CN106189173A

CN106189173A - Fan products formed

Info

Publication number: CN106189173A
Application number: CN201610274006.7A
Authority: CN
Inventors: 仓光匡人; 山口徹
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2015-06-01
Filing date: 2016-04-28
Publication date: 2016-12-07
Anticipated expiration: 2036-04-28
Also published as: JP2016222828A; JP6472331B2; CN106189173B; TW201643035A; TWI636868B

Abstract

The present invention provides fan products formed, even if its in high temperature environments and rotate at high speed state operating, the deformation of impeller is also few.The fan products formed of the present invention is characterised by, it contains thermoplastic resin composition, in the Measurement of Dynamic Viscoelasticity of described thermoplastic resin composition, the ratio of storage modulus E2 of 110 DEG C ' storage modulus E1 ' relative to 85 DEG C (E2 '/E1 ') it is more than 0.90, ratio storage modulus when the storage modulus of 110 DEG C is E2 ', the proportion of 23 DEG C is ρ (E2 '/ρ) it is 4, more than 000MPa.

Description

Fan products formed

Technical field

The present invention relates to a kind of fan products formed.More particularly it relates in high temperature environments and High Temperature Rotating Time can suppress the fan products formed that impeller deforms.

Background technology

In the past, used butylene terephthalate system resin (PBT system resin) as the cooling of electric, electronic equipment etc. Use fan.But, the proportion of PBT system resin is high, and the temperature dependency of mechanical strength is big, therefore exists at high temperature ring Under border, during operating, impeller deforms the problems such as increase.

As the fan of the resin used beyond PBT system resin, have studied the fan etc. comprising impeller, described impeller By being added with polyphenylene oxide in phenylethylene resin series, the resin combination of inorganic fill material constitutes (with reference to patent literary composition Offer 1).Suppress to deform such fan (ginseng additionally, be investigated by connecting by bar-shaped connection member between impeller According to patent documentation 2).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2000-73992 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2010-236446 publication

Summary of the invention

The problem that invention is to be solved

But, the invention described in patent documentation 1 is the patent relating to recirculation, due to containing substantial amounts of polyphenyl second Alkene, therefore thermostability is low, and in high temperature environments and rotate at high speed during state operating, impeller when fan rotates has can Can deform.Additionally, the fan of patent documentation 2 record is fixed by connection member between impeller, but deposit The problems such as effect cannot be obtained at the circumferential deformation caused for centrifugal force.

That is, even if not yet knowing at present one to possess in high temperature environments and state operating rotate at high speed, deformation are also few The fan of impeller.

Therefore, it is an object of the invention to provide a kind of fan products formed, even if it is in high temperature environments and with high-speed rotary Turning state operating, the deformation of impeller is also few.

For solving the means of problem

The present inventor conscientiously studies, found that by following thermoplastic resin composition is used for fan products formed, Can solve the problem that the problems referred to above, described thermoplastic resin composition in Measurement of Dynamic Viscoelasticity, the storage modulus of 110 DEG C / the E1 ' of the E2 ' storage modulus E1 relative to 85 DEG C ' ratio (E2 ') and the storage modulus of 110 DEG C be E2 ', the ratio of 23 DEG C It is heavily particular range for the ratio storage modulus (E2 '/ρ) during ρ.

That is, present invention is as follows.

[1] a kind of fan products formed, wherein, it contains thermoplastic resin composition, described thermoplastic resin composition The ratio of in Measurement of Dynamic Viscoelasticity, storage modulus E2 of 110 DEG C ' storage modulus E1 ' relative to 85 DEG C (E2 '/E1 ') it is more than 0.90,

Ratio storage modulus when the storage modulus of 110 DEG C is E2 ', the proportion of 23 DEG C is ρ (E2 '/ρ) be 4,000MPa with On.

[2] a kind of fan products formed, wherein, in above-mentioned [1], the flame retardancy level of above-mentioned thermoplastic resin composition (depends on According to UL94.Implement with the test film thickness of 0.75mm) as V-0.

[3] a kind of fan products formed, wherein, in above-mentioned [1] or [2], above-mentioned thermoplastic resin composition is polyphenylene oxide Based resin composition.

[4] a kind of fan products formed, wherein, in above-mentioned [1] in any one of [3], above-mentioned thermoplastic resin composition Polyphenylene ether resin composition for following: polyphenylene oxide (A), phenylethylene resin series (B) and the gross mass of glass fibre (C) Being more than 90 mass %, if above-mentioned gross mass is 100 mass %, above-mentioned polyphenylene ether resin composition contains polyphenyl Ether (A) 45～75 mass %, phenylethylene resin series (B) 0～5 mass %, glass fibre (C) 25～50 mass %.

[5] a kind of fan products formed, wherein, in above-mentioned [1] in any one of [4], above-mentioned thermoplastic resin composition Contain organic phosphorus flame retardant (D) further, if polyphenylene oxide (A), phenylethylene resin series (B), glass fibre (C) and have When the gross mass of machine phosphorus flame retardant (D) is 100 mass %, the content of organic phosphorus flame retardant (D) is 5～20 matter Amount %.

[6] a kind of fan products formed, wherein, in above-mentioned [5], if the quality of above-mentioned organic phosphorus flame retardant (D) is 100 Quality %, above-mentioned organic phosphorus flame retardant (D) is containing the free triphenyl phosphates of choosing more than 70 mass % and phosphonitrile composition Group in the compound of more than a kind.

[7] a kind of fan products formed, wherein, in above-mentioned [1] in any one of [6], its maximum gauge be 200mm with Under.

Invention effect

Fan products formed according to the present invention, using the teaching of the invention it is possible to provide though a kind of in high temperature environments and rotate at high speed state fortune The fan products formed that rotary impeller deforms less, cooling effectiveness is high.

Accompanying drawing explanation

Fig. 1 is in the embodiment of the present application for evaluating the rearview of the fan products formed of fan deflection.

Fig. 2 is in the embodiment of the present application for evaluating the side view of the fan products formed of fan deflection.

Fig. 3 is in the embodiment of the present application for evaluating the fan products formed of fan deflection, A-A in Fig. 1 Sectional view.

