KR102668078B1 - Polyarylene sulfide resin composition and molded product thereof, and electric vehicle part - Google Patents

Abstract

The present invention relates to a polyarylene sulfide resin and at least one other resin selected from the group consisting of an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. A polyarylene sulfide resin composition for electric vehicle parts containing components, wherein the polyarylene sulfide resin includes a diiodo aromatic compound, simple sulfur, and a polymerization inhibitor. It can be obtained by a method comprising reacting in a molten mixture containing the compound, the above-described elemental sulfur, and the above-mentioned polymerization inhibitor, wherein the polyarylene sulfide resin is a carboxyl group derived from the above-mentioned polymerization inhibitor and a salt of the carboxyl group. It has at least one group selected from the group consisting of, and the polyarylene sulfide resin has an Mw/Mtop of 0.80 to 1.70, wherein the Mw and Mtop are the weight average molecular weight and peak measured by gel permeation chromatography, respectively. The molecular weight is, and the resin composition relates to a polyarylene sulfide resin composition for electric vehicle parts in the form of pellets.
According to the present invention, the amount of gas generated by heating can be suppressed. Furthermore, according to the present invention, a molded article of a polyarylene sulfide resin composition excellent in properties such as tracking resistance, mechanical strength, epoxy adhesion, metal adhesion, cavity balance, and hot water resistance is obtained.

Description

Polyarylene sulfide resin composition, molded product thereof, and electric vehicle parts {POLYARYLENE SULFIDE RESIN COMPOSITION AND MOLDED PRODUCT THEREOF, AND ELECTRIC VEHICLE PART}

The present invention relates to polyarylene sulfide resin compositions, molded products thereof, and electric vehicle parts.

Electric vehicles, which have recently been attracting attention, have many parts that operate at high voltage, and resin molded products are used for these electric vehicle parts. As a use of the resin molded product, for example, an ignition coil case for an automobile in which the resin molded product is used as a coil case and the ignition coil is sealed with an epoxy resin composition or the like within the coil case, or spark plugs and ignition coils. An example is the coil case in this integrated distributorless ignition system (hereinafter sometimes abbreviated as “DLI system”).

These electric vehicle parts are required to have tracking resistance so that they are unlikely to ignite even under high voltage. Additionally, for example, for the coil case as described above, it is desirable to have excellent adhesion to epoxy resin or metal.

In relation to this, for example, polyphenylene sulfide resin (hereinafter sometimes abbreviated as "PPS resin") and polyarylene sulfide resin (hereinafter sometimes abbreviated as "PAS resin"), which contain It has been proposed to mold the resin composition and use it for automobile parts as described above (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 2000-103964

However, in compositions containing conventional polyarylene sulfide resins, the amount of gas generated by heating during molding or other processing is relatively large. For this reason, when a low molecular weight compound containing a sulfur atom, which is a gas component, and a metal material such as copper come into contact, the two react by repeatedly applying a high voltage, causing tri (dendritic destruction traces). The possibility of this occurring also increased, and there was a risk that tracking resistance would deteriorate due to this. In particular, electric vehicles that use a motor as a driving force require driving energy equivalent to that of a gasoline engine when starting, so they are equipped with a lithium-ion secondary battery, have a battery voltage of 100 to 400 V, and are additionally equipped with a boosting circuit. It is driven by high voltage up to 650V. In automotive parts that require high safety, especially electric vehicle parts, there are many parts that operate under high voltage and high current, so ignition in the event of abnormalities is at a higher level compared to conventional automobiles using lead acid batteries. Prevention and combustion prevention performance are required, and not only is it excellent in flame retardancy, but it is also required to further suppress the tracking phenomenon that causes ignition. In addition, in the resin composition or its molded product, there was still room for improvement in properties such as mechanical strength, epoxy adhesion, metal adhesion, and cavity balance.

Therefore, the problem that the present invention seeks to solve is a polyarylene sulfide that can suppress the amount of gas generated by heating and has excellent tracking resistance, mechanical strength, metal adhesion, and cavity balance characteristics in a resin composition or a molded product thereof. The object is to provide a resin composition, a molded article for an electric vehicle using the resin composition, and electric vehicle parts including the molded article.

As a result of various studies, the present inventors have found that the above problem can be solved by using a polyarylene sulfide resin obtained by melt-polymerizing a diiodo aromatic compound, simple sulfur, and a polymerization inhibitor. We found this out and completed the present invention.

That is, the present invention is a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than polyarylene sulfide resin, an elastomer, and at least one kind of crosslinkable resin selected from the group consisting of a crosslinkable functional group having two or more crosslinkable functional groups. Containing other components (hereinafter, sometimes simply referred to as "the other components"), the polyarylene sulfide resin includes a diiodo aromatic compound, simple sulfur, and a polymerization inhibitor, a diiodo aromatic compound, It relates to a polyarylene sulfide resin composition for electric vehicle parts, which can be obtained by a method comprising reacting in a molten mixture containing elemental sulfur and a polymerization inhibitor.

According to the present invention, the amount of gas generated by heating can be suppressed. Furthermore, according to the present invention, a molded article of a polyarylene sulfide resin composition excellent in properties such as tracking resistance, mechanical strength, epoxy adhesion, metal adhesion, cavity balance, and hot water resistance is obtained.

Additionally, cavity balance is related to the uniformity of the filling degree of each cavity when a plurality of molded articles are molded simultaneously through injection molding using a mold having a plurality of cavities. If the cavity balance of the molding material is insufficient, molding defects in which some cavities are not sufficiently filled tend to occur.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The polyarylene sulfide resin used in this embodiment is obtained by reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor. It can be obtained by a method including: According to this method, compared to conventional methods including the Phillips method, polyarylene sulfide resin can be obtained as a polymer with a relatively high molecular weight.

A diiodo aromatic compound has an aromatic ring and two iodine atoms directly bonded to the aromatic ring. As diiodo aromatic compounds, diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether and diiododi. Phenylsulfone, etc. may be mentioned, but it is not limited to these. The substitution positions of the two iodine atoms are not particularly limited, but the two substitution positions are preferably positioned as far apart as possible within the molecule. Preferred substitution positions are the para position and the 4,4'- position.

The aromatic ring of the diiodo aromatic compound is at least one selected from the group consisting of phenyl group, halogen atom other than iodine atom, hydroxy group, nitro group, amino group, alkoxy group having 1 to 6 carbon atoms, carboxy group, carboxylate, aryl sulfone and aryl ketone. It may be substituted by a substituent of the species. However, from the viewpoint of the crystallinity and heat resistance of the polyarylene sulfide resin, the ratio of the substituted diiodo aromatic compound to the unsubstituted diiodo aromatic compound is preferably in the range of 0.0001 to 5% by mass. Preferably it is in the range of 0.001 to 1 mass%.

