CN105593302A - Polyarylene sulfide resin composition and molded product thereof, and electric vehicle part - Google Patents

Abstract

Provided are: a polyarylene sulfide resin composition which generates a gas in a reduced amount upon heating, and has excellent tracking resistance, mechanical strength, adhesiveness to metals and cavity balance properties or can be molded into an article having these excellent properties; a molded article for electric vehicle parts, which is produced using the resin composition; and an electric vehicle part equipped with the molded article. Specifically, a polyarylene sulfide resin composition for electric vehicle parts, which comprises a polyarylene sulfide resin and at least one another component selected from the group consisting of an inorganic filler, a thermoplastic resin other than a polyarylene sulfide resin, an elastomer and a crosslinkable resin having at least two crosslinkable functional groups, wherein the polyarylene sulfide resin is produced by a method comprising reacting a diiodo aromatic compound, elemental sulfur and a polymerization inhibitor with one another in a molten mixture containing the diiodo aromatic compound, the elemental sulfur and the polymerization inhibitor; a molded article for electric vehicle parts, which is produced using the resin composition; and an electric vehicle part equipped with the molded article.

Description

Polyarylene sulfide resin composition and formed products thereof and electric-vehicle part

Technical field

The present invention relates to polyarylene sulfide resin composition and formed products thereof and electric-vehicle part.

Background technology

The electric automobile receiving publicity in recent years has the parts of much working under high voltage, and this electric-vehicle part uses resin forming product. As the purposes of resin forming product, for example, can list: resin forming product is made to coil box, the automobile ignition coil cassette obtaining with seal point fire coils such as composition epoxy resins in this coil box; Or the integrated DIS forming of spark plug and ignition coil is (below sometimes referred to as " DLI system ". ) in coil box.

For this electric-vehicle part, even if require to be also difficult for such resistance to electric trace on fire under high voltage. In addition, for example, about coil box as described above, expect the excellent in adhesion of itself and epoxy resin or metal.

On the other hand, for example, proposed to comprise with polyphenylene sulfide resin (below sometimes referred to as " PPS resin ". ) for the polyarylene sulfide resin of representative is (below sometimes referred to as " pas resin ". ) resin combination form processing, for automobile component as described above (for example, with reference to patent documentation 1).

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2000-103964 communique

Summary of the invention

The problem that invention will solve

But in the existing composition that comprises polyarylene sulfide resin, the amount that adds the gas that the heating in man-hour etc. produces because being shaped is many. Therefore, while becoming gas componant and be the state that the low molecular weight compound of sulfur atom-containing contacts with metal materials such as copper, by repeatedly applying high voltage, both are reacted, the possibility that produces trees (resinoid depredation) is also high, worries to cause thus that resistance to electric trace reduces. Particularly driving force is used in the electric automobile of engine, the petrolic driving-energy that need to be equal to when starting, therefore possesses lithium rechargeable battery, under in cell voltage 100～400V, drives, while being further equipped with booster circuit, under the high voltage of 650V, drive. For requiring the automotive field parts of high security, parts especially used for electric vehicle, because the parts of working under high voltage, high electric current are many, therefore compared with using the existing type automobile of lead accumulator, require anti-on fire, anti-when abnormal to prolong burning performance with higher level, require excellent in flame retardance not only but also further suppress to become the creepage trace phenomenon of reason of fire. In addition, in resin combination or its formed products, the leeway that the characteristics such as mechanical strength, epoxy resin adaptation, metal adaptation, die cavity balance are also still improved.

Therefore, the problem to be solved in the present invention is, polyarylene sulfide resin composition that the gas generated and resin combination that can suppress to be caused by heating or its formed products have excellent resistance to electric trace, mechanical strength, metal adaptation, die cavity equilibrium response is provided, uses the formed products used for electric vehicle of this resin combination and possesses the electric-vehicle part of this formed products.

For the scheme of dealing with problems

The inventor etc. have carried out various research, found that, by using the polyarylene sulfide resin that diiodo-aromatic compound and elemental sulfur and polymerization inhibitor melt polymerization are obtained, can address the above problem, thereby complete the present invention.

That is, the present invention relates to a kind of electric-vehicle part polyarylene sulfide resin composition, it contains: polyarylene sulfide resin; With select free inorganic filler, thermoplastic resin, elastomer except polyarylene sulfide resin and there is at least a kind of other composition (below sometimes referred to as " aforementioned other composition ") in the group of crosslinkable resin composition of more than 2 bridging property functional group, polyarylene sulfide resin can be by comprising that the method that diiodo-aromatic compound, elemental sulfur and polymerization inhibitor are reacted in the molten mixture that comprises diiodo-aromatic compound, elemental sulfur and polymerization inhibitor obtains.

The effect of invention

According to the present invention, that can suppress to be caused by heating be gas generated. In addition, according to the present invention, can obtain the formed products of the polyarylene sulfide resin composition of the excellents such as resistance to electric trace, mechanical strength, epoxy resin adaptation, metal adaptation, die cavity balance, hot water resistance.

It should be noted that the uniformity of the compactedness of each die cavity when die cavity equilibrium relation is shaped multiple formed products to the injection moulding of mould by use with multiple die cavitys simultaneously. If the die cavity balance of moulding material is insufficient, exist the easily a part of die cavity of generation fully not filled so cacoplastic tendency.

Detailed description of the invention

Below, be elaborated for the preferred embodiment of the present invention. But the present invention is not limited to following embodiment.

The polyarylene sulfide resin of using in present embodiment can utilize and comprise that the method that diiodo-aromatic compound, elemental sulfur and polymerization inhibitor are reacted in the molten mixture that contains diiodo-aromatic compound, elemental sulfur and polymerization inhibitor obtains. According to such method, compared with existing method taking Phillips method as representative, can obtain polyarylene sulfide resin with the form of the higher polymer of molecular weight.

Diiodo-aromatic compound has aromatic ring and 2 iodine atoms with aromatic ring Direct Bonding. As diiodo-aromatic compound, can enumerate diiodo-benzene, two iodotoluenes, diiodo-dimethylbenzene, diiodonaphthalene, DIBP, diiodo-benzophenone, diiodo-diphenyl ether and diiodo-diphenyl sulphone (DPS) etc., but be not limited to these. The position of substitution of 2 iodine atoms is not particularly limited, and to be preferably located at position far away as far as possible in molecule be desirable to 2 the position of substitution. Preferred the position of substitution is contraposition and 4,4 '-position.

At least a kind of substituting group that the aromatic ring of diiodo-aromatic compound can be selected from alkoxyl, carboxyl, carboxylate, aryl sulfone and the aryl ketones of phenyl, halogen atom except iodine atom, hydroxyl, nitro, amino, carbon number 1～6 replaces. But, from the viewpoint such as degree of crystallinity and heat resistance of polyarylene sulfide resin, the diiodo-aromatic compound being substituted is preferably the scope of 0.0001～5 quality %, the more preferably scope of 0.001～1 quality % with respect to the ratio of unsubstituted diiodo-aromatic compound.