Fig. 4 is in the embodiment of the present application for evaluating the fan products formed of fan deflection, front view in Fig. 1.

Fig. 5 is in the embodiment of the present application for measuring the side view of the device of fan deflection.

Symbol description

1 fan products formed

2DC brushless motor

3 aluminium casings

4 laser sensor light projectors

5 laser sensor light-receiving devices

Detailed description of the invention

Hereinafter, the specific embodiment of the invention (hereinafter referred to as " present embodiment ") is described in detail. The invention is not restricted to following record, various deformation can be carried out in the range of its main points and implement.

The fan products formed of present embodiment contains thermoplastic resin composition, and described thermoplastic resin composition is dynamically The ratio of in determination of viscoelasticity, storage modulus E2 of 110 DEG C ' storage modulus E1 ' relative to 85 DEG C (E2 '/E1 ') be Ratio storage modulus when the storage modulus of more than 0.90,110 DEG C is E2 ', the proportion of 23 DEG C is ρ (E2 '/ρ) be More than 4,000MPa.

It should be noted that in this manual, sometimes by storage modulus E1 of 85 DEG C in Measurement of Dynamic Viscoelasticity ' Referred to as " E1 ' ", by storage modulus E2 of 110 DEG C in Measurement of Dynamic Viscoelasticity ' referred to as " E2 ' ".In this theory In bright book, E1 ', E2 ' refer to the value utilizing the method described in " (1) storage modulus " of aftermentioned [evaluation] to measure.

Additionally, in this manual, sometimes by the storage modulus of 110 DEG C be E2 ', the proportion of 23 DEG C be ρ time ratio Storage modulus (E2 '/ρ) is referred to as " the ratio storage moduluss of 110 DEG C " or " E2 '/ρ ".

[thermoplastic resin composition]

For above-mentioned thermoplastic resin composition, and the E2 ' ratio relative to E1 ' (E2 '/E1 ') it is more than 0.90.Pass through Making E2 '/E1 ' is more than 0.90, it is possible to obtain based on the temperature dependency of the impeller deflection of ambient temperature when using little Fan products formed.Above-mentioned E2 '/E1 ' is preferably more than 0.93, more preferably more than 0.95.

For above-mentioned thermoplastic resin composition, and the ratio storage modulus of 110 DEG C (E2 '/ρ) it is 4, more than 000MPa.Herein, ρ is at 23 DEG C of proportions measured according to ISO1183.It is 4, more than 000MPa by making the ratio storage modulus of 110 DEG C, Even if the fan products formed that in high temperature environments and rotate at high speed state operating impeller deflection is the fewest can be obtained.On State E2 '/ρ and be preferably 4, more than 200MPa, more preferably 4, more than 500MPa.

Even if additionally, from be obtained in that in high temperature environments and rotate at high speed state operating impeller deflection the most less From the viewpoint of fan products formed, the proportion ρ of 23 DEG C of above-mentioned thermoplastic resin composition is preferably less than 1.5, more It is preferably less than 1.4.

As the method controlling E2 '/E1 ' and E2 '/ρ, polyphenylene ether resin composition is preferably used as manufacturing The method of the thermoplastic resin composition of fan products formed.

For above-mentioned thermoplastic resin composition, measure according to UL94, the anti-flammability water of sample thickness 0.75mm Flat preferably V-0.As the method controlling anti-flammability, can enumerate: use polyphenylene ether resin composition as upper The method stating thermoplastic resin composition；Use the method etc. of the thermoplastic resin composition containing fire retardant.

Above-mentioned thermoplastic resin composition is preferably polyphenylene ether resin composition, more specifically, more preferably contains Polyphenylene oxide (A) also contains the free phenylethylene resin series of choosing (B), glass fibre (C), organic phosphorus flame retardant as required (D), the Polyphony Ether resin of at least one in the group that polyamide series resin (E1) and polyphenylene sulfide system resin (E2) form Compositions.

-polyphenylene oxide (A)-

Polyphenylene oxide (A) has following formula (1) and/or the repetitive of (2), preferably Component units by formula (1) or (2) The homopolymer (homopolymer) constituted or the copolymer (copolymer) of the Component units comprising formula (1) and/or (2).

[chemical formula 1]

[chemical formula 2]

(in above-mentioned formula (1), (2), R₁、R₂、R₃、R₄、R₅And R₆Being each independently carbon number is 1～4 Alkyl, carbon number be other monovalencies in the aryl of 6～12, the group of the choosing freely the most such as composition such as halogen atom and hydrogen Group.Wherein, R is not included₅And R₆It is the situation of hydrogen.)

It should be noted that as other univalent perssads above-mentioned, preferably hydrogen.Additionally, abovementioned alkyl and above-mentioned aryl Hydrogen atom also may be used through halogen atom, hydroxyl, alkoxyl replacement.Further, the preferred carbon number of abovementioned alkyl be 1～ 3, the preferred carbon number of above-mentioned aryl is 6～8.

It should be noted that the number of repeat unit in above-mentioned formula (1), (2) can be divided according to the molecular weight of polyphenylene oxide (A) Cloth and different, it is not particularly limited.

As the homopolymer in polyphenylene oxide (A), can enumerate but be not limited to the most poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether, Poly-(2-methyl-6-ethyl-1,4-phenylene) ether, poly-(2,6-diethyl-1,4-phenylene) ether, poly-(2-ethyl-6-n-pro-pyl -1,4-phenylene) ether, poly-(2,6-diη-propyl-1,4-phenylene) ether, poly-(2-methyl-6-normal-butyl-1,4-phenylene) ether, Poly-(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly-(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly-(2-methyl-6- Ethoxy-Isosorbide-5-Nitrae-phenylene) ether and poly-(2-methyl-6-chloroethyl-Isosorbide-5-Nitrae-phenylene) ether etc., the appearance particularly obtained from raw material From the viewpoint of easy property and processability, the most poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether.