Simple sulfur refers to a substance composed only of sulfur atoms (S ₈ , S ₆ , S ₄ , S ₂ , etc.), and its form is not limited. Specifically, simple sulfur commercially available as a defense pharmaceutical may be used, or a mixture containing S ₈ and S ₆ that is available for general purposes may be used. The purity of elemental sulfur is also not particularly limited. Elemental sulfur may be in granular or powder form as long as it is solid at room temperature (23°C). The particle size of elemental sulfur is not particularly limited, but is preferably in the range of 0.001 to 10 mm, more preferably in the range of 0.01 to 5 mm, and even more preferably in the range of 0.01 to 3 mm.

The polymerization inhibitor can be used without particular limitation as long as it is a compound that inhibits or stops the polymerization reaction of polyarylene sulfide resin. The polymerization inhibitor preferably contains a compound capable of introducing at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group, and a salt of a carboxyl group at the terminal of the main chain of the polyarylene sulfide resin. That is, as the polymerization inhibitor, a compound having 1 or 2 or more of at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group, and a salt of a carboxyl group is preferable. Additionally, the polymerization inhibitor may have the above functional group, or may generate the above functional group through a polymerization termination reaction or the like.

As a polymerization inhibitor having a hydroxy group or an amino group, for example, a compound represented by the following formula (1) or (2) can be used as the polymerization inhibitor.

According to the compound represented by general formula (1), a monovalent group represented by the following formula (1-1) is introduced as an end group of the main chain. Y in formula (1-1) is a hydroxy group, amino group, etc. derived from a polymerization inhibitor.

According to the compound represented by general formula (2), a monovalent group represented by the following formula (2-1) is introduced as an end group of the main chain. A hydroxy group derived from a compound represented by general formula (1) can be introduced into the polyarylene sulfide resin by, for example, bonding with a sulfur radical and the carbon atom of the carbonyl group in formula (2).

The group represented by formula (1-1) or (2-1) is sulfur generated by radical cleavage of the disulfide bond derived from the raw material (single sulfur) in the main chain of the polyarylene sulfide resin under the melting temperature. It is thought that the radical is introduced into the polyarylene sulfide resin when the compound represented by the general formula (1) or the compound represented by the general formula (2) combines. The presence of structural units of these specific structures is characteristic of polyarylene sulfide resins obtained by melt polymerization using a compound represented by general formula (1) or (2).

Examples of compounds represented by general formula (1) include 2-iodophenol, 2-aminoaniline, and the like. Examples of the compound represented by general formula (2) include 2-iodobenzophenone.

As a polymerization inhibitor having a carboxyl group, for example, one or more compounds selected from compounds represented by the following general formulas (3), (4), or (5) can be used.

In general formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent group represented by the following general formula (a), (b) or (c), and either R ¹ or R ² At least one of them is a monovalent group represented by general formula (a), (b) or (c). In general formula (4), Z represents an iodine atom or a mercapto group, and R ³ represents a monovalent group represented by the following general formula (a), (b) or (c). In general formula (5), R ⁴ represents a monovalent group represented by general formula (a), (b) or (c).

X in general formulas (a) to (c) is a hydrogen atom or an alkali metal atom, but a hydrogen atom is preferred because it improves reactivity. Examples of alkali metal atoms include sodium, lithium, potassium, rubidium, and cesium, but sodium is preferred. In general formula (b), R ¹⁰ represents an alkylene group having 1 to 6 carbon atoms. In general formula (c), R ¹¹ represents an alkylene group having 1 to 3 carbon atoms, R ¹² represents an alkyl group having 1 to 5 carbon atoms.

According to the compound represented by general formula (3), (4) or (5), a monovalent group represented by the following formula (6) or (7) is introduced as an end group of the main chain. The presence of structural units at the terminals of these specific structures is characteristic of polyarylene sulfide resins obtained by melt polymerization using compounds represented by general formula (3), (4), or (5).

(In the formula, R ⁵ represents a monovalent group represented by general formula (a), (b) or (c))

(In the formula, R ⁶ represents a monovalent group represented by general formula (a), (b) or (c))

As a polymerization inhibitor, a compound that does not have a functional group such as a carboxyl group may be used. Examples of such compounds include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, and N-cyclohexyl-2-benzothia. At least one compound selected from zolylsulfenamide, 2-(morpholinothio)benzothiazole, and N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide can be used.

The polyarylene sulfide resin according to the present embodiment is produced by performing melt polymerization in a molten mixture obtained by heating a mixture containing a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, and, if necessary, a catalyst. do. The ratio of the diiodo aromatic compound in the molten mixture is preferably in the range of 0.5 to 2 mol, more preferably in the range of 0.8 to 1.2 mol, based on 1 mol of elemental sulfur. Additionally, the proportion of the polymerization inhibitor in the mixture is preferably in the range of 0.0001 to 0.1 mol, more preferably in the range of 0.0005 to 0.05 mol, based on 1 mol of solid sulfur.

The timing of adding the polymerization inhibitor is not particularly limited, but the mixture containing the diiodo aromatic compound, elemental sulfur, and a catalyst added as necessary is heated so that the temperature of the mixture is preferably 200°C to 320°C. The polymerization inhibitor can be added when the temperature reaches the range, more preferably within the range of 250 to 320°C.

The polymerization rate can be controlled by adding a nitro compound as a catalyst to the molten mixture. As this nitro compound, various nitrobenzene derivatives can usually be used. Nitrobenzene derivatives include, for example, 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, and 2,6-diiodo. and do-4-nitroamine. The amount of the catalyst is generally just the amount added as a catalyst, and for example, it is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of elemental sulfur.

The conditions for melt polymerization are appropriately adjusted so that the polymerization reaction proceeds appropriately. The temperature of melt polymerization is preferably in the range of 175°C or higher and the melting point of the polyarylene sulfide resin to be produced +100°C or lower, and more preferably in the range of 180 to 350°C. Melt polymerization is performed at an absolute pressure preferably in the range of 1 [cPa] to 100 [kPa], more preferably in the range of 13 [cPa] to 60 [kPa]. The conditions for melt polymerization do not need to be constant. For example, at the beginning of polymerization, the temperature is preferably in the range of 175 to 270°C, more preferably in the range of 180 to 250°C, and the absolute pressure is in the range of 6.7 to 100 [kPa], and then, Polymerization is carried out while continuously or stepwise raising the temperature and reducing the pressure. In the later stages of polymerization, the temperature is preferably in the range of 270°C or higher and the melting point of the polyarylene sulfide resin to be produced +100°C or lower, more preferably 300 to 350°C. Polymerization can be performed within the range of ℃ and the absolute pressure within the range of 1 [cPa] to 6 [kPa]. In this specification, the melting point of the resin means a value measured based on JIS K 7121 using a differential scanning calorimeter (DSC device Pyris Diamond manufactured by PerkinElmer).