Elemental sulfur refers to the material (S being only made up of sulphur atom₈、S₆、S₄、S₂Deng), its form is not particularly limited. Particularly, can be used as Pharmacopeia of Japan medicine and commercially available elemental sulfur, can be also the S that comprises that can generally obtain₈And S₆Deng mixture. The purity of elemental sulfur is also not particularly limited. Elemental sulfur, as long as be solid under room temperature (23 DEG C), can be granular or Powdered. The particle diameter of elemental sulfur is not particularly limited, and is preferably the scope of 0.001～10mm, the more preferably scope of 0.01～5mm, the more preferably scope of 0.01～3mm.

Polymerization inhibitor, as long as stop or stop the compound of this polymerisation in the polymerisation of polyarylene sulfide resin, can use without particular limitation. Polymerization inhibitor preferably comprises the compound that can import at the end of the main chain of polyarylene sulfide resin at least one group in the group of the salt composition that selects free hydroxyl, amino, carboxyl and carboxyl. ,, as polymerization inhibitor, preferably there is the compound of at least one group in the group of the above salt composition that selects free hydroxyl, amino, carboxyl and carboxyl of 1 or 2. In addition, polymerization inhibitor can have above-mentioned functional group, also can generate above-mentioned functional group by the cessation reaction of polymerization etc.

As thering is hydroxyl or amino polymerization inhibitor, for example, can use the compound shown in following formula (1) or (2) as polymerization inhibitor.

According to the compound shown in general formula (1), import the end group of the univalent perssad shown in following formula (1-1) as main chain. Y in formula (1-1) is hydroxyl, the amino etc. that is derived from polymerization inhibitor.

According to the compound shown in general formula (2), import the end group of the univalent perssad shown in following formula (2-1) as main chain. The carbon atom of the carbonyl of the hydroxyl that is derived from the compound shown in general formula (1) in for example can through type (2) and Thiyl Radical bonding and be directed in polyarylene sulfide resin.

Think: in the main chain of polyarylene sulfide resin, be derived from raw material (elemental sulfur) and the disulfide bond that exists under melt temperature free radical cracking and the Thiyl Radical that produces, with the compound shown in general formula (1) or the compound bonding shown in general formula (2), thereby the formula of making (1-1) or (2-1) shown in group be directed in polyarylene sulfide resin. The existence of the construction unit of these ad hoc structures is features of the polyarylene sulfide resin that obtains of the melt polymerization by having used the compound shown in general formula (1) or (2).

As the compound shown in general formula (1), for example, can enumerate 2-iodophenol, 2-amino aniline etc. As the compound shown in general formula (2), can enumerate 2-iodine benzophenone.

As the polymerization inhibitor with carboxyl, for example, can use the more than a kind compound being selected from the compound shown in following general formula (3), (4) or (5).

In general formula (3), R¹And R²Represent independently of one another hydrogen atom or following general formula (a), (b) or (c) shown in univalent perssad, R¹Or R²At least any one be general formula (a), (b) or (c) shown in univalent perssad. In general formula (4), Z represents iodine atom or sulfydryl, R³Represent following general formula (a), (b) or (c) shown in univalent perssad. In general formula (5), R⁴Represent general formula (a), (b) or (c) shown in univalent perssad.

X in general formula (a)～(c) is hydrogen atom or alkali metal atom, becomes good aspect from reactivity, preferably hydrogen atom. As alkali metal atom, can enumerate sodium, lithium, potassium, rubidium and caesium etc., preferably sodium. In general formula (b), R¹⁰Represent the alkyl of carbon number 1～6. In general formula (c), R¹¹Represent the alkyl of hydrogen atom or carbon number 1～3, R¹²Represent the alkyl of carbon number 1～5.

According to the compound shown in general formula (3), (4) or (5), import the end group of the univalent perssad shown in following formula (6) or (7) as main chain. The existence of the construction unit of the end of these ad hoc structures is features of the polyarylene sulfide resin that obtains of the melt polymerization by having used the compound shown in general formula (3), (4) or (5).

(in formula, R⁵Represent general formula (a), (b) or (c) shown in univalent perssad. )

(in formula, R⁶Represent general formula (a), (b) or (c) shown in univalent perssad. )

As polymerization inhibitor, can use compound not having the functional groups such as carboxyl etc. As such compound, for example can use and be selected from diphenyl disulfide, single iodobenzene, benzenethiol, 2,2 '-dibenzothiazyl disulfide, 2-mercaptobenzothiazole, N cyclohexyl 2 benzothiazole sulfenamide, 2-(morpholinothio) benzothiazole and N, N '-dicyclohexyl-1, at least a kind of compound in 3-benzothiazole-2-sulfenamide.

The polyarylene sulfide resin of present embodiment generates as follows: in the molten mixture that the mixture heating of the catalyst that comprises diiodo-aromatic compound, elemental sulfur, polymerization inhibitor and add is as required obtained, carry out melt polymerization, thereby generate. For the ratio of the diiodo-aromatic compound in molten mixture, with respect to 1 mole of elemental sulfur, be preferably the scope of 0.5～2 mole, the scope of 0.8～1.2 mole more preferably. In addition, for the ratio of the polymerization inhibitor in mixture, with respect to 1 mole of solid sulfur, be preferably the scope of 0.0001～0.1 mole, the scope of 0.0005～0.05 mole more preferably.

Add and be not particularly limited in period of polymerization inhibitor, can reach the scope of preferably 200 DEG C～320 DEG C in the temperature that the mixture heating of the catalyst that comprises diiodo-aromatic compound, elemental sulfur and add is as required made to mixture, more preferably moment of scope of 250～320 DEG C is added polymerization inhibitor.

Can in molten mixture, add nitro compound and regulate polymerization speed as catalyst. As this nitro compound, conventionally can use various nitrobenzene derivatives. As nitrobenzene derivative, for example, can enumerate the iodo-4-nitrobenzene of 1,3-bis-, the iodo-4-nitrobenzene of 1-, 2, the iodo-4-nitrophenol of 6-bis-and the iodo-4-nitra-amine of 2,6-bis-. The amount of catalyst is the amount of adding usually used as catalyst, for example, with respect to elemental sulfur 100 mass parts, is preferably the scope of 0.01～20 mass parts.