As the copolymer in polyphenylene oxide (A), can enumerate but be not limited to such as 2,6-xylenol and 2,3,6-front threes The copolymer of the copolymer of base phenol, 2,6-xylenol and orthoresol and 2,3,6-pseudocuminol and orthoresol Copolymer etc based on the copolymer of polyphenylene oxide structure, the easiness particularly obtained from raw material and processability From the viewpoint of, preferably 2,6-xylenol and the copolymer of 2,3,6-TMP, from the viewpoint of physical property improving Set out, and the copolymer of more preferably 2,6-xylenol and 2,3,6-TMP (especially with 2,6-dimethyl benzene Phenol moieties 90～70 mass % and the copolymer of 2,3,6-trimethylbenzene phenol moieties 10～30 mass %).

Above-mentioned various polyphenylene oxide (A) can be used alone a kind, it is also possible to share two or more.

For polyphenylene oxide (A), as long as the degree the most excessively reduced for the thermostability of thermoplastic resin composition, the most permissible Containing having the polyphenylene oxide as part-structure of other the various phenylene ether units beyond above-mentioned formula (1), (2).Make For this phenylene ether units, can enumerate but be not limited to such as Japanese Unexamined Patent Publication 01-297428 publication and Japanese Unexamined Patent Publication The unit being derived from 2-(dialkylaminomethyl group)-6-methylphenylene ether described in clear 63-301222 publication, it is derived from The unit etc. of 2-(N-alkyl-N-phenvlaminomethvl)-6-methylphenylene ether.

Polyphenylene oxide (A) can be bonded the unit etc. being derived from diphenoquinone in the main chain of polyphenylene oxide.

Further, polyphenylene oxide (A) can have a following composition: part or all making polyphenylene oxide is anti-with functionalized agent Should (modified), be thus replaced into functionalized polyphenylene ether, described functionalized agent include acyl functional group and choosing free carboxylic acid, The functional group of more than a kind in the group of anhydride, amide, acid imide, amine, ortho esters, hydroxyl and ammonium carboxylate salt composition.

From the viewpoint of the molding processibility of thermoplastic resin composition, the weight average molecular weight Mw phase of polyphenylene oxide (A) For the ratio (Mw/Mn value) preferably more than 2.0, more preferably more than 2.5 of number-average molecular weight Mn, further More preferably more than 3.0, additionally, from the viewpoint of the mechanical properties of thermoplastic resin composition, it is preferably 5.5 Hereinafter, more preferably less than 4.5.

It should be noted that weight average molecular weight Mw and number-average molecular weight Mn are by based on GPC (gel permeation chromatography) The polystyrene conversion molecular weight measured obtains.

From the viewpoint of sufficient mechanical properties, the reduced viscosity of polyphenylene oxide (A) is preferably more than 0.25dl/g, more It is preferably more than 0.30dl/g, is even more preferably more than 0.33dl/g, additionally, go out from the viewpoint of molding processibility Sending out, it is preferably below 0.65dl/g, more preferably below 0.55dl/g, is even more preferably below 0.42dl/g.

It should be noted that reduced viscosity can use Ubbelohde viscometer, use chloroform solvent at 30 DEG C, 0.5g/dl Solution is measured.

When being 100 mass % with the gross mass of polyphenylene oxide (A), phenylethylene resin series (B) and glass fibre (C), polyphenylene oxide (A) content is preferably more than 20 mass %, more than more preferably 25 mass %, is even more preferably 45 mass % Above, more than particularly preferably 55 mass %.Furthermore it is preferred that be below 75 mass %, more preferably 70 mass % Hereinafter, it is even more preferably below 65 mass %.By making the content of polyphenylene oxide (A) be more than 45 mass %, by This plays the effect giving thermostability with anti-flammability, and from the viewpoint of molding processibility, the content of polyphenylene oxide (A) is 75 mass % the following is preferred.

From the viewpoint of giving sufficient thermostability, anti-flammability, polyphenylene oxide (A), phenylethylene resin series (B), glass Fiber (C), organic phosphorus flame retardant (D) gross mass 100 mass % in the content of polyphenylene oxide (A) be preferably 25 matter Amount more than %, more than more preferably 35 mass %, is even more preferably more than 40 mass %, additionally, from molding From the viewpoint of processability, it is preferably below 75 mass %, below more preferably 60 mass %, the most excellent Elect below 55 mass % as.

-phenylethylene resin series (B)-

From the viewpoint of improvement molding mobility, above-mentioned thermoplastic resin composition can be contained phenylethylene resin series (B)。

In above-mentioned thermoplastic resin composition, phenylethylene resin series (B) is for gather styrenic in rubber mass In the presence of compound or non-in the presence of be polymerized the polymer obtained or by styrenic with can be with this polystyrene The compound of compound copolymerization in the presence of rubber polymer or non-in the presence of the copolymer that obtains of copolymerization.

Above-mentioned styrenic refers to that cinnamic 1 or plural hydrogen atom are replaced by the base of 1 valency and obtain The compound arrived.

As above-mentioned styrenic, can enumerate but be not limited to such as styrene, α-methyl styrene, 2,4- Dimethyl styrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethyl styrene etc., especially It is from the viewpoint of the raw-material balance obtaining easiness and compositions characteristic of stabilizing quality, optimization styrene.

As can enumerating with the compound of above-mentioned styrenic copolymerization but be not limited to such as metering system The acid methyl acrylic ester such as methyl ester, ethyl methacrylate；The unsaturated nitrile compound such as acrylonitrile, methacrylonitrile Class；The unsaturated acid anhydrides etc. such as maleic anhydride.

It should be noted that in above-mentioned phenylethylene resin series, will be polymerized in the presence of rubber polymer or copolymerization will obtain Polymer or copolymer be referred to as " phenylethylene resin series through rubber-reinforced ", will be in the presence of rubber polymer be non- Polymer or copolymer that polymerization or copolymerization obtain are referred to as " phenylethylene resin series without rubber-reinforced ".

From the viewpoint of the mechanical properties of fan products formed, preferably without rubber-reinforced phenylethylene resin series as benzene Vinylite (B).

When being 100 mass % with the gross mass of polyphenylene oxide (A), phenylethylene resin series (B) and glass fibre (C), styrene It is that the content of resin (B) is preferably below 5 mass %, below more preferably 3 mass %, the most substantially Do not contain.It is below 5 mass % by the content of phenylethylene resin series (B), thus thermostability and excellent in flame retardance, The most preferred.