Melt polymerization is preferably performed in a non-oxidizing atmosphere from the viewpoint of obtaining a high degree of polymerization while preventing oxidative crosslinking reaction. In a non-oxidizing atmosphere, the oxygen concentration in the gas phase is preferably in the range of less than 5 volume%, more preferably in the range of less than 2 volume%, and even more preferably, the gas phase does not substantially contain oxygen. . The non-oxidizing atmosphere is preferably an inert gas atmosphere such as nitrogen, helium, and argon.

Melt polymerization can be performed, for example, using a melt kneader equipped with a heating device, a pressure reducing device, and a stirring device. Examples of melt kneaders include Banbury mixers, kneaders, continuous kneaders, single-screw extruders, and twin-screw extruders.

The melt mixture for melt polymerization preferably contains substantially no solvent. More specifically, the amount of solvent contained in the molten mixture is preferably 10 parts by mass with respect to a total of 100 parts by mass of the diiodo aromatic compound, elemental sulfur, polymerization inhibitor, and, if necessary, the catalyst. The range is as follows, more preferably in the range of 5 parts by mass or less, and even more preferably in the range of 1 part by mass or less. The amount of solvent may be 0 part by mass or more, 0.01 part by mass or more, or 0.1 part by mass or more.

After cooling the molten mixture (reaction product) after melt polymerization to obtain a solid mixture, the polymerization reaction may be further advanced by heating the mixture under reduced pressure or atmospheric pressure in a non-oxidizing atmosphere. By this, not only can the molecular weight be further increased, but also the generated iodine molecules are sublimated and removed, so that the iodine atom concentration in the polyarylene sulfide resin can be suppressed to a low level. A solid mixture can be obtained by cooling to a temperature preferably in the range of 100 to 260°C, more preferably in the range of 130 to 250°C, and even more preferably in the range of 150 to 230°C. Heating after cooling to a solid state can be performed under the same temperature and pressure conditions as for melt polymerization.

The reaction product containing the polyarylene sulfide resin obtained through the melt polymerization process can also be used to produce a resin composition by methods such as directly adding it to a melt kneader, but the solvent in which the reaction product is dissolved is used. It is preferable to prepare a melt by adding and extract the reaction product from the reaction apparatus in the state of the melt because not only is productivity excellent, but reactivity is also improved. The addition of the solvent in which the reaction product is dissolved is preferably performed after melt polymerization, but may also be performed later in the melt polymerization reaction. Additionally, the molten mixture (reaction product) is cooled as described above to obtain a solid mixture. Afterwards, the polymerization reaction may be further advanced by heating the mixture under increased pressure, reduced pressure, or atmospheric pressure in a non-oxidizing atmosphere. The step of preparing the melt may be performed under a non-oxidizing atmosphere. In addition, the temperature of heating dissolution may be in the range above the melting point of the solvent in which the reaction product is dissolved, and is preferably in the range of 200 to 350°C, more preferably in the range of 210 to 250°C, and is preferably carried out under pressure. .

The mixing ratio of the solvent in which the reaction product is dissolved, used to prepare the melt, is preferably in the range of 90 to 1000 parts by mass, more preferably, with respect to 100 parts by mass of the reaction product containing the polyarylene sulfide resin. Typically, it is in the range of 200 to 400 parts by mass.

As a solvent in which the reaction product dissolves, for example, a solvent used as a polymerization reaction solvent in solution polymerization such as the Phillips method can be used. Examples of preferred solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazoly. Aliphatic cyclic amide compounds such as dinoic acid, ε-caprolactam, and N-methyl-ε-caprolactam, hexamethyltriamide phosphate (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide. Amide compounds such as (DMA), etherified polyethylene glycol compounds such as polyethylene glycol dialkyl ether (polymerization degree of 2000 or less and having an alkyl group of 1 to 20 carbon atoms), tetramethylene sulfoxide, and dimethyl sulfoxide. Sulfoxide compounds such as seed (DMSO) can be mentioned. Examples of other usable solvents include benzophenone, diphenyl ether, diphenyl sulfide, 4,4'-dibromoviphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxa. Diazole, 2,5-diphenyloxazole, triphenylmethanol, N,N-diphenylformamide, benzyl, anthracene, 4-benzoylbiphenyl, dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, Pentachlorophenol, 1-benzyl-2-pyrrolidione, 9-fluorenone, 2-benzoylnaphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrroli Dinone, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4-dibenzoylbutane, phenanthrene, 4-benzoylbiphenyl, 1,1-diphenylacetone, o,o '-biphenol, 2,6-diphenylphenol, triphenylene, 2-phenylphenol, thiantrene, 3-phenoxybenzyl alcohol, 4-phenylphenol, 9,10-dichloroanthracene, triphenylmethane, 4, 4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluoranthene, diphenyl phthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-bromody Phenyl ether, pyrene, 9,9'-bi-fluorene, 4,4'-isopropylidene-diphenol, ε-caprolactam, N-cyclohexyl-2-pyrrolidone, diphenyl isophthalate, diphenyl One or more solvents selected from the group consisting of terephthalate and 1-chloronaphthalene can be mentioned.

The melt taken out from the reaction device is preferably post-processed and then melt-kneaded with the other components to prepare a resin composition because the reactivity becomes better. The method of post-processing the dissolved product is not particularly limited, but examples include the following method.

(1) The solvent is distilled off from the dissolved substance as is or after adding an acid or base under reduced pressure or normal pressure, and then the solid matter after the solvent distillation is dissolved in water and the solvent used in the dissolved substance (or a low molecular weight polymer). A method of washing once or twice or more with a solvent selected from organic solvents having equal solubility), acetone, methyl ethyl ketone, and alcohol, and further neutralizing, washing with water, filtering, and drying.

(2) Solvents such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons are added to the melt (soluble in the solvent of the melt, and at least polyarylene sulfide) A method in which a solid product containing a polyarylene sulfide resin and an inorganic salt is precipitated by adding a poor solvent for the resin as a precipitant, and the solid product is filtered, washed, and dried.