The condition of melt polymerization is carried out to suitable adjusting, polymerisation is suitably carried out. More than the temperature of melt polymerization is preferably 175 DEG C and fusing point+100 of the polyarylene sulfide resin generating DEG C following scope, the more preferably scope of 180～350 DEG C. Melt polymerization is preferably 1[cPa at absolute pressure]～100[kPa] scope, 13[cPa more preferably]～60[kPa] and scope in carry out. The condition of melt polymerization does not need constant. For example, it is preferably scope, the more preferably scope of 180～250 DEG C of 175～270 DEG C that the polymerization initial stage can make temperature, and making absolute pressure is 6.7～100[kPa] scope, then, polymerization is carried out on the limit of heating up and reduce pressure continuously or periodically, limit, it is the fusing point+100 DEG C following scope of preferably 270 DEG C of above and polyarylene sulfide resins of generating, the more preferably scope of 300～350 DEG C that the polymerization later stage makes temperature, and making absolute pressure is 1[cPa]～6[kPa] scope carry out polymerization. In this description, the fusing point of resin refers to the value that uses differential scanning calorimetry (DSC) (PerkinElmerCo., the DSC device PyrisDiamond that Ltd. manufactures), measures according to JISK7121.

For melt polymerization, from preventing oxidation cross-linked reaction and obtaining the viewpoint of high polymerization degree, preferably under non-oxidizing atmosphere, carry out. In non-oxidizing atmosphere, the oxygen concentration of gas phase is preferably the scope that is less than the scope of 5 volume %, is more preferably less than 2 volume %, the further preferred oxygen-free in fact gas of gas phase. Non-oxidizing atmosphere is preferably the non-active gas atmosphere such as nitrogen, helium and argon gas.

Melt polymerization for example can carry out with the melting mixing machine that possesses heater, decompressor and agitating device. As melting mixing machine, for example, can enumerate Banbury mixer, kneader, continuous mixer, single screw extrusion machine and double screw extruder.

Molten mixture for melt polymerization does not preferably contain in fact solvent. More specifically, the amount of the solvent containing in molten mixture is with respect to diiodo-aromatic compound, elemental sulfur, polymerization inhibitor with total 100 mass parts of the catalyst adding as required, is preferably scope below 10 mass parts, the more preferably scope below 5 mass parts, the scope below 1 mass parts more preferably. The amount of solvent can be that 0 mass parts is above, scope more than 0.01 mass parts or scope more than 0.1 mass parts.

Also can be by cooling the molten mixture after melt polymerization (product) and obtain after the mixture of solid state, under reduced pressure or under the atmospheric pressure of non-oxidizing atmosphere, add hot mixt, thereby polymerisation is further carried out. Thus, not only can further increase molecular weight, and make the iodine molecule generating distil and be removed, therefore, the iodine atomic concentration in polyarylene sulfide resin can be suppressed to reduced levels. By being cooled to preferably the scope of 100～260 DEG C, more preferably scope, the further preferred temperature of the scope of 150～230 DEG C of 130～250 DEG C, can obtain the mixture of solid state. The heating being cooled to after solid state can be carried out under the temperature same with melt polymerization and pressure condition.

The product that comprises the polyarylene sulfide resin obtaining by melt polymerization operation also can be manufactured resin combination for directly dropping into the methods such as melting mixing machine by keeping intact, but in this product, adding membership dissolves the solvent of this product and prepares dissolved matter, while taking out product with the state of this dissolved matter from reaction unit, not only productivity ratio excellence, and then reactivity is also good, therefore preferred. The interpolation that can dissolve the solvent of this product is preferably carried out after melt polymerization, but also can carry out in the reaction later stage of melt polymerization, in addition, also can be as mentioned above by cooling molten mixture (product) and obtain after the mixture of solid state, add depress, reduce pressure under or under the atmospheric pressure of non-oxidizing atmosphere, add hot mixt and make polymerisation further carry out rear interpolation. Preparing the operation of this dissolved matter can carry out under non-oxidizing atmosphere. In addition, as the temperature of heating for dissolving, as long as dissolve the scope more than fusing point of solvent of previous reaction product in meeting, be preferably the scope of 200～350 DEG C, the scope of 210～250 DEG C more preferably, preferably carry out adding to depress.

For the compounding ratio that uses in order to prepare aforementioned dissolved matter, can dissolve the solvent of previous reaction product, with respect to product 100 mass parts that comprise polyarylene sulfide resin, be preferably the scope of 90～1000 mass parts, the scope of 200～400 mass parts more preferably.

As the solvent of meeting solubilizing reaction product, for example, can use the solvent using as polymerization solvent in the polymerisation in solutions such as Phillips method. as the example of preferred solvent, can enumerate: METHYLPYRROLIDONE (being abbreviated as below NMP), CHP, 2-Pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, epsilon-caprolactams, the aliphatic cyclic amide compounds such as N-methyl-epsilon-caprolactams, HPT (HMPA), tetramethylurea (TMU), dimethyl formamide (DMF), and the amide compound such as dimethylacetylamide (DMA), (degree of polymerization is below 2000 to polyethylene glycol dialkyl ether, there is the alkyl of carbon number 1～20) etc. etherificate polyethylene glycol compound, and tetramethylene sulfoxide, and the sulfoxide compound such as dimethyl sulfoxide (DMSO) (DMSO). as the example of other spendable solvents, can enumerate the more than a kind solvent in the group of selecting freely following material composition: benzophenone, diphenyl ether, diphenyl sulfide, 4,4 '-'-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, 2,5-diphenyl-oxazole, triphenylcarbinol, N, N-diphenylformamide, benzil, anthracene, 4-benzoyl biphenyl, dibenzoyl methane, 2-biphenyl carboxylic acids, dibenzothiophenes, pentachlorophenol, 1-benzyl-2-Pyrrolidone, 9-Fluorenone, 2-benzoyl naphthalene, 1-bromonaphthalene, 1,3-, bis-phenoxy group benzene, fluorenes, 1-phenyl-2-Pyrrolidone, 1-methoxynaphthalene, 1-ethyoxyl naphthalene, 1,3-diphenyl acetone, Isosorbide-5-Nitrae-dibenzoyl butane, luxuriant and rich with fragrance, 4-benzoyl biphenyl, 1,1-diphenyl acetone, neighbour, neighbour '-xenol, 2,6-diphenylphenol, benzophenanthrene, 2-phenylphenol, thianthrene, 3-phenoxy benzenemethanol, 4-phenylphenol, 9,10-, bis-chrloroanthracenes, triphenyl methane, 4,4 '-dimethoxy-benzophenone, 9,10-diphenylanthrancene, fluoranthene, diphenyl phthalate, diphenyl carbonate, 2,6-dimethoxy-naphthalene, 2,7-dimethoxy-naphthalene, 4-dibromodiphenyl ether, pyrene, 9,9 '-bis-fluorenes, 4,4 '-isopropylidene-xenol, epsilon-caprolactams, CHP, diphenyl iso-phthalate, diphenyl phthalate and 1-chloronaphthalene.

This dissolved matter taking out from reaction unit is in the time carrying out post processing, prepare resin combination with aforementioned other composition melting mixing, and reactivity becomes better, therefore preferred. As the method for the post processing of dissolved matter, be not particularly limited, for example can enumerate following methods.

(1) this dissolved matter kept intact or add after acid or alkali, solvent is removed in distillation under reduced pressure or under atmospheric pressure, then, distillation is removed to solid matter after solvent with being selected from solvent clean in the solvent that uses in water, this dissolved matter organic solvent of equal solubility (or have for low polymer), acetone, MEK and alcohols etc. more than 1 time or 2 times, and then neutralize, wash, filter and dry method.