From the viewpoint of giving sufficient thermostability, anti-flammability, polyphenylene oxide (A), phenylethylene resin series (B), glass The content of the phenylethylene resin series (B) in gross mass 100 mass % of fiber (C) and organic phosphorus flame retardant (D) is preferred It is below 5 mass %, below more preferably 3 mass %.

-glass fibre (C)-

Above-mentioned thermoplastic resin composition preferably comprises glass fibre (C).In above-mentioned thermoplastic resin composition, go out It is compounded glass fibre (C) in the purpose improving mechanical strength.

Kind as the glass of glass fibre (C), it is possible to use known material, can enumerate such as E glass, C Glass, S glass, A glass etc..Glass fibre (C) refers to the glass of fiber shape, with block sheet glass or glass Powder distinguishes.

From the rigidity of molded body caused due to fibre beakage when extrusion, molding, thermostability, resistance to impact, resistance to From the viewpoint of for a long time decline of property etc. and production stability, the average fiber footpath of glass fibre (C) be preferably 5 μm with On, more than more preferably 7 μm, additionally, from giving sufficient mechanical properties, the sight of holding molding surface outward appearance Point sets out, and it is preferably below 15 μm, below more preferably 13 μm.

From the viewpoint of operability, the average length of glass fibre (C) is preferably more than 0.5mm, more preferably 1mm Above, furthermore it is preferred that be below 10mm, more preferably below 6mm.

Additionally, from rigidity, durability and molding processibility, molded appearance balance from the viewpoint of, glass fibre (C) The average L/D ratio ratio of fiber footpath (length with) be preferably more than 70, more preferably more than 100, most preferably 200 Above, furthermore it is preferred that be less than 1200, more preferably less than 1000, most preferably less than 800.

Above-mentioned glass fibre (C) can carry out surface process with surface treated agent, such as silane compound.For surface The silane compound processed is generally used for carrying out glass filler, mineral filler etc. the situation of surface process.As silane The concrete example of compound, can enumerate vinyl trichlorosilane, VTES, γ-methacryloxypropyl The epoxy silicon such as the vinyl silane compounds such as base propyl trimethoxy silicane, γ-glycidoxypropyltrime,hoxysilane The sulfur system silane compounds such as hydride compounds, double-(3-triethoxysilylpropyltetrasulfide) tetrasulfide；γ-mercaptopropyi three The mercaptosilane compound such as methoxy silane；γ aminopropyltriethoxy silane, γ-urea propyl-triethoxysilicane etc. Amino silane compounds etc., from the viewpoint of realizing the purpose of the present invention, particularly preferred amino silane compounds.This A little silane compounds can be used alone a kind, it is also possible to share two or more.Additionally, these silane compounds are permissible It is pre-mixed with the astringent such as epoxy or polyurethane series, carries out surface process with this mixture.

When being 100 mass % with the gross mass of polyphenylene oxide (A), phenylethylene resin series (B) and glass fibre (C), glass fibers The content of dimension (C) is preferably more than 20 mass %, more than more preferably 25 mass %, is even more preferably 30 matter Amount more than %, furthermore it is preferred that be below 80 mass %, below more preferably 50 mass %, be even more preferably Below 45 mass %, below particularly preferably 40 mass %.It is more than 20 mass % by the content of glass fibre (C), Thus playing the mechanical strength improving thermoplastic resin composition, the effect of suppression impeller deformation, is 50 matter by it Amount below %, it is possible to increase the anti-flammability of thermoplastic resin composition, the most preferably.

From improvement thermoplastic resin composition mechanical properties from the viewpoint of, polyphenylene oxide (A), phenylethylene resin series (B), Glass fibre (C), organic phosphorus flame retardant (D) gross mass 100 mass % in glass fibre (C) content be preferably More than 20 mass %, more than more preferably 30 mass %, additionally, from giving thermoplastic resin composition's anti-flammability Viewpoint is set out, and it is preferably below 80 mass %, below more preferably 50 mass %, is even more preferably 45 Below quality %.

-organic phosphorus flame retardant (D)-

Above-mentioned thermoplastic resin composition preferably further contains organic phosphorus flame retardant (D).Herein, organophosphor system resistance Combustion agent refers to the fire retardant that is made up of phosphorous organic compound, is different from be made up of phosphorous inorganic compound fire-retardant The fire retardant that agent and the salt by organic phosphoric acid Yu metal are constituted.

As organic phosphorus flame retardant (D), specifically, it is preferably selected from the group being made up of triphenyl phosphate and phosphonitrile The compound of more than a kind.If the quality of organic phosphorus flame retardant (D) is 100 mass %, more preferably contain 70 The compound of more than quality % more than a kind in the group selecting free triphenyl phosphate and phosphonitrile composition.Thus, play Give anti-flammability and the effect keeping thermostability.Wherein, from the viewpoint of the effect being readily obtained the present invention, preferably Phosphonitrile.

Be used alone triphenyl phosphate as organic phosphorus flame retardant (D) in the case of, from the effect fully obtaining the present invention From the viewpoint of Guo, polyphenylene oxide (A), phenylethylene resin series (B), glass fibre (C), organic phosphorus flame retardant (D) The content of the triphenyl phosphate in gross mass 100 mass % is preferably more than 5 mass %.Furthermore it is preferred that be 13 matter Amount below %, from the viewpoint of improving thermostability, it is more preferably below 10 mass %.

As phosphonitrile, the material containing the Component units shown in following formula (3) can be enumerated.

[changing 3]

(in above-mentioned formula (3), X represents Ph (phenyl) or OPh (phenoxy group).)

As phosphonitrile, as long as the material containing the Component units shown in above-mentioned formula (3), the most do not limit, permissible Enumerate such as cyclic phosphazene compound, chain phosphazene compound, the crosslinking phosphazene compound etc. of crosslinked base crosslinking.