(3) The solvent used in the melt (or an organic solvent having an equivalent solubility for low-molecular-weight polymers) was added to the melt, stirred, and then filtered to remove the low-molecular-weight polymer, followed by water, acetone, methyl ethyl ketone, and A method of washing once or twice or more with a solvent selected from alcohol, etc., followed by neutralization, washing with water, filtration, and drying.

In addition, in the post-treatment methods as exemplified in (1) to (3) above, drying of the polyarylene sulfide resin may be performed in a vacuum, in air or in an inert gas atmosphere such as nitrogen. The polyarylene sulfide resin can also be oxidized and crosslinked by heat treatment in an oxidizing atmosphere with an oxygen concentration of 5 to 30% by volume or under reduced pressure conditions.

The reaction produced by polyarylene sulfide resin through melt polymerization is exemplified below.

Reaction formulas (1) to (5) are, for example, when diphenyl disulfide having a substituent R containing a group represented by general formula (a), (b) or (c) is used as a polymerization inhibitor, This is an example of a reaction produced by polyphenylene sulfide. Reaction formula (1) is a reaction in which the -S-S- bond in the polymerization inhibitor undergoes radical cleavage at the melting temperature. Reaction formula (2) shows that the sulfur radical generated in reaction formula (1) attacks the carbon atom adjacent to the terminal iodine atom of the growing main chain, and the iodine atom is desorbed, thereby stopping polymerization and introducing a substituent R at the end of the main chain. It is a reaction that works. Reaction formula (3) is a reaction in which the disulfide bond that exists in the main chain of the polyarylene sulfide resin derived from the raw material (single sulfur) undergoes radical cleavage under the melting temperature. Reaction formula (4) is a reaction in which polymerization is stopped and a substituent R is introduced to the terminal of the main chain by recombination of the sulfur radical generated in reaction formula (3) with the sulfur radical generated in reaction formula (1). The desorbed iodine atom is in a free state (iodine radical), or iodine radicals recombine with each other as shown in reaction formula (5), thereby producing an iodine molecule.

The reaction product containing polyarylene sulfide resin obtained by melt polymerization contains iodine atoms derived from the raw materials. Therefore, polyarylene sulfide resin is usually used in the form of a mixture containing iodine atoms for the preparation of a resin composition for spinning. The concentration of iodine atoms in the mixture is, for example, in the range of 0.01 to 10,000 ppm relative to the polyarylene sulfide resin, and preferably in the range of 10 to 5,000 ppm. It is also possible to suppress the iodine atom concentration to a low level by utilizing the sublimation property of iodine molecules, and in that case, it is possible to set it to the range of 900 ppm or less, preferably 100 ppm or less, and furthermore, 10 ppm or less. It is possible to further remove iodine atoms below the detection limit, but this is not practical considering productivity. The detection limit is, for example, about 0.01 ppm. Since the polyarylene sulfide resin of the present embodiment obtained by melt polymerization or the reaction product containing the same contains an iodine atom, for example, solution polymerization of a dichloro aromatic compound in an organic polar solvent such as the Phillips method It can be clearly distinguished from polyarylene sulfide obtained by law.

As can be understood from the above reaction formula, the polyarylene sulfide resin obtained by melt polymerization has a main chain mainly composed of an arylene sulfide unit consisting of an aromatic ring derived from a diiodo aromatic compound and a sulfur atom directly bonded thereto, It contains a predetermined substituent R attached to the terminal of the main chain. The predetermined substituent R is bonded to the aromatic ring at the terminal of the main chain directly or through a partial structure derived from a polymerization inhibitor.

Polyphenylene sulfide resin as the polyarylene sulfide resin according to one embodiment has, for example, the following general formula (10):

It has a main chain containing a repeating unit (arylene sulfide unit) represented by . The repeating unit represented by formula (10) has the following formula (10a) bonded at the para position:

The following equation (10b) combining the repeating unit represented by and at the meta position:

It is more preferable that it is a repeating unit expressed as . Among these, the repeating unit bonded at the para position represented by formula (10a) is preferable in terms of heat resistance and crystallinity of the resin.

The polyphenylene sulfide resin according to one embodiment has the following general formula (11):

(In the formula, R ²⁰ and R ²¹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group)

It may include a repeating unit having a substituent as a side chain bonded to an aromatic ring, represented by . However, from the viewpoint of a decrease in crystallinity and heat resistance, it is preferable that the polyphenylene sulfide resin does not substantially contain the repeating unit of the general formula (11). More specifically, the ratio of the repeating unit represented by formula (11) is preferably 2% by mass or less relative to the sum of the repeating unit represented by formula (10) and the repeating unit represented by formula (11). , more preferably 0.2% by mass or less.

The polyarylene sulfide resin of the present embodiment is mainly composed of the above-mentioned arylene sulfide units, but is usually derived from the simple sulfur of the raw material, and has the following formula (20):

Constituent units based on disulfide bonds represented by are also included in the main chain. In terms of heat resistance and mechanical strength, the ratio of the structural unit represented by formula (20) is preferably 2.9% by mass or less relative to the total of the arylene sulfide unit and the constituent portion represented by formula (20). range, more preferably 1.2% by mass or less. It is preferable that the polyarylene sulfide resin contains the structural unit represented by formula (20) because the adhesion between the polyarylene sulfide resin composition and the metal improves.

Mw/Mtop of the polyarylene sulfide resin according to this embodiment is preferably in the range of 0.80 to 1.70, more preferably in the range of 0.90 to 1.30. By setting Mw/Mtop in this range, the processability of polyarylene sulfide resin can be improved and good cavity balance can be provided. In this specification, Mw represents the weight average molecular weight measured by gel permeation chromatography, and Mtop represents the average molecular weight (peak molecular weight) at the point where the detection intensity of the chromatogram obtained by the same measurement is maximum. Mw/Mtop represents the distribution of the molecular weight of the measurement target. Typically, when this value is close to 1, it indicates that the molecular weight distribution is narrow, and as this value increases, it indicates that the molecular weight distribution is wide. In addition, the measurement conditions for gel permeation chromatography are the same as those in the examples of this specification. However, it is possible to change the measurement conditions to the extent that it does not substantially affect the values of Mw and Mw/Mtop.