(2) in this dissolved matter, add water, acetone, MEK, alcohol, ether, halogenated hydrocarbons, aromatic hydrocarbon and aliphatic hydrocarbon equal solvent (solvent that dissolves in the solvent of this dissolved matter and be at least poor solvent for polyarylene sulfide resin) as sedimentation agent, make the solid shape product sedimentation that comprises polyarylene sulfide resin and inorganic salts etc., solid shape product is filtered, cleaned and dry method.

(3) after adding the solvent that uses in this dissolved matter organic solvent of equal solubility (or have for low polymer) to stir in this dissolved matter, filter and remove low-molecular weight polymer, then use the solvent clean being selected from water, acetone, MEK and alcohol etc. more than 1 time or 2 times, then neutralize, wash, filter and dry method.

It should be noted that, in the illustrated such post-processing approach in above-mentioned (1)～(3), the dry of polyarylene sulfide resin can carry out in a vacuum, also can be in air or the non-active gas atmosphere of nitrogen and so in carry out. Also can be in the oxidizing atmosphere of scope of 5～30 volume % or heat-treat under reduced pressure in oxygen concentration, polyarylene sulfide resin be carried out oxidation cross-linked.

Below exemplify the reaction that generates polyarylene sulfide resin by melt polymerization.

Reaction equation (1)

Reaction equation (2)

Reaction equation (3)

Reaction equation (4)

Reaction equation (5)

Reaction equation (1)～(5) be use for example have comprise general formula (a), (b) or (c) shown in the diphenyl disulfide of substituent R of group example during as polymerization inhibitor, that generate the reaction of polyphenylene sulfide. Reaction equation (1) is in polymerization inhibitor-S-S-key issues the reaction of being conigenous by basic capsule solution in melt temperature. Reaction equation (2) is the adjacent carbon atom of the Thiyl Radical that produces in reaction equation (1) the end iodine atom of attacking the main chain in growth and iodine atom is departed from, thereby makes polymerization stop and import at the end of main chain simultaneously the reaction of substituent R. Reaction equation (3) is in the main chain of polyarylene sulfide resin, to be derived from raw material (elemental sulfur) and the disulfide bond that exists issues the reaction of being conigenous by basic capsule solution in melt temperature. Reaction equation (4) is that the Thiyl Radical by producing in reaction equation (3) makes polymerization termination with the bonding again of the Thiyl Radical producing in reaction equation (1) and substituent R imported to the reacting of end of main chain simultaneously. The iodine atom departing from free state (iodine free radical) or as reaction equation (5) iodine free radical bonding and generate iodine molecule more each other.

The product that comprises the polyarylene sulfide resin obtaining by melt polymerization contains the iodine atom that is derived from raw material. Therefore, polyarylene sulfide resin is used to the preparation etc. of spinning resin combination conventionally with the state of the mixture that contains iodine atom. Scope that the concentration of the iodine atom in this mixture is for example 0.01～10000ppm with respect to polyarylene sulfide resin, be preferably the scope of 10～5000ppm. Utilize the sublimability of iodine molecule, also iodine atomic concentration can be suppressed to reduced levels, in this case, also can be made as the scope below 900ppm, the scope below preferred 100ppm, the further preferably scope below 10ppm. And then, although also can remove iodine atom to detectability, impracticable while considering productivity ratio. Detectability is for example 0.01ppm left and right. For the polyarylene sulfide resin of the present embodiment obtaining by melt polymerization or the product that comprises it, the poly arylidene thio-ester that can obtain with the solution polymerization process that for example utilizes the dichloro aromatic compounds such as Phillips method in organic polar solvent in this point that comprises iodine atom is distinguished clearly.

Also be appreciated that by above-mentioned reaction equation, the polyarylene sulfide resin obtaining by melt polymerization comprises: the main chain mainly being formed by fragrant thio-ether units and with the substituent R of the regulation of the end bonding of this main chain, described fragrant thio-ether units comprises and is derived from the aromatic ring of diiodo-aromatic compound and the sulphur atom with its Direct Bonding. The substituent R of regulation is bonded directly to the aromatic ring of main chain end or is situated between and is bonded on the aromatic ring of end of main chain by being derived from the part-structure of polymerization inhibitor.

As the polyphenylene sulfide of the polyarylene sulfide resin of an embodiment, for example, there is the main chain that comprises the repetitive shown in following general formula (10) (fragrant thio-ether units).

Repetitive shown in formula (10) is more preferably with the repetitive shown in the following formula (10a) of para-linkage and with the repetitive shown in the following formula (10b) of ortho position bonding.

Wherein, the repetitive with para-linkage shown in formula (10a) the heat resistance of resin and crystalline aspect preferred.

The polyphenylene sulfide of an embodiment can comprise shown in following general formula (11), have as with the substituent repetitive of the side chain of aromatic ring bonding:

(in formula, R²⁰And R²¹Represent independently of one another hydrogen atom, the alkyl of carbon number 1～4, nitro, amino, phenyl, methoxy or ethoxy. ). But from the viewpoint of degree of crystallinity and heat resistance reduction, polyphenylene sulfide does not preferably contain in fact the repetitive of general formula (11). More specifically, about the ratio of the repetitive shown in formula (11), with respect to the summation of the repetitive shown in the repetitive shown in formula (10) and formula (11), be preferably below 2 quality %, more preferably below 0.2 quality %.

The polyarylene sulfide resin of present embodiment is mainly made up of above-mentioned fragrant thio-ether units, conventionally in main chain, also comprises the construction unit of disulfide bond elemental sulfur, shown in following formula (20) that is derived from raw material.

From the aspect of heat resistance, mechanical strength, for the ratio of the construction unit shown in formula (20), with respect to the summation of the structure position shown in fragrant thio-ether units and formula (20), be preferably scope below 2.9 quality %, the scope below 1.2 quality % more preferably. By making the construction unit shown in polyarylene sulfide resin contained (20), improve polyarylene sulfide resin composition and metal adaptation aspect preferred.

The Mw/Mtop of the polyarylene sulfide resin of present embodiment is preferably 0.80～1.70 scope, 0.90～1.30 scope more preferably. Be such scope by making Mw/Mtop, can improve the processability of polyarylene sulfide resin, can give good die cavity balance. In this description, Mw represents the weight average molecular weight by gel permeation chromatography, and Mtop represents that the detected intensity of the chromatogram obtaining by this mensuration reaches the mean molecule quantity (peak molecular weight) of maximum point. Mw/Mtop represents the distribution of the molecular weight of determination object, and conventionally, this value approaches the narrowly distributing that represents molecular weight at 1 o'clock, along with this value becomes large, represents that the distribution of molecular weight broadens. It should be noted that, the condition determination of gel permeation chromatography adopts the condition determination identical with the embodiment of this description. But, can substantially not affect in the scope of value of Mw, Mw/Mtop and change condition determination.