In above-mentioned thermoplastic resin composition, from the viewpoint of giving better anti-flammability, as phosphonitrile, excellent Select cyclic phosphazene compound, the most ring-type phenoxy phosphazene compound.Additionally, from molding processibility, anti-flammability Viewpoint is set out, as phosphonitrile, it is desirable to for containing the trimer more than 70 mass %, more than suitably 85 mass % Ring-type phenoxy phosphazene compound.

Be used alone phosphonitrile as organic phosphorus flame retardant (D) in the case of, polyphenylene oxide (A), phenylethylene resin series (B), Glass fibre (C), organic phosphorus flame retardant (D) as long as gross mass 100 mass % in the content of phosphonitrile be 5～20 Quality %, is not particularly limited.

It should be noted that in organic phosphorus flame retardant (D) less than the part of 30 mass % can be triphenyl phosphate and Compound beyond phosphonitrile, can be the aromatic phosphoric ester beyond such as triphenyl phosphate.

As aromatic phosphoric ester, it is preferably but not limited to such as triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (two Tolyl) ester, phosphoric acid cresyl diphenyl ester, di(2-ethylhexyl)phosphate tolyl diphenyl ester, di(2-ethylhexyl)phosphate (xylyl) phenyl ester, hydroxyl The triphenyls such as nonenoic acid bis-phenol phosphate ester, resorcinol biphosphonate, bisphenol-A biphosphonate replace the fragrance of type Race's phosphoric acid ester, wherein, more preferably triphenyl phosphate.

In the case of using the aromatic phosphoric ester mixture with phosphonitrile as organic phosphorus flame retardant (D), from giving more From the viewpoint of good molding mobility and mechanical properties, in above-mentioned thermoplastic resin composition, preferably by fragrance Race's phosphate ester uses with the ratio of share of 5:95～30:70 with the mass ratio (aromatic phosphoric ester: phosphonitrile) of phosphonitrile, More preferably use with the ratio of share of 10:90～25:75, even more preferably share with 20:80～25:75 Ratio uses.

From the viewpoint of anti-flammability, with polyphenylene oxide (A), phenylethylene resin series (B), glass fibre (C) and organophosphor system When the gross mass of fire retardant (D) is 100 mass %, the content of organic phosphorus flame retardant (D) is preferably more than 5 mass %. Additionally, from the viewpoint of thermostability, it is preferably below 20 mass %, below more preferably 13 mass %, enters One step is more preferably below 10 mass %.

-polyamide series resin (E1)-

As polyamide series resin (E1), if having in the repeat units of the polymer backbone amido link-NH-C (= O)-, its kind is not particularly limited.Polyamide series resin generally can utilize diamidogen and dicarboxylic acids polycondensation, The ring-opening polymerisation of lactams, the polycondensation etc. of amino carboxylic acid obtain, but the manufacture method of polyamide series resin is not limited to this, Can also be for the polyamide series resin utilizing additive method to obtain.

As diamidogen, aliphatic diamine, ester ring type diamidogen, aromatic diamine etc. can be enumerated.Concrete as diamidogen Example, can enumerate such as tetra-methylenedimine, hexamethylene diamine, 11 methylene diamine, ten dimethylene diamidogen, Ten trimethylene diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methyl nine Methylene diamine, 1,9-nonamethylene diamine, 2-methyl isophthalic acid, 8-octamethylenediamine, ethylenediamine, propane diamine, 1,4-butanediamine, 1,6-are own Diamidogen, 1,8-octamethylenediamine, 1,10-decamethylene diamine, 1,12-dodecamethylene diamine, 3-methyl isophthalic acid, 5-pentanediamine, 2,2,4-trimethyl -1,6-hexamethylene diamine, 2,4,4-trimethyl-1,6-hexamethylene diamine, 5-methyl isophthalic acid, the aliphatic diamine such as 9-nonamethylene diamine；The double amino of 1,3- The ester ring type diamidogen such as the double aminomethyl cyclohexane of hexahydrotoluene, 1,4-；M-diaminobenzene., p-phenylenediamine, isophthalic diformazan The aromatic diamine such as amine, p dimethylamine etc..

As dicarboxylic acids, aliphatic dicarboxylic acid, ester ring type dicarboxylic acids, aromatic dicarboxylic acid etc. can be enumerated.As two The concrete example of carboxylic acid, can enumerate such as malonic acid, dimethyl malonic acid, succinic acid, 3,3-diethyl succinic acid, 1,3-propanedicarboxylic acid, 2,2-dimethylated pentanedioic acid, adipic acid, 2-methyl adipic acid, trimethyladipic acid, suberic acid, heptan two The aliphatic dicarboxylic acids such as acid, Azelaic Acid, decanedioic acid, dodecanedioic acid；1,1,3-tridecandioic acid, 1,3-Pentamethylene. two The ester ring type dicarboxylic acids such as carboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid；P-phthalic acid, isophthalic two Naphthalene dicarboxylic acids, dimeric dibasic acid, the 1,4-phenylenes such as formic acid, 2,6 naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids Two epoxide oxalic acid, 1,3-phenylenedioxydiacetic acid, biphenyl dicarboxylic acid, diphenyl methane-4,4 '-dicarboxylic acids, two Phenylsulfone-4,4 '-the aromatic dicarboxylic acid such as dicarboxylic acids, 4,4 '-diphenyldicarboxylic acid etc..These dicarboxylic acids can individually make With a kind, it is also possible to share two or more.

As lactams, such as epsilon-caprolactams, ω-oenantholcatam, omega-lauric lactam etc. can be enumerated.

As amino carboxylic acid, such as episilon amino caproic acid, 7-aminoheptylic acid, 8-aminocaprylic acid, 9-amino nonyl can be enumerated Acid, 11-amino undecanoic acid, 12 amino dodecanoic acid, 13-amino tridecanoic acid etc..

Diamidogen, dicarboxylic acids, lactams, amino carboxylic acid can individually use a kind, it is also possible to share 2 kinds with On.Further, it is also possible to use, diamidogen, dicarboxylic acids, lactams, amino carboxylic acid etc. are polymerized in polymer reactor The polyamide series resin carrying out macromolecule quantization in extruder etc. to the stage of the oligomer of low-molecular-weight and obtain.