The weight average molecular weight of the polyarylene sulfide resin according to the present embodiment is not particularly limited as long as the effect of the present invention is not impaired, but the lower limit is preferably 28,000 or more from the viewpoint of excellent mechanical strength, and is in the range of 30,000 or more. It is more desirable. On the other hand, the upper limit is preferably in the range of 100,000 or less because it can provide better cavity balance, more preferably in the range of 60,000 or less, and most preferably in the range of 55,000 or less. Additionally, from the viewpoint of being excellent in mechanical strength and providing good cavity balance, a polyarylene sulfide resin in the range of 28,000 to 60,000, more preferably a polyarylene sulfide resin in the range of 30,000 to 55,000; Additionally, you may use a polyarylene sulfide resin whose weight average molecular weight is in the range of more than 60,000 and less than or equal to 100,000.

The non-Newtonian index of the polyarylene sulfide resin is preferably in the range of 0.95 to 1.75, and more preferably in the range of 1.0 to 1.70. By setting the non-Newtonian index in this range, the processability of polyarylene sulfide resin can be improved and good cavity balance can be provided. In this specification, the non-Newtonian index refers to an index that satisfies the following relationship between shear rate and shear stress under the condition of a temperature of 300°C. The non-Newtonian index can be an indicator of the molecular weight of the measurement object or the molecular structure such as straight chain, branched, or cross-linked. Typically, if this value is close to 1, it indicates that the molecular structure of the resin is linear, As this value increases, it indicates that more branched or cross-linked structures are included.

D=α×S ⁿ

(In the above formula, D represents the shear rate, S represents the shear stress, α represents a constant, and n represents a non-Newtonian exponent)

The polyarylene sulfide resin having the above-mentioned specific range of Mw/Mtop and non-Newtonian index includes, for example, a diiodo aromatic compound, a simple sulfur, and a polymerization inhibitor, a diiodo aromatic compound, and a simple sulfur. In a method of reacting (melt polymerization) in a molten mixture containing a polymerization inhibitor, it is possible to obtain such a polyarylene sulfide resin by increasing its molecular weight to some extent.

The melting point of the polyarylene sulfide resin according to the present embodiment is preferably in the range of 250 to 300°C, more preferably in the range of 265 to 300°C. The melt viscosity (V6) at 300°C of the polyarylene sulfide resin is preferably in the range of 1 to 2000 [Pa·s], and more preferably in the range of 5 to 1700 [Pa·s]. Here, the melt viscosity (V6) was measured using a flow tester at a temperature of 300°C, a load of 1.96 MPa, and an orifice with a ratio of orifice length to orifice diameter (orifice length/orifice diameter) of 10/1 for 6 minutes. It refers to the melt viscosity after maintenance.

The polyarylene sulfide resin composition according to this embodiment may contain one type or two or more types of inorganic fillers. By mixing inorganic fillers, a composition with high rigidity and high heat resistance and stability is obtained. Examples of inorganic fillers include powdered fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate-shaped fillers such as talc and mica, granular fillers such as glass beads, silica beads and glass balloons, glass fibers, Examples include fibrous fillers such as carbon fiber and wollastonite fiber, and glass flakes. It is particularly preferable that the polyarylene sulfide resin composition contains at least one kind of inorganic filler selected from the group consisting of glass fiber, carbon fiber, carbon black, and calcium carbonate.

The content of the inorganic filler is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 5 to 200 parts by mass, and even more preferably in the range of 15 to 150 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. am. When the content of the inorganic filler is within this range, a more excellent effect is obtained in terms of maintaining the mechanical strength of the molded article.

The polyarylene sulfide resin composition according to the present embodiment may contain a resin other than polyarylene sulfide resin selected from thermoplastic resins, elastomers, and crosslinkable resins. These resins can also be blended in a resin composition together with an inorganic filler.

Thermoplastic resins to be blended in the polyarylene sulfide resin composition include, for example, polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, Examples include polyether ketone, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, silicone resin, and liquid crystal polymer (liquid crystal polyester, etc.).

Polyamide is a polymer having an amide bond (-NHCO-). Examples of polyamide resins include (i) polymers obtained from polycondensation of diamines and dicarboxylic acids, (ii) polymers obtained from polycondensation of aminocarboxylic acids, and (iii) polymers obtained from ring-opening polymerization of lactams. there is. Polyamide can be used individually or in combination of two or more types.

Examples of diamines for obtaining polyamide include aliphatic diamines, aromatic diamines, and alicyclic diamines. As aliphatic diamine, diamine with 3 to 18 carbon atoms having a linear or branched chain is preferable. Examples of suitable aliphatic diamines include 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1, 8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecanediamine, 1,12-dodecamethylenediamine , 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexadecamethylenediamine, 1,17-heptadecamethylenediamine, 1,18- Octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine. These can be used individually or in combination of two or more types.

As the aromatic diamine, a diamine having 6 to 27 carbon atoms and having a phenylene group is preferable. Examples of suitable aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodi Phenyl sulfide, 4,4'-di(m-aminophenoxy)diphenylsulfone, 4,4'-di(p-aminophenoxy)diphenylsulfone, benzidine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis(4-aminophenyl)propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4'-bis(4-aminophenoxy Si) Biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amino) Phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-diamino-3,3'-diethyl-5 ,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 2,4-diaminotoluene, and 2,2'-dimethylbenzidine. I can hear it. These can be used individually or in combination of two or more types.

As the alicyclic diamine, a diamine having 4 to 15 carbon atoms and having a cyclohexylene group is preferable. Examples of suitable alicyclic diamines include 4,4'-diamino-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, and 4,4'-diamino-3,3'-dimethyl. -dicyclohexylenemethane, 1,4-diaminocyclohexane, and piperazine. These can be used individually or in combination of two or more types.

Dicarboxylic acids for obtaining polyamide include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.

As the aliphatic dicarboxylic acid, a saturated or unsaturated dicarboxylic acid having 2 to 18 carbon atoms is preferable. Examples of suitable aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, and tetradecane. Examples include diacid, pentadecanedioic acid, octadecanodioic acid, maleic acid, and fumaric acid. These can be used individually or in combination of two or more types.

As the aromatic dicarboxylic acid, a dicarboxylic acid having 8 to 15 carbon atoms and having a phenylene group is preferable. Examples of suitable aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and diphenylmethane-4,4'-dicarboxylic acid. , diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. I can hear it. These can be used individually or in combination of two or more types. Additionally, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can also be used within the range of melt molding.

As the aminocarboxylic acid, an aminocarboxylic acid having 4 to 18 carbon atoms is preferable. Examples of suitable aminocarboxylic acids include 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminodecanoic acid. Examples include aminododecanoic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. These can be used individually or in combination of two or more types.

