (1A) dumbbell test piece was molded at a resin temperature of 310°C and a mold temperature of 140°C using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries. The tensile strength of the obtained test piece was measured according to ISO527 under the conditions of a distance between fulcrums of 114 mm, a tensile speed of 5 mm/min, a temperature of 23° C. and a relative humidity of 50%.

[Dielectric constant]
Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, a square plate of 80 mm×80 mm×3 mm thick was molded at a resin temperature of 310° C. and a mold temperature of 150° C. The square plate thus obtained was measured with a dielectric loss measuring device TR-10C manufactured by Ando Electric in accordance with the transformer bridge method of ASTM D-150 (2011). The measurement frequency was 1 MHz, the main electrode diameter was 50 mmφ, and the electrodes were coated with conductive paste.

[Number average dispersion diameter of primary dispersed phase]
Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, resin temperature: 310 ° C, mold temperature: 140 ° C, ISO (1A) dumbbell test piece is molded, from the center part -80 ° C atmosphere Cut a thin piece of 0.1 μm or less in the cross-sectional area direction of the test piece, Hitachi H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification 500,000 to 600,000 times), 1 Photographs were taken at 1000x magnification. From the photograph, for (a) the dispersed portion of (d) alloy component dispersed in the PPS resin, for any 100 primary dispersed phases, first measure the maximum and minimum diameters of each, and obtain the average value. , and then the number average value obtained from them was taken as the number average dispersion diameter of the primary dispersed phase.

[Weight average molecular weight of PPS resin]
The weight average molecular weight (Mw) of the PPS resin was calculated in terms of polystyrene using gel permeation chromatography (GPC). GPC measurement conditions are shown below.
Equipment: SSC-7110 (Senshu Science)
Column name: Shodex UT806M x 2
Eluent: 1-chloronaphthalene Detector: Refractive index detector Column temperature: 210°C
Pre-temperature bath temperature: 250°C
Pump thermostat temperature: 50°C
Detector temperature: 210°C
Flow rate: 1.0 mL/min
Sample injection volume: 300 μL (slurry: about 0.2% by weight).

[Carboxyl Group Amount of PPS Resin]
The carboxyl group content of the PPS resin was calculated using a Fourier transform infrared spectrometer (hereinafter abbreviated as FT-IR).

First, benzoic acid was measured by FT-IR as a standard substance, and the absorption intensity (b1) of the peak at 3066 cm ^-1 which is the absorption of the CH bond of the benzene ring and the peak at 1704 cm ^-1 which is the absorption of the carboxyl group. The absorption intensity (c1) was read, and the amount of carboxyl groups (U1) per unit of benzene ring (U1) = (c1)/[(b1)/5] was determined. Next, the PPS resin was melt-pressed at 320° C. for 1 minute and then quenched to obtain an amorphous film, which was then subjected to FT-IR measurement. Reading the absorption intensity (b2) at 3066 cm ^-1 and the absorption intensity (c2) at 1704 cm ^-1 , the amount of carboxyl groups (U2) per 1 unit of benzene ring, (U2) = (c2) / [(b2) / 4] asked. The carboxyl group content per 1 g of PPS resin was calculated from the following formula.
The amount of carboxyl groups in the PPS resin (μmol/g)=(U2)/(U1)/108.161×1000000.

[Examples 1 to 6, Comparative Examples 1 to 4]
After dry blending the PPS resin, silane coupling agent, and alloy components shown in Table 1 at the ratios shown in Table 1, a TEX30α twin-screw extruder (L/D = 45) manufactured by Japan Steel Works, Ltd. equipped with a side feeder and a vacuum vent. ), the screw arrangement was set to three kneading portions, the ratio of the kneading portions to the total length of the screw was set to 25%, and the cylinder temperature was set to 320° C. for melt-kneading. Glass fibers were fed into the twin-screw extruder using a side feeder. After that, it was pelletized by a strand cutter. After drying the obtained pellets at 130° C. for 8 hours, they were subjected to injection molding, and the obtained molded articles were subjected to morphology observation, tensile test, and dielectric constant measurement.

The results of the above Examples and Comparative Examples will be described.

In Examples 1 to 4, (a) PPS resin, (b) glass fiber made of glass having a relative dielectric constant of 5.5 or less, and (c) a silane coupling agent are specified to have a specific composition, resulting in excellent tensile strength. and low dielectric constant.

On the other hand, in Comparative Example 1, in which the composition of (b) the glass fiber made of glass having a dielectric constant of 5.5 or less exceeds 150 parts by weight, the reinforcing effect of the glass fiber is not sufficiently exhibited, and the glass fiber is fragile and easily broken. A PPS resin composition with sufficient tensile strength cannot be obtained. Moreover, the obtained PPS resin composition also has a dielectric constant exceeding 3.8, and sufficient dielectric properties cannot be obtained.

(c) Comparative Example 2, in which no silane coupling agent was added, resulted in significantly inferior tensile strength compared to Example 2, in which a silane coupling agent was used. Compared to Example 2, in Comparative Example 2, the effect of modifying the PPS resin (increase in toughness) by the silane coupling agent was not obtained, and it is thought that the strength was lowered.

(b) Comparative Example 3, in which glass fibers made of glass having a relative dielectric constant of 5.5 or less were not blended, and glass fibers made of glass having a relative dielectric constant of more than 5.5 were blended, had excellent tensile strength, but the same Compared to Example 2, which uses a large amount of glass fiber, the result is a much higher dielectric constant, and a PPS resin composition having both mechanical strength and low dielectric constant cannot be obtained.

In Examples 5 and 6, in addition to (a) PPS resin, (b) glass fiber made of glass having a dielectric constant of 5.5 or less, (c) a silane coupling agent, and (d) an olefin-based alloy component By blending a thermoplastic elastomer or a fluororesin, it exhibits a low dielectric constant while maintaining high tensile strength.

On the other hand, Comparative Example 4, in which (b) the glass fiber made of glass having a relative dielectric constant of 5.5 or less was not blended, resulted in significantly inferior tensile strength, failing to satisfy practical strength.

Claims (2)

(a) to 100 parts by weight of polyphenylene sulfide resin, (b) 25 to 100 parts by weight of glass fiber made of glass having a dielectric constant of 5.5 or less, and (c) 0.1 to 10 parts by weight of a silane coupling agent. , and (d) a polyphenylene sulfide resin composition containing 5 to 80 parts by weight of any resin selected from thermoplastic elastomers and fluororesins, and an electron microscope of a molded article made of the resin composition The observed resin phase separation structure is characterized by component (a) forming a continuous phase (sea phase) and component (d) forming a primary dispersed phase (island phase) having a number average dispersion diameter of 1 μm or less. A polyphenylene sulfide resin composition. 2. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin (a) has a carboxyl group content of 25 to 400 μmol/g.