As polyamide series resin (E1), such as polyamide 6, polyamide 6 can be enumerated, 6, polyamide 4,6, polyamides Amine 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6/6,6, polyamide 6/6,12, polyamide MXD (m-xylene diamine), 6, polyamide 6, T, polyamide 9, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I, Polyamide 6,6/6, T, polyamide 6,6/6, I, polyamide 6/6, T/6, I, polyamide 6,6/6, T/6, I, polyamide 6/12/6, T, Polyamide 6,6/12/6, T, polyamide 6/12/6, I, polyamide 6,6/12/6, I, polyamide 9, T etc..These polyamide can To be used alone a kind, it is also possible to share two or more.

From the viewpoint of thermostability with the dimensional stability during water suction of products formed, preferred polyamide system resin (E1) contains There is semiaromatic polyamide composition.Semiaromatic polyamide composition is containing (a) dicarboxylic acid units, the polymer of (b) diamine unit, Refer at least some of material for aromatic compound of either one of (a) dicarboxylic acid units and (b) diamine unit.Make For semiaromatic polyamide composition, described further below semiaromatic polyamide composition is preferably used.

From the viewpoint of anti-flammability with thermostability, preferably semiaromatic polyamide composition contains terephthalic acid units as (a) Dicarboxylic acid units.A the content of the terephthalic acid units in () dicarboxylic acid units is preferably 60～100 moles of %, more excellent Elect 75～100 moles of %, more preferably 90～100 moles of %, the most all dicarboxyls as Acid unit (a) is terephthalic acid units.

Other dicarboxylic acid units beyond terephthalic acid units in (a) dicarboxylic acid units of semiaromatic polyamide composition Content is preferably smaller than 40 moles of %, more preferably less than 25 moles %, is further preferably no larger than 10 moles of %, further More preferably contain substantially no.

As other dicarboxylic acid units beyond terephthalic acid units, can enumerate beyond such as by p-phthalic acid The unit that above-mentioned dicarboxylic acids is derivative.These dicarboxylic acid units can be used alone a kind, it is also possible to share two or more. Particularly preferably by the unit that the aromatic dicarboxylic acid beyond p-phthalic acid is derivative.Can be further in melting molding In the range of comprise the unit derivative by the polybasic carboxylic acid of trimellitic acid, trimesic acid, PMA etc. more than 3 yuan.

From the viewpoint of dimensional stability when the fan products formed of present embodiment absorbs water, preferably semi-aromatic polyamides Amine contains (b-1) 1,9-nonamethylene diamine unit and/or (b-2) 2-methyl isophthalic acid, and 8-octamethylenediamine unit is as (b) diamine unit.

B (b-1) the 1,9-nonamethylene diamine unit in () diamine unit and (b-2) 2-methyl isophthalic acid, the total content of 8-octamethylenediamine unit is preferred Being 60～100 moles of %, more preferably 75～100 moles %, more preferably 90～100 moles of %, enter one Walk the most essentially all of diamine unit by (b-1) 1,9-nonamethylene diamine unit and/or (b-2) 2-methyl isophthalic acid, 8-octamethylenediamine Unit is constituted.

In (b) diamine unit in semiaromatic polyamide composition, 1,9-nonamethylene diamine unit and 2-methyl isophthalic acid, 8-octamethylenediamine unit The content of other diamine unit in addition is preferably smaller than 40 moles of %, more preferably less than 25 moles %, further preferably Less than 10 moles of %, even more preferably contain substantially no.

As 1,9-nonamethylene diamine unit and 2-methyl isophthalic acid, other diamine unit beyond 8-octamethylenediamine unit, example can be enumerated Such as ethylenediamine, propane diamine, 1,4-butanediamine, 1,6-hexamethylene diamine, 1,8-octamethylenediamine, 1,10-decamethylene diamine, 1,12-dodecane Diamidogen, 3-methyl isophthalic acid, 5-pentanediamine, 2,2,4-trimethyl-1,6-hexamethylene diamine, 2,4,4-trimethyl-1,6-hexamethylene diamine, 5-methyl The aliphatic diamines such as-1,9-nonamethylene diamine；The ester ring type diamidogen such as cyclohexanediamine, methyl cyclohexane diamidogen, isophorone diamine； P-phenylenediamine, m-diaminobenzene., benzene dimethylamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, 4,4 '- The unit etc. that diamino-diphenyl ether etc. is derived by aromatic diamine.These diamine unit can be used alone a kind, also Can be share two or more.

With (b-1) the 1,9-nonamethylene diamine unit in (b) diamine unit contained in semiaromatic polyamide composition and (b-2) 2-methyl When the total amount of-1,8-octamethylenediamine unit is 100 moles of %, the content of (b-1) 1,9-nonamethylene diamine unit is preferably 60 moles of % Above, more preferably 75 moles more than %, more preferably 80 moles of more than %.By making containing of (b-1) unit Amount is in above-mentioned scope, it is possible to while improving thermostability further, more effectively suppress the water absorption of products formed.With When the total amount of (b-1) unit in () diamine unit and (b-2) unit is 100 moles of % b, the content of (b-1) unit is preferably 95 moles of below %, more preferably 90 moles below %, more preferably 85 moles of below %.By making (b-1) The content of unit is in above-mentioned scope, it is possible to improving the same of the mechanical property such as resistance to impact and tensile elongation amount further Time, the appearance making fan products formed is more excellent.

As polyamide series resin (E1), it is also possible to use and utilize extruder etc. to make two or more polyamide series resin altogether Polymerization and the polyamide series resin that obtains.

The viscosity number (according to ISO307:1994, the viscosity number measured with 96% sulphuric acid) of polyamide series resin (E1) is preferably For more than 50mL/g, more preferably more than 70mL/g, it is even more preferably more than 100mL/g.Additionally, it is excellent Elect below 250mL/g as, more preferably below 200mL/g, be even more preferably below 150mL/g.