Examples of lactams for obtaining polyamide include ε-caprolactam, ω-laurolactam, ζ-enantholactam, and η-capryllactam. These can be used individually or in combination of two or more types.

Preferred combinations of polyamide raw materials include ε-caprolactam (nylon 6), 1,6-hexamethylenediamine/adipic acid (nylon 6,6), and 1,4-tetramethylenediamine/adipic acid (nylon 4). ,6), 1,6-hexamethylenediamine/terephthalic acid, 1,6-hexamethylenediamine/terephthalic acid/ε-caprolactam, 1,6-hexamethylenediamine/terephthalic acid/adipic acid, 1,9-nonamethylenediamine /terephthalic acid, 1,9-nonamethylenediamine/terephthalic acid/ε-caprolactam, 1,9-nonamethylenediamine/1,6-hexamethylenediamine/terephthalic acid/adipic acid, and m-xylylenediamine/adipic acid. can be mentioned. Among these, 1,4-tetramethylenediamine/adipic acid (nylon 4,6), 1,6-hexamethylenediamine/terephthalic acid/ε-caprolactam, 1,6-hexamethylenediamine/terephthalic acid/adipic acid, Poly obtained from 1,9-nonamethylenediamine/terephthalic acid, 1,9-nonamethylenediamine/terephthalic acid/ε-caprolactam, or 1,9-nonamethylenediamine/1,6-hexamethylenediamine/terephthalic acid/adipic acid Amide resins are more preferred.

The content of the thermoplastic resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 3 to 100 parts by mass, and even more preferably in the range of 5 to 45 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. am. When the content of thermoplastic resin other than polyarylene sulfide resin is within this range, the effect of further improvement in heat resistance, chemical resistance, and mechanical properties is obtained.

As an elastomer to be blended in a polyarylene sulfide resin composition, a thermoplastic elastomer is often used. Examples of thermoplastic elastomers include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. In addition, in this specification, thermoplastic elastomers are classified as elastomers other than the above-described thermoplastic resins.

The elastomer (particularly the thermoplastic elastomer) preferably has a functional group capable of reacting with at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group, and a salt of a carboxyl group. Accordingly, it is possible to obtain a resin composition that is particularly excellent in terms of adhesiveness and impact resistance, and can also suppress the amount of gas generated by heating. Such functional groups include epoxy group, amino group, hydroxyl group, carboxyl group, mercapto group, isocyanate group, oxazoline group, and formula: R(CO)O(CO)- or R(CO)O- (wherein R is carbon A group represented by (represents an alkyl group having 1 to 8 atoms) can be mentioned. A thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an α-olefin and a vinyl polymerizable compound having the above functional group. Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms, such as ethylene, propylene, and butene-1. Examples of vinyl polymerizable compounds having the above functional group include α,β-unsaturated carboxylic acids and alkyl esters thereof such as (meth)acrylic acid and (meth)acrylic acid ester, maleic acid, fumaric acid, itaconic acid, and other carbon atoms of 4 to 4. Examples include α,β-unsaturated dicarboxylic acid and its derivatives (mono or diester, acid anhydride, etc.) of 10, and glycidyl (meth)acrylate. Among these, a group consisting of an epoxy group, a carboxyl group, and a group represented by the formula: R(CO)O(CO)- or R(CO)O- (wherein R represents an alkyl group having 1 to 8 carbon atoms) Ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the above are preferred in terms of improving toughness and impact resistance.

The content of the elastomer cannot be uniformly specified because it varies depending on its type and application, but for example, it is preferably in the range of 1 to 300 parts by mass, more preferably 3 parts by mass, per 100 parts by mass of polyarylene sulfide resin. It is in the range of -100 parts by mass, more preferably in the range of 5 to 45 parts by mass. When the elastomer content is within this range, an even more excellent effect is obtained in terms of ensuring the heat resistance and toughness of the molded product.

The crosslinkable resin blended with the polyarylene sulfide resin composition has two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, phenolic hydroxyl group, amino group, amide group, carboxyl group, acid anhydride group, and isocyanate group. Examples of crosslinkable resins include epoxy resins, phenol resins, and urethane resins.

As the epoxy resin, an aromatic epoxy resin is preferable. The aromatic epoxy resin may have a halogen group, a hydroxyl group, or the like. Examples of suitable aromatic epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, biphenyl-type epoxy resin, tetramethylbiphenyl-type epoxy resin, phenol novolac-type epoxy resin, and cresolano. Rock-type epoxy resin, bisphenol A novolak-type epoxy resin, triphenylmethane-type epoxy resin, tetraphenylethane-type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl-type epoxy resin, naphthol novolak-type epoxy. Resin, naphthol aralkyl type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol coaxial novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, and biphenyl novolak type epoxy resin. You can. These aromatic epoxy resins can be used individually or in combination of two or more types. Among these aromatic epoxy resins, novolak-type epoxy resins are preferable, and cresol novolak-type epoxy resins are more preferable because they have excellent compatibility with other resin components.

The content of the crosslinkable resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 3 to 100 parts by mass, and still more preferably 5 to 30 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. It is a range. When the content of the crosslinkable resin is within this range, the effect of improving the rigidity and heat resistance of the molded product is particularly significantly achieved.

The polyarylene sulfide resin composition may contain a silane compound having a functional group capable of reacting with at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group, and a salt of a carboxyl group. Accordingly, it is possible to obtain a resin composition that improves the compatibility of the polyarylene sulfide resin with other components and can suppress the amount of gas generated by heating. Examples of such silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ- Silane coupling agents such as glycidoxypropylmethyldiethoxysilane and γ-glycidoxypropylmethyldimethoxysilane can be mentioned.

For example, the content of the silane compound is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. When the content of the silane compound is within this range, the effect of improving compatibility between the polyarylene sulfide resin and the other components mentioned above is obtained.

The polyarylene sulfide resin composition according to the present embodiment may contain other additives such as a mold release agent, colorant, heat stabilizer, ultraviolet stabilizer, foaming agent, rust inhibitor, flame retardant, and lubricant. The content of the additive is preferably in the range of 1 to 10 parts by mass, for example, with respect to 100 parts by mass of the polyarylene sulfide resin.

The polyarylene sulfide resin composition can be obtained in the form of, for example, a pellet-like compound by melt-kneading the polyarylene sulfide resin obtained by the above method and the other components above. The temperature of melt kneading is preferably, for example, in the range of 250 to 350°C, and more preferably in the range of 290 to 330°C. Melt kneading can be performed using a twin screw extruder or the like.