For the weight average molecular weight of the polyarylene sulfide resin of present embodiment, only otherwise damage effect of the present invention, be just not particularly limited, for its lower limit, from the aspect of mechanical excellent strength, be preferably more than 28000 and then more than 30000 scope more preferably. On the other hand, for the upper limit, from giving the aspect of better die cavity balance, be preferably the scope below 100000, and then the scope below 60000 more preferably, and then most preferably be the scope below 55000. And then, from mechanical excellent strength and can give the viewpoint of good die cavity balance, can be with the polyarylene sulfide resin of 28000～60000 scope, more preferably use together with the polyarylene sulfide resin of 30000～55000 scope weight average molecular weight in exceeding 60000 and be the polyarylene sulfide resin of the scope below 100000.

The non-newtonian index of polyarylene sulfide resin is preferably 0.95～1.75 scope, 1.0～1.70 scope more preferably. Be such scope by making non-newtonian index, can improve the processability of polyarylene sulfide resin, can give good die cavity balance. In this description, non-newtonian index refers to the index of the following relational expression of shear rate under the condition of 300 DEG C of satisfied temperatures and shear stress. Non-newtonian index can become the molecular weight of determination object or straight chain, side chain, crosslinked so relevant index of molecular structure, conventionally, this value approaches at 1 o'clock, represents that the molecular structure of resin is straight chain shape, along with this value becomes large, represent to comprise more side chain, cross-linked structure.

D＝α×Sⁿ

(in above-mentioned formula, D represents shear rate, and S represents shear stress, and α represents constant, and n represents non-newtonian index. )

There is the Mw/Mtop of above-mentioned particular range and the polyarylene sulfide resin of non-newtonian index for example can obtain as follows: diiodo-aromatic compound, elemental sulfur and polymerization inhibitor are reacted in the method for (polymerisation in solution) in the molten mixture that contains diiodo-aromatic compound, elemental sulfur and polymerization inhibitor, make the macromolecule quantification to a certain degree of described polyarylene sulfide resin, thereby obtain.

The fusing point of the polyarylene sulfide resin of present embodiment is preferably the scope of 250～300 DEG C, the scope of 265～300 DEG C more preferably. Melt viscosity (V6) at 300 DEG C of polyarylene sulfide resin is preferably 1～2000[Pas] scope, 5～1700[Pas more preferably] scope. Herein, melt viscosity (V6) refers to that using flow tester under 300 DEG C of temperature, load 1.96MPa, to use aperture length and the ratio (aperture length/orifice diameter) of orifice diameter is that 10/1 aperture keeps the melt viscosity after 6 minutes.

The polyarylene sulfide resin composition of present embodiment can contain one kind or two or more inorganic filler. By compounding inorganic filler, can obtain the composition of high rigidity, high heat-resistant stability. As inorganic filler, for example, can enumerate: bat wool and the glass flakes such as the plate-like fillers such as the pulverulent filler such as carbon black, calcium carbonate, silica and titanium oxide, talcum and mica, glass microballoon, silica microballon and glass hollow ball equigranular filler, glass fibre, carbon fiber and calcium silica fiber. Polyarylene sulfide resin composition particularly preferably contains at least a kind of inorganic filler in the group of selecting free glass fibre, carbon fiber, carbon black and calcium carbonate composition.

The content of inorganic filler is with respect to polyarylene sulfide resin 100 mass parts, is preferably the scope of 1～300 mass parts, more preferably scope, the scope of 15～150 mass parts more preferably of 5～200 mass parts. By making the content of inorganic filler in described scope, aspect keeping in the mechanical strength of formed products, can obtain more excellent effect.

The polyarylene sulfide resin composition of present embodiment can contain and is selected from resin thermoplastic resin, elastomer and crosslinkable resin, except polyarylene sulfide resin. These resins also can be compounded in resin combination together with inorganic filler.

As the thermoplastic resin of compounding in polyarylene sulfide resin composition, for example, can enumerate polyester, polyamide, polyimides, PEI, Merlon, polyphenylene oxide, polysulfones, polyether sulfone, polyether-ether-ketone, polyether-ketone, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), poly-difluoroethylene, polystyrene, ABS resin, organic siliconresin and liquid crystal polymer (liquid crystal polyester etc.).

Polyamide is the polymer with amido link (NHCO-). As polyamide, for example, can enumerate: the polymer (i) being obtained by the polycondensation of diamines and dicarboxylic acids, the polymer that (ii) obtained by the polycondensation of amino carboxylic acid and (iii) polymer of being obtained by the ring-opening polymerisation of lactams etc. Polyamide can be used singly or in combination two or more.

As the example of the diamines for obtaining polyamide, can enumerate fatty family diamines, fragrant family diamines and alicyclic ring family Diamines. As fatty family diamines, preferably straight chain shape or there is the diamines of the carbon number 3～18 of side chain. As the example of suitable fatty family diamines, can enumerate 1,3-propane diamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 2-methyl isophthalic acid, 8-octamethylenediamine, 1,9-nonamethylene diamine, 1,10-decamethylene diamine, 1,11-hendecane diamines, 1,12-dodecane diamines, 1,13-tridecane diamines, 1,14-tetradecane diamines, 1,15-pentadecane diamines, 1,16-hexadecane diamines, 1,17-heptadecane diamines, 1,18-octadecamethylene diamine, 2,2,4-trimethyl hexamethylene diamine and 2,4,4-trimethyl hexamethylene diamine. They can be used singly or in combination two or more.

As fragrant family diamines, preferably there is the diamines of the carbon number 6～27 of phenylene. as the example of suitable fragrant family diamines, can enumerate: o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), m-xylene diamine, p dimethylamine, 3,4-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,3 '-DADPS, DDS, 4,4 '-diaminodiphenyl sulfide, 4,4 '-bis-(m-aminophenyl oxygen base) diphenyl sulphone (DPS), 4,4 '-bis-(p-aminophenyl oxygen base) diphenyl sulphone (DPS), benzidine, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, two (4-aminophenyl) propane of 2,2-, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas of 2,2-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, two (3-amino-benzene oxygen) benzene of 1,3-, two (3-amino-benzene oxygen) benzene of 1,3-, 4,4 '-diaminourea-3,3 '-diethyl-5,5 '-dimethyl diphenylmethane, 4,4 '-diaminourea-3,3 ', 5,5 '-tetramethyl diphenyl methane, 2,4-diaminotoluene, and 2,2 '-dimethylbenzidine. they can be used singly or in combination two or more.

As alicyclic ring family diamines, preferably there is the diamines of the carbon number 4～15 of cyclohexylidene. As the example of suitable alicyclic ring family diamines, can enumerate 4,4 '-diaminourea-bis-cyclohexylidene methane, 4,4 '-diaminourea-bis-cyclohexylidene propane, 4,4 '-diaminourea-3,3 '-dimethyl-bis-cyclohexylidene methane, Isosorbide-5-Nitrae-DACH and piperazine. They can be used singly or in combination two or more.