It is more than 50mL/g by making the viscosity number of polyamide series resin (E1), improves anti-flammability the most further, squeeze The processability gone out etc., and further suppression molding time the generation of gas.And, by making viscosity number be 50mL/g Above, it is possible to reduce the generation of film dirt, and when can increase considerably injection moulding can the jet number of normal molding, have Help greatly improving of mouldability.Additionally, be below 250mL/g by making viscosity number, thus in the effect above On the basis of, the effect of mouldability improvement obtaining thin molded article etc.

By using the polyamide series resin in the range of above-mentioned viscosity number, obtaining more excellent effect is Worth Expecting , but in the case of expectation obtains further excellent effect, further preferably according to the kind of polyamide series resin Class controls the viscosity number for the following stated.

Such as using polyamide 9, T, polyamide 6, the semiaromatic polyamide composition such as 6/6, I is as polyamide series resin (E1) In the case of, from the viewpoint of the balance of toughness and molding mobility, and do not use semiaromatic polyamide composition as polyamides The situation of amine system resin is compared, and suitable range of viscosities is slightly different.Use polyamide 9, in the case of T, suitable Viscosity number range preferably from more than 70mL/g, more preferably more than 100mL/g.Additionally, viscosity number is preferably Below 150mL/g, more preferably below 120mL/g.

Use polyamide 6, in the case of 6/6, I, viscosity number is preferably more than 50mL/g, more preferably 70mL/g with On.Additionally, viscosity number is preferably below 150mL/g, more preferably below 130mL/g, be even more preferably Below 120mL/g.

The inventors discovered that, in the case of using polyamide series resin (E1) in above-mentioned thermoplastic resin composition, heat The mouldability of thermoplastic resin composition and the balance of resistance to impact are affected by the viscosity number of polyamide series resin (E1) Bigger.From this viewpoint, be there is by use the polyamide series resin of above-mentioned viscosity number, can be appreciated that the special of characteristic Property improve.

Polyamide series resin (E1) can be the mixture of the different two or more polyamide series resin of viscosity number.Above-mentioned The viscosity number of the polyamide series resin (E1) in thermoplastic resin composition can utilize following method to confirm.

First, after using HFIP to be dissolved by the resinous principle of thermoplastic resin composition, utilize Methanol makes resinous principle contained in soluble ingredient precipitate and separate and recover.Further with formic acid or sulfuric acid dissolution After this separation and recovery thing, use the separation and recovery soluble ingredient such as centrifuge.Methanol is utilized to make this soluble ingredient reprecipitation, And separate and recover polyamide series resin composition, afterwards, confirm viscosity number by measuring.

From the viewpoint of dimensional stability when products formed absorbs water, the appearance of products formed, as polyamide-based tree Fat (E1), particularly preferably by hexamethyleneadipamide unit 70～95 mass %, hexa-methylene-isophthalamide unit 5～ The semiaromatic polyamide composition that 30 mass % are constituted.It should be noted that hexamethylene adipamide can by such as adipic acid with Hexamethylene diamine obtains.Hexa-methylene-isophthalamide can be obtained with hexamethylene diamine by such as M-phthalic acid Arrive.

The terminal groups of polyamide series resin (E1) is related to the reaction with polyphenylene oxide (A).Generally polyamide series resin has Amino, carboxyl are as terminal groups.When general end carboxy concentration increases, there is resistance to impact reduction, mobility improves Trend.

From the viewpoint of the balance of properties making above-mentioned thermoplastic resin composition is better, polyamide series resin (E1) Terminal amino group concentration is preferably less than 1.0 relative to the ratio (mole) of end carboxy concentration, more preferably 0.05～0.8. By making the terminal amino group concentration of polyamide series resin (E1) relative to the ratio of end carboxy concentration at above-mentioned scope, energy Enough mobility maintaining thermoplastic resin composition with higher level and the balance of resistance to impact.

The terminal amino group concentration of polyamide series resin (E1) is preferably more than 1 μm ol/g, and more than more preferably 5 μm ol/g, It is even more preferably more than 10 μm ol/g, more than particularly preferably 20 μm ol/g.Furthermore it is preferred that be 80 μm ol/g Hereinafter, below more preferably 60 μm ol/g, it is even more preferably below 45 μm ol/g, particularly preferably 40 μm ol/g Below.By making terminal amino group concentration in above-mentioned scope, it is possible to maintain the stream of thermoplastic resin composition with higher level Dynamic property and the balance of resistance to impact.

The end carboxy concentration of polyamide series resin (E1) is preferably more than 20 μm ol/g, more preferably 30 μm ol/g with On.Furthermore it is preferred that be below 150 μm ol/g, below more preferably 130 μm ol/g.By making end carboxy concentration In above-mentioned scope, it is possible to maintain the mobility of thermoplastic resin composition and the balance of resistance to impact with higher level.

The concentration of each terminal groups of these polyamide series resin can use known method to be adjusted.Example can be enumerated Add selected from diamine compound, list in the way of reaching the terminal groups concentration of regulation when the polymerization at polyamide series resin The method etc. of more than a kind in amines, dicarboxylic acid compound and monocarboxylic acid compound etc..

Terminal amino group concentration and end carboxy concentration can utilize various method to be measured.From precision, the sight of simplicity Point sets out, the most such as, utilize¹The side that H-NMR obtains according to the integrated value of the characteristic signals corresponding with each terminal groups Method.Such as the concrete example of quantitative approach of terminal groups concentration of polyamide series resin, Japanese Unexamined Patent Publication can be enumerated Method described in the embodiment of 07-228689 publication.Specifically, from the standpoint of precision, simplicity, For the quantity of each terminal groups, preferably by¹H-NMR (surveys in 50 DEG C in 500MHz, heavy-hydrogenated trifluoroacetic acid Fixed), obtain according to the integrated value of the characteristic signals corresponding with each terminal groups.Cannot be blocked utilizing end-capping reagent The characteristic signals of end identify in the case of, the intrinsic viscosity [η] of polyamide series resin can be measured, Use the relation of following formula, calculate molecule chain end base sum.