The polyarylene sulfide resin composition according to the present embodiment, alone or in combination with materials such as the other components, is subjected to various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding, and has heat resistance, molding processability, It can be processed into molded products with excellent dimensional stability. The polyarylene sulfide resin composition according to the present embodiment generates a small amount of gas when heated, enabling easy production of high-quality molded articles.

When the polyarylene sulfide resin composition according to this embodiment is used for electric vehicle parts, the amount of gas generated by heating can be reduced. For this reason, it is possible to reduce the contact between low-molecular-weight compounds containing sulfur atoms, which are gas components, and metal materials such as copper, and as a result, even when high voltages are repeatedly applied, the reaction between the two can be suppressed. It is possible to improve tracking resistance by suppressing the occurrence and growth of trees (marks of dendritic destruction).

In this way, the polyarylene sulfide resin composition of the present invention has a lithium ion secondary battery and can be suitably used in the field of electric vehicles such as hybrid vehicles (HV) and electric vehicles (EV), which require particularly high safety. Therefore, electric vehicle parts obtained by molding the polyarylene sulfide resin composition of the present invention include, for example, power modules, converters, condensers, insulators, motor terminal blocks, batteries, electric compressors, battery current sensors, junction blocks, etc. There is a case for storing it. The molded article is particularly suitably used as a case for an ignition coil of a DLI system.

[Example]

Hereinafter, the present invention will be described in more detail through examples. However, the present invention is not limited to these examples.

1. Evaluation method

[Bending characteristics]

· Standard test method… ASTM D-790

·Test piece… 3.2 mm (thickness) × 12.7 mm (width) × 127 mm (length)

·Test result… Average value of number of tests n=10

[Hot water resistance]

The test piece was immersed in hot water at 95°C, and the change in bending strength over time was examined.

·Test piece… 3.2 mm (thickness) × 12.7 mm (width) × 127 mm (length)

·Bending strength test method… ASTM D-790

·Evaluation items… Retention rate of bending strength relative to initial strength after 1000 hours and 3000 hours

·Test result… Average value of number of tests n=5

[Metal adhesion strength]

A polyarylene sulfide resin composition of the same size was injected and molded on a 4 × 10 × 49 mm metal piece (SUS304) set in a mold, and a tensile test was performed under the conditions of a chuck spacing of 20 mm and a tensile speed of 1 mm/min. was performed to measure the metal adhesion strength.

[Epoxy adhesion strength]

A test piece of 3 mm (thickness) )/Silica (filling rate of 50 mass%), curing agent: hexahydrophthalic anhydride, base/curing agent = 100/30 (mass ratio)) was applied to a thickness of 40 to 50 ㎛. After fixing these with clips, the epoxy resin was cured by heating at 85°C for 3 hours, then at 150°C for 3 hours, and further slowly cooling. After that, the tensile shear strength was measured at a tensile speed of 5 mm/min, and the actual load was recorded.

[cavity balance]

Using a washer mold with 40 cavities, PPS compound was injection molded under the minimum molding conditions such that the cavity (C1) closest to the primary spool was completely filled. The molding conditions were a 75-ton molding machine, cylinder temperature of 320°C, mold temperature of 140°C, and no holding pressure.

After forming, the filling degree of the cavity (C1) and the cavity (C10) furthest from the primary spool on the same runner were compared. The degree of filling (% by mass) was obtained from the mass ratio of the molded article in the cavity (C10) to the molded article in the cavity (C1). It can be said that the higher the filling degree of the cavity (C10), the better the cavity balance. Based on the degree of filling, the cavity balance of each composition was determined based on the following standards.

AA: range from 100 to 90 mass%

A: range of 89 to 80 mass%

B: range of 79 to 70 mass%

C: range of 69 to 60 mass%

D: Range below 59% mass

[Gas generation amount]

Using a gas chromatograph mass spectrometer, a predetermined sample of polyarylene sulfide resin or resin composition was heated at 325°C for 15 minutes, and the amount of gas generated at that time was quantified as mass%.

[Tracking resistance]

A test piece of 2 mm (thickness) × 50 mm (width) × 100 mm (length) was formed, measured along the resin flow direction using a method based on ASTM D3638, and the breakdown voltage and drop number were plotted, and the number of drops was 50. The voltage of (滴) was read.

2. Synthesis of polyphenylene sulfide resin (PPS resin)

(Synthesis Example 1: Synthesis of PPS-1)

p-diiodobenzene (Tokyo Chemical Co., Ltd., p-diiodobenzene purity 98.0% or more) 300.0 g, solid sulfur (manufactured by Kanto Chemical Co., Ltd., sulfur (powder)) 27.00 g, 4 , 2.0 g of 4'-dithiobisbenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd., 4,4'-dithiobisbenzoic acid, Technical Grade) was heated to 180°C and dissolved and mixed under nitrogen. Next, the temperature was raised to 220°C, and the pressure was reduced to an absolute pressure of 26.6 kPa. The obtained molten mixture was melt-polymerized for 8 hours by gradually changing the temperature and pressure so that the temperature was 320°C and the absolute pressure was 133 Pa. After completion of the reaction, 200 g of NMP was added, heated and stirred at 220°C, and the obtained melt was filtered. 320 g of NMP was added to the dissolved substance after filtration, and cake washing filtration was performed. 1 L of ion-exchanged water was added to the obtained cake containing NMP, and the mixture was stirred at 200°C for 10 minutes in an autoclave. Next, the cake was filtered, and 1 liter of 70°C ion-exchanged water was added to the filtered cake to wash the cake. 1 L of ion-exchanged water was added to the obtained water-containing cake and stirred for 10 minutes. Next, the cake was filtered, and 1 liter of 70°C ion-exchanged water was added to the filtered cake to wash the cake. After repeating this operation once again, the cake was dried at 120°C for 4 hours to obtain 91 g of PPS resin (PPS-1).

(Synthesis Example 2: Synthesis of PPS-2)

91 g of PPS resin (PPS-2) was prepared in the same manner as in Synthesis Example 1 except that “2-iodoaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)” was used instead of “4,4’-dithiobisbenzoic acid.” got it

(Synthesis Example 3: Synthesis of PPS-3)

91 g of PPS resin (PPS-3) was obtained in the same manner as in Synthesis Example 1 except that “diphenyl disulfide (Sumitomo Seika Co., Ltd., DPDS)” was used instead of “4,4’-dithiobisbenzoic acid.”