As the dicarboxylic acids for obtaining polyamide, can enumerate fatty family dicarboxylic acids, fragrant family dicarboxylic acids and alicyclic ring family dicarboxylic acids.

As fatty family dicarboxylic acids, the preferably saturated or undersaturated dicarboxylic acids of carbon number 2～18. As the example of suitable fatty family dicarboxylic acids, can enumerate: oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, octadecane diacid, maleic acid and fumaric acid. They can be used singly or in combination two or more.

As fragrant family dicarboxylic acids, preferably there is the dicarboxylic acids of the carbon number 8～15 of phenylene. As the example of suitable fragrant family dicarboxylic acids, can enumerate: M-phthalic acid, terephthalic acid (TPA), methyl terephthalic acid (TPA), biphenyl-2,2 '-dioctyl phthalate, biphenyl-4,4 '-dioctyl phthalate, diphenyl methane-4,4 '-dioctyl phthalate, diphenyl ether-4,4 '-dioctyl phthalate, diphenyl sulphone (DPS)-4,4 '-dioctyl phthalate, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid and Isosorbide-5-Nitrae-naphthalenedicarboxylic acid. They can be used singly or in combination two or more. And then, also can be can use the polybasic carboxylic acids such as trimellitic acid, trimesic acid and Pyromellitic Acid in the scope of melt-shaping.

As amino carboxylic acid, the preferably amino carboxylic acid of carbon number 4～18. As the example of suitable amino carboxylic acid, can enumerate: 4-Aminobutanoicacid, 6-aminocaprolc acid, 7-aminoheptylic acid, 8-aminocaprylic acid, 9 aminononanoic acid, the amino capric acid of 10-, the amino hendecanoic acid of 11-, 12 amino dodecanoic acid, the amino tetradecanoic acid of 14-, the amino hexadecanoic acid of 16-and the amino octadecanoid acid of 18-. They can be used singly or in combination two or more.

As the lactams for obtaining polyamide, for example, can enumerate epsilon-caprolactams, omega-lauric lactam, ζ-oenantholcatam and η-spicy inner formyl amine. They can be used singly or in combination two or more.

As the combination of the raw material of preferred polyamide, can enumerate: epsilon-caprolactams (nylon 6), 1,6-hexamethylene diamine/adipic acid (nylon 6,6), 1,4-butanediamine/adipic acid (nylon 4,6), 1,6-hexamethylene diamine/terephthalic acid (TPA), 1,6-hexamethylene diamine/terephthalic acid (TPA)/epsilon-caprolactams, 1,6-hexamethylene diamine/terephthalic acid (TPA)/adipic acid, 1,9-nonamethylene diamine/terephthalic acid (TPA), 1,9-nonamethylene diamine/terephthalic acid (TPA)/epsilon-caprolactams, 1,9-nonamethylene diamine/1,6-hexamethylene diamine/terephthalic acid (TPA)/adipic acid and m-xylene diamine/adipic acid. Wherein, further preferably by 1,4-butanediamine/adipic acid (nylon 4,6), 1,6-hexamethylene diamine/terephthalic acid (TPA)/epsilon-caprolactams, 1,6-hexamethylene diamine/terephthalic acid (TPA)/adipic acid, 1,9-nonamethylene diamine/terephthalic acid (TPA), 1,9-nonamethylene diamine/terephthalic acid (TPA)/epsilon-caprolactams or 1,9-nonamethylene diamine/1, the polyamide that 6-hexamethylene diamine/terephthalic acid (TPA)/adipic acid obtains.

The content of thermoplastic resin is preferably the scope of 1～300 mass parts, more preferably scope, the scope of 5～45 mass parts more preferably of 3～100 mass parts with respect to polyarylene sulfide resin 100 mass parts. By making the content of the thermoplastic resin except polyarylene sulfide resin in above-mentioned scope, can obtain heat resistance, chemical proofing and mechanical properties and further improve such effect.

As the elastomer of compounding in polyarylene sulfide resin composition, usually use thermoplastic elastomer (TPE). As thermoplastic elastomer (TPE), for example, can enumerate polyolefin elastomer, Fuoroelastomer and silicon-type elastomer. It should be noted that, in this description, thermoplastic elastomer (TPE) is classified as elastomer, instead of is classified as aforementioned thermoplastic resin.

Elastomer (particularly thermoplastic elastomer (TPE)) preferably have can with the functional group that selects at least one radical reaction in the group of salt composition of free hydroxyl, amino, carboxyl and carboxyl. Thus, can obtain gas generated resin combination excellent especially at the aspect such as cementability and resistance to impact and that can suppress to be caused by heating. As described functional group, can enumerate: epoxy radicals, amino, hydroxyl, carboxyl, sulfydryl, NCO, oxazolinyl and formula: R (CO) O (CO)-or R (CO) O-(in formula, R represents the alkyl of carbon number 1～8) shown in group. The thermoplastic elastomer (TPE) with described functional group for example can obtain by alpha-olefin and the copolymerization of the vinyl polymerized compound with aforementioned functional groups. Alpha-olefin for example can be enumerated the alpha-olefines of the carbon numbers 2～8 such as ethene, propylene and 1-butylene. As the vinyl polymerized compound with aforementioned functional groups, for example can enumerate: the α such as (methyl) acrylic acid and (methyl) acrylate, the α of beta-unsaturated carboxylic acid and Arrcostab thereof, maleic acid, fumaric acid, itaconic acid and other carbon number 4～10, β-unsaturated dicarboxylic and derivative thereof (monoesters or diester and acid anhydrides thereof etc.) and (methyl) glycidyl acrylate etc. Wherein, from the aspect of the raising of toughness and resistance to impact, preferably have select free epoxy radicals, carboxyl and formula: R (CO) O (CO)-or R (CO) O-(in formula, R represents the alkyl of carbon number 1～8) shown in the group of group composition in ethylene-propylene copolymer and the ethylene-butene copolymer of at least a kind of functional group.

Elastomeric content is according to its kind, purposes and different, therefore can not specify entirely, for example, with respect to polyarylene sulfide resin 100 mass parts, be preferably the scope of 1～300 mass parts, more preferably scope, the scope of 5～45 mass parts more preferably of 3～100 mass parts. By making elastomeric content in above-mentioned scope, can obtain guarantee the heat resistance of formed products, toughness aspect more excellent effect.

In polyarylene sulfide resin composition, the crosslinkable resin of compounding has more than 2 bridging property functional group. As bridging property functional group, can enumerate epoxy radicals, phenol hydroxyl, amino, amide groups, carboxyl, anhydride group and NCO etc. As crosslinkable resin, for example, can enumerate epoxy resin, phenolic resins and polyurethane resin.

As epoxy resin, preferred fragrance family epoxy resin. fragrance family epoxy resin can have halogen group or hydroxyl etc. as the example of suitable fragrant family epoxy resin, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, triphenyl methane type epoxy resin, tetraphenyl ethane type epoxy resin, dicyclopentadiene-phenol addition reaction-type epoxy resin, phenol aralkyl-type epoxy resin, naphthol novolac varnish type epoxy resin, naphthols aralkyl-type epoxy resin, naphthols-phenol cocondensation phenolic resin varnish type epoxy resin, naphthols-cresols cocondensation phenolic resin varnish type epoxy resin, aromatic hydrocarbon formaldehyde resin phenol-formaldehyde resin modified type epoxy resin, and biphenyl phenolic resin varnish type epoxy resin. these fragrant family epoxy resin can be used singly or in combination two or more. in these fragrant family epoxy resin, from the aspect of the compatibility excellence of other resinous principle, particularly preferably phenolic resin varnish type epoxy resin, more preferably cresols phenolic resin varnish type epoxy resin.

The content of crosslinkable resin, with respect to polyarylene sulfide resin 100 mass parts, is preferably the scope of 1～300 mass parts, the more preferably scope of 3～100 mass parts, the more preferably scope of 5～30 mass parts. By making the content of crosslinkable resin in above-mentioned scope, rigidity and the heat resistance that can obtain especially significantly formed products improve such effect.

Polyarylene sulfide resin composition can contain silane compound, described silane compound have can with the functional group that selects at least one radical reaction in the group of salt composition of free hydroxyl, amino, carboxyl and carboxyl. Thus, the compatibility of polyarylene sulfide resin and other composition improves, and in addition, can obtain the gas generated resin combination that can suppress to be caused by heating. As described silane compound, for example can enumerate: the silane couplers such as γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl group methyldiethoxysilane and γ-glycidoxy propyl group methyl dimethoxysilane.

The content of silane compound, for example with respect to polyarylene sulfide resin 100 mass parts, is preferably the scope of 0.01～10 mass parts, further the scope of 0.1～5 mass parts more preferably. By making the content of silane compound in above-mentioned scope, the compatibility that can obtain polyarylene sulfide resin and aforementioned other composition improves such effect.

The polyarylene sulfide resin composition of present embodiment can contain other additives such as releasing agent, colouring agent, heat-resisting stabilizing agent, ultra-violet stabilizer, blowing agent, antirust agent, fire retardant and lubricant. Add the content of drug for example with respect to polyarylene sulfide resin 100 mass parts, be preferably the scope of 1～10 mass parts.

Polyarylene sulfide resin composition can be by for example, by the method for the polyarylene sulfide resin that utilizes said method to obtain and aforementioned other composition melting mixing, obtain with forms such as the compounds of partical. The temperature of melting mixing is for example preferably the scope of 250～350 DEG C, further the scope of 290～330 DEG C more preferably. Melting mixing can use double screw extruder etc. to carry out.

The polyarylene sulfide resin composition of present embodiment can be separately or with the combination of materials such as aforementioned other composition be processed into by the various melt-processed methods of injection moulding, extrusion molding, compression molding and blow molding and so on the formed products that heat resistance, shaping processability, dimensional stability etc. are excellent. Gas generated few when heated of the polyarylene sulfide resin composition of present embodiment, so can easily manufacture the formed products of high-quality.

When the polyarylene sulfide resin composition of present embodiment is used for to electric-vehicle part, can reduce caused by heating gas generated. Therefore, can reduce gas componant is the low molecular weight compound of sulfur atom-containing and contacting of the metal materials such as copper, its result, even if repeatedly applying the reaction that also can suppress both in high-tension situation, can suppress generation, the progress of trees (resinoid depredation), improve resistance to electric trace.

So, polyarylene sulfide resin composition of the present invention can be aptly possessing lithium rechargeable battery and especially requiring the electric automobile field of high security for hybrid vehicle (HV), electric automobile (EV) and so on. Therefore, the electric-vehicle part obtaining about polyarylene sulfide resin composition of the present invention is shaped, for example, can list the housing for holding power model, current transformer, condenser, insulator, engine terminal box, battery, motor compressor, battery current sensor, tagblock etc. The especially suitable ignition coil housing as DLI system of this formed products.

Embodiment

Below, enumerating embodiment further illustrates the present invention. But the present invention is not limited to these embodiment.

1. evaluation assessment

[flexural property]

Standard test method ... ASTMD-790

Test film ... 3.2mm (thick) × 12.7mm (wide) × 127mm (length)

Result of the test ... the mean value of test number n=10

[hot water resistance]

Test film is immersed in the hot water of 95 DEG C, investigates the rheological parameters' change with time of bending strength.

Test film ... 3.2mm (thick) × 12.7mm (wide) × 127mm (length)

The test method of bending strength ... ASTMD-790

Assessment item ... bending strength after 1000 hours, 3000 hours is with respect to the conservation rate of initial strength

Result of the test ... the mean value of test number n=5

[metal dhering strength]

Sheet metal (SUS304) to 4 × 10 × 49mm that is placed in mould is above injected the polyarylene sulfide resin composition of same size amount, and make its shaping, this formed products is implemented to tension test under the condition of 20mm, draw speed 1mm/ between chuck minute, measure metal dhering strength.

[epoxy resin dhering strength]

The test film of shaping 3mm (thick) × 25mm (wide) × 75mm (length), the mode taking bond area as 25mm × 10mm on test film is with thickness 40～50 μ m epoxy resin coatings (host: EPICLON850 (Dainippon Ink Chemicals's manufacture)/silica (filling rate 50 quality %), curing agent: hexahydrophthalic anhydride, host/curing agent=100/30 (mass ratio)). After they are fixing with fixture, at 85 DEG C, heat 3 hours, then at 150 DEG C, heat 3 hours, then Slow cooling, thus make epoxy resin cure. Then, measure tensile shear strength with the draw speed of 5mm/ minute, record real load.

[die cavity balance]

Use has the gasket mould of 40 die cavitys, under the condition that can be completely filled at the die cavity (C1) of the position of the most close sprue gate with minimum molding condition by PPS compound injection moulding. Molding condition is 75 tons of forming machines, 320 DEG C of barrel temperatures, 140 DEG C of mold temperatures, without pressurize.

Die cavity after moulding (C1) is compared with the compactedness apart from sprue gate die cavity (C10) farthest in identical runner. Compactedness (quality %) is obtained with respect to the mass ratio of the formed products of die cavity (C1) by the formed products of die cavity (C10). The compactedness that can say die cavity (C10) is higher, die cavity balance is more excellent. According to compactedness, utilize following benchmark to judge the die cavity balance of each composition.

The scope of AA:100～90 quality %

The scope of A:89～80 quality %

The scope of B:79～70 quality %

The scope of C:69～60 quality %

Scope below D:59% quality

[gas generated]

Use gas chromatography-mass spectrum device, the sample of the ormal weight of polyarylene sulfide resin or resin combination is heated 15 minutes at 325 DEG C, the gas generated form with quality % is now carried out quantitatively.