(Synthesis Example 4: Synthesis of PPS-4)

600 g of N-methylpyrrolidone and 336.3 g (2.0 mol) of sodium sulfide pentahydrate were added to a 2-liter autoclave, and the water-NMP mixture was distilled off by raising the temperature to 200°C in a nitrogen atmosphere. Next, a solution of 292.53 g (1.99 mol) of p-dichlorobenzene and 1.62 g (0.01 mol) of 2,5-dichloroaniline dissolved in 230 g of NMP was added to this system, incubated at 220°C for 5 hours, and further at 240°C. The reaction was performed under nitrogen atmosphere for 2 hours. The contents were taken out from the reaction vessel after cooling, a portion was sampled, and unreacted 2,5-dichloroaniline was quantified using a gas chromatograph. Additionally, the remaining slurry was washed several times with hot water, and the polymer cake was separated by filtration. This cake was dried under reduced pressure at 80°C to obtain powdered amino group-containing polyphenylene sulfide (PPS-4).

The properties of PPS-1 to PPS-4 obtained in Synthesis Examples 1 to 4 are shown in Table 1.

[Table 1]

[Raw material]

To prepare the PPS resin composition, the following materials were prepared.

(thermoplastic elastomer)

ELA: Copolymer of ethylene/glycidyl methacrylic acid (3% by mass)/methyl acrylate (27% by mass) (Sumitomo Chemical Co., Ltd., “Bondfast 7L”)

(Silane coupling agent)

Epoxysilane: γ-glycidoxypropyltrimethoxysilane

(Inorganic filler)

GF: Glass fiber chopped strand (fiber diameter 10㎛, length 3㎜)

[Production and evaluation of compounds]

After mixing each raw material uniformly with a tumbler with the composition shown in Table 2, it was melt-kneaded at 300°C using a twin-screw kneading extruder (TEM-35B, Toshibagikai) to obtain a pellet-like compound. The obtained compound was injection molded under the conditions of a cylinder temperature of 300°C and a mold temperature of 140°C, and test pieces used for bending properties, metal adhesion strength, cavity balance, and hot water resistance tests were produced and various evaluations were performed. Additionally, the amount of gas generated was measured for the PPS resin alone and the compound. The evaluation results are shown in Table 2.

[Table 2]

As is clear from the results shown in Table 2, PPS-1, PPS-2, and PPS-3 have mechanical properties (bending strength, bending elongation at break), metal adhesion strength, epoxy adhesion strength, cavity balance, hot water resistance, and gas generation amount. , In terms of tracking resistance, it was superior to PPS-4.

Claims (10)

Polyarylene sulfide resin,
At least one other component selected from the group consisting of an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups.
A polyarylene sulfide resin composition for electric vehicle parts containing,
The polyarylene sulfide resin reacts with a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, elemental sulfur, and the polymerization inhibitor. It can be obtained by a method that includes asking,
The polyarylene sulfide resin has at least one group selected from the group consisting of a carboxyl group derived from the polymerization inhibitor and a salt of the carboxyl group,
The polyarylene sulfide resin has a Mw/Mtop of 0.80 to 1.70, where Mw and Mtop are the weight average molecular weight and peak molecular weight measured by gel permeation chromatography, respectively,
The resin composition is used by pellet dealers
Polyarylene sulfide resin composition for electric vehicle parts. According to paragraph 1,
The polyarylene sulfide resin,
In the main chain, the following formula (20)

A polyarylene sulfide resin for electric vehicle parts, which is a mixture containing a polyarylene sulfide resin having a disulfide bond represented by and iodine atoms in a ratio ranging from 0.01 to 10,000 ppm with respect to the polyarylene sulfide resin. Composition. According to paragraph 2,
In the main chain, the following formula (20)

A polyarylene sulfide resin having a disulfide bond represented by,
The following general formula (a) at the terminal:

A monovalent group represented by the following general formula (b)

A monovalent group represented by or the general formula (c) below:

(However, ⁱⁿ general formulas (a) to (c), ), wherein R ¹¹ represents an alkylene group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 5 carbon atoms. A polyarylene sulfide resin composition for electric vehicle parts having a monovalent group represented by: . The method of claim 1, 2, or 3,
The polyarylene sulfide resin has a non-Newtonian index of 0.95 to 1.75 at 300°C and Mw/Mtop of 0.80 to 1.70, wherein Mw and Mtop are each a weight average measured by gel permeation chromatography. Polyarylene sulfide resin composition for electric vehicle parts with molecular weight and peak molecular weight. A molded article for electric vehicle parts obtained by molding the polyarylene sulfide resin composition according to claim 1, 2, or 3. An electric vehicle part comprising the molded product according to claim 5. Polyarylene sulfide resin,
At least one other component selected from the group consisting of an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups.
A method for producing a polyarylene sulfide resin composition for electric vehicle parts, comprising melt-kneading,
The polyarylene sulfide resin comprises reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, elemental sulfur, and the polymerization inhibitor. What is obtained by means,
The polyarylene sulfide resin has at least one group selected from the group consisting of a carboxyl group derived from the polymerization inhibitor and a salt of the carboxyl group,
The polyarylene sulfide resin has a Mw/Mtop of 0.80 to 1.70, wherein Mw and Mtop are the weight average molecular weight and peak molecular weight measured by gel permeation chromatography, respectively, and
The resin composition is in the form of pellets.
A method for producing a polyarylene sulfide resin composition for electric vehicle parts, characterized by: In clause 7,
The polyarylene sulfide resin has a non-Newtonian index of 0.95 to 1.75 at 300°C and Mw/Mtop of 0.80 to 1.70, wherein Mw and Mtop are each a weight average measured by gel permeation chromatography. Molecular weight and peak molecular weight, a method for producing a polyarylene sulfide resin composition for electric vehicle parts. In clause 7,
The polymerization inhibitor has the following general formula (3), (4) or (5):



[In General Formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent group represented by the following general formula (a), (b) or (c), and R ¹ or R ² At least one of them is a monovalent group represented by general formula (a), (b) or (c). In General Formula (4), Z represents an iodine atom or a mercapto group, and R ³ represents a monovalent group represented by the following general formula (a), (b) or (c). In general formula (5), R ⁴ represents a monovalent group represented by general formula (a), (b) or (c).



(However, ⁱⁿ general formulas (a) to (c), ), wherein R ¹¹ represents an alkylene group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 5 carbon atoms), a polyarylene sulfide resin for electric vehicle parts, including a compound represented by Method for producing the composition. A method for producing a molded article for electric vehicle parts, comprising injection molding, extrusion molding, compression molding, or blow molding the polyarylene sulfide resin composition according to claim 1,
A method for producing a molded article for electric vehicle parts, characterized in that the polyarylene sulfide resin composition is in the form of a pellet.