[resistance to electric trace]

The test film of shaping 2mm (thick) × 50mm (wide) × 100mm (length), by the method according to ASTMD3638, along resin flows direction detection, by breakdown voltage and the mapping of dropping number, reads the voltage of 50.

2. polyphenylene sulfide (PPS resin) is synthetic

(synthesis example 1:PPS-1's is synthetic)

By paradiiodobenzene (Tokyo changes into Co., Ltd., paradiiodobenzene purity more than 98.0%) 300.0g, solid sulfur (Kanto Kagaku K. K.'s manufacture, sulphur (powder)) 27.00g, 4, (Wako Pure Chemical Industries, Ltd.'s manufacture, 4 of 4 '-bis-thiobis benzoic acid, 4 '-bis-thiobis benzoic acid, TechnicalGrade) 2.0g heats, they dissolved, is mixed under nitrogen at 180 DEG C. Then, be warming up to 220 DEG C, be decompressed to absolute pressure 26.6kPa. For the molten mixture obtaining, the mode that reaches 133Pa with absolute pressure at 320 DEG C periodically changes temperature and pressure, carries out 8 hours melt polymerizations. After reaction finishes, add NMP200g, at 220 DEG C, add thermal agitation, gained dissolved matter is filtered. In dissolved matter after filtration, add NMP320g, carry out filter cake cleaning and filtering. In the filter cake that contains NMP obtaining, add ion exchange water 1L, in autoclave, in 200 DEG C of stirrings 10 minutes. Then, filter filter cake, in the filter cake after filtration, add the ion exchange water 1L of 70 DEG C, carry out filter cake cleaning. In the moisture filter cake of gained, add ion exchange water 1L, stir 10 minutes. Then, filter filter cake, in the filter cake after filtration, add the ion exchange water 1L of 70 DEG C, carry out filter cake cleaning. Repeat again after this operation, filter cake is dried to 4 hours at 120 DEG C, obtain PPS resin (PPS-1) 91g.

(synthesis example 2:PPS-2's is synthetic)

Use " 2-Iodoaniline (Tokyo changes into Co., Ltd. and manufactures) " replacement " 4,4 '-bis-thiobis benzoic acid ", in addition, similarly operate with synthesis example 1, obtain PPS resin (PPS-2) 91g.

(synthesis example 3:PPS-3's is synthetic)

Use " diphenyl disulfide (Sumitomo Seika Co., Ltd, DPDS) " replacement " 4,4 '-bis-thiobis benzoic acid ", in addition, similarly operate with synthesis example 1, obtain PPS resin (PPS-3) 91g.

(synthesis example 4:PPS-4's is synthetic)

In the autoclave of 2L, drop into 1-METHYLPYRROLIDONE 600g and five hydrated sodium sulfide 336.3g (2.0mol), be warming up to 200 DEG C under nitrogen atmosphere, water-NMP mixture is removed in distillation thus. Then, to adding the solution that p-dichloro-benzenes 292.53g (1.99mol) and 2,5-dichloroaniline 1.62g (0.01mol) is dissolved in to gained in NMP230g in this system, under nitrogen atmosphere, in 220 DEG C of reactions 5 hours, and then in 240 DEG C of reactions 2 hours. Content from reaction vessel taking-up is cooling, a sampling part, with gas chromatograph, to unreacted 2,5-dichloroaniline carries out quantitatively. In addition, residual slurry is cleaned several times to leaching polymer filter cake with hot water. By this filter cake drying under reduced pressure at 80 DEG C, obtain powder containing amino polyphenylene sulfide (PPS-4).

The proterties of the PPS-1～PPS-4 obtaining in synthesis example 1～4 is shown in to table 1.

[table 1]

3. polyphenyl thioether resin composition (PPS compound)

[raw material]

In order to prepare PPS resin combination, prepare following material.

(thermoplastic elastomer (TPE))

ELA: the copolymer (Sumitomo Chemical Company Ltd's manufacture, " BONDFAST7L ") of ethylene/methacrylic acid ethylene oxidic ester (3 quality %)/methyl acrylate (27 quality %)

(silane coupler)

Epoxy silane: γ-glycidoxypropyltrime,hoxysilane

(inorganic filler)

GF: fiberglas chopped strand (fibre diameter 10 μ m, length 3mm)

[making of compound and evaluation]

According to the formula composition shown in table 2, the mixed machine of utilization bucket, each raw material is evenly mixed, then use twin-screw mixer extruder (TEM-35B, toshiba machine) at 300 DEG C, to carry out melting mixing, obtain granular compound. The compound obtaining is carried out to injection moulding under the condition of 300 DEG C of barrel temperatures, 140 DEG C of mold temperatures, make the test film using in flexural property, metal dhering strength, die cavity balance and hot water resistance test, carry out various evaluations. In addition, for independent PPS resin and compound mensurated gas composition generation. Evaluation result is shown in to table 2.

[table 2]

Result as shown in Table 2 shows, PPS-1, PPS-2 and PPS-3 are being better than PPS-4 aspect mechanical property (bending strength, bend fracture percentage elongation), metal dhering strength, epoxy resin dhering strength, die cavity balance, hot water resistance, gas generated, resistance to electric trace.

Claims (6)

1. an electric-vehicle part polyarylene sulfide resin composition, it contains:

Polyarylene sulfide resin; With

Select free inorganic filler, thermoplastic resin except described polyarylene sulfide resin, elastomer andThere is at least a kind of other composition in the group of crosslinkable resin composition of more than 2 bridging property functional group,

Described polyarylene sulfide resin can utilize and comprise and make diiodo-aromatic compound, elemental sulfur and polymerization inhibitorAnti-in the molten mixture that comprises described diiodo-aromatic compound, described elemental sulfur and described polymerization inhibitorThe method of answering obtains.

2. electric-vehicle part polyarylene sulfide resin composition according to claim 1, wherein,Described polyarylene sulfide resin have be derived from described polymerization inhibitor select free hydroxyl, amino, carboxyl and carboxylAt least one group in the group of salt composition.

3. electric-vehicle part polyarylene sulfide resin composition according to claim 1 and 2, itsIn, described polyarylene sulfide resin has 0.80～1.70 Mw/Mtop,

Described Mw and Mtop utilize the weight average molecular weight of gel permeation chromatography and peak value to divideSon amount.

4. combine with polyarylene sulfide resin according to the electric-vehicle part described in any one in claim 1～3Thing, wherein, described polyarylene sulfide resin have 0.95～1.75 at 300 DEG C non-newtonian index and0.80～1.70 Mw/Mtop,

Described Mw and Mtop utilize the weight average molecular weight of gel permeation chromatography and peak value to divideSon amount.

5. an electric-vehicle part formed products, it is by gathering described in any one in claim 1～4Arylidene thio-ester resin composition is shaped and obtains.

6. an electric-vehicle part, it possesses formed products claimed in claim 5.