Mn=21900 [η]-7900 (Mn represents number-average molecular weight)

Molecule chain end base sum (eq/g)=2/Mn

The 10 of the terminal groups of the strand of preferred polyamide system resin～95% utilize end-capping reagent to be blocked.Polyamide It is the ratio (ending ratio) that is blocked of the terminal groups of the strand of resin more preferably more than 40%, more preferably More than 60%.By making ending ratio in above-mentioned scope, it is possible to more effectively suppression thermoplastic resin composition's melt molding Time viscosity, and the appearance of the products formed obtained by improving further, add the heat-resistant stability etc. in man-hour. Additionally, ending ratio is preferably less than 95%, more preferably less than 90%.By make ending ratio in above-mentioned scope, by This improves the appearance of resistance to impact, products formed further.

Can be to terminal carboxyl group, terminal amino group present in this polyamide series resin with utilize end-capping reagent to carry out end-blocking The quantity of terminal groups is measured respectively, obtains the ending ratio of polyamide series resin (E1) according to following formula (I).

Ending ratio (%)=[(alpha-beta)/α] × 100 (I)

(in formula, α represent the terminal groups of strand sum (unit=mole；It is generally equal to polyamide molecule quantity 2 times.), β represents the sum (unit=mole) of the carboxyl terminal remained without end-blocking and amino base end.)

As end-capping reagent, as long as having and the amino of polyamide series resin end and/or single official of the reactivity of carboxyl The compound of energy property, is not particularly limited, from viewpoints such as the reactive stability with end-blocking end, the most singly Carboxylic acid, monoamine, from viewpoints, more preferably monocarboxylic acid such as the easiness of operation.In addition to this it is possible to use acid Acid anhydride, monoisocyanates, single etheride, monoesters class, single methanol class etc. are as end-capping reagent.

As the monocarboxylic acid as end-capping reagent, as long as having the reactivity with amino, it is not particularly limited, Ke Yiju Go out such as acetic acid, propanoic acid, butanoic acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, myristic acid, Petiolus Trachycarpi The aliphatic monocarboxylic acids such as acid, stearic acid, neopentanoic acid, isopropylformic acid.；The ester ring type monocarboxylic acids such as cyclohexane-carboxylic acid；Benzoic acid, The aromatic monocarboxylates such as toluic acid, α-naphthalene-carboxylic acid, β-naphthalene-carboxylic acid, methyl naphthalene carboxylic acid, phenylacetic acid；They Arbitrary mixture etc..Among these, from viewpoints such as reactive, the stability of end-blocking end and economy, excellent Select acetic acid, propanoic acid, butanoic acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, myristic acid, Palmic acid, Stearic acid, benzoic acid, more preferably acetic acid, benzoic acid.

As the monoamine as end-capping reagent, as long as there is reactivity with carboxyl, being not particularly limited, example can be enumerated As methylamine, ethamine, propylamine, butylamine, hexylamine, octylame, decyl amine, stearylamine, dimethylamine, diethylamine, di-n-propylamine, The aliphatic monoamines such as dibutyl amine；The ester ring type monoamine such as cyclohexylamine, hexanamine；Aniline, toluidines, diphenylamines, naphthalene The aromatic series monoamines such as amine；Their arbitrary mixture etc..Among these, from reactivity, boiling point, end-blocking end The viewpoint such as stability and economy is set out, preferably butylamine, hexylamine, octylame, decyl amine, stearylamine, cyclohexylamine, aniline, More preferably butylamine, hexylamine, octylame.

For the purpose of the heat-resistant stability improving above-mentioned thermoplastic resin composition further, except polyamide series resin (E1), outside, thermoplastic resin composition can also exist transition metal (not including ferrum), halogen atom.

For the kind of transition metal (not including ferrum), as long as being not ferrum, being not particularly limited, can enumerate such as Copper, cerium, nickel, cobalt etc., among these, from the viewpoint of long-term thermal stability, preferably copper.Additionally, for halogen The kind of atom, is not particularly limited, from the viewpoint of preventing the corrosion such as production equipment, and preferably bromine, iodine.

When being 100 mass % with the total amount of above-mentioned thermoplastic resin composition, the content of transition metal (not including ferrum) with Quality criteria meter, preferably more than 1ppm, more preferably more than 5ppm.Furthermore it is preferred that less than 200ppm, more Preferably smaller than 100ppm.

When being 100 mass % with the total amount of above-mentioned thermoplastic resin composition, the content of halogen atom in terms of quality criteria, It is preferably more than 500ppm, more preferably more than 700ppm.Preferably smaller than 1500ppm, more preferably less than 1200ppm。

The method to above-mentioned thermoplastic resin composition is added as by these transition metal (not including ferrum), halogen atom, It is not particularly limited, can enumerate such as in the operation of melting mixing polyamide series resin (E1) and polyphenylene oxide (A), The method that they are added with the form of powder body；The side being added when the polymerization of polyamide series resin (E1) Method；After manufacturing the master batch material of the polyamide series resin (E1) being added with transition metal, halogen atom with high concentration, this is gathered The master batch material of amide system resin (E1) adds the method etc. to thermoplastic resin composition.Preferred side in these methods Method be added during the polymerization of polyamide series resin (E1) method, add with high concentration in polyamide series resin (E1) Add transition metal and/or halogen atom make master batch material after the method that is added.

From the viewpoint of reducing the deflection hot environment further, the polyamides in above-mentioned thermoplastic resin composition The content of amine system resin (E1) is preferably below 50 mass %, below more preferably 40 mass %.Additionally, from entering one From the viewpoint of step reduces the deflection under hot environment, with polyphenylene oxide (A), phenylethylene resin series (B) and glass fibre (C), when gross mass is 100 mass %, the content of polyamide series resin (E1) is preferably below 80 mass %.

-polyphenylene sulfide system resin (E2)-

Polyphenylene sulfide (is abbreviated as " PPS " the most sometimes.) for containing the weight of the phenylene sulfide represented with following formula (4) The polymer of multiple unit.In polyphenylene sulfide, the content of this repetitive is preferably 50 moles of more than %, and more preferably 70 Mole more than %, is even more preferably 90 moles of more than %.

[-Ar-S-]···(4)

(in above-mentioned formula (4), S represents that sulphur atom, Ar represent arlydene.)

As above-mentioned arlydene, can enumerate such as to phenylene, metaphenylene, substituted phenylene (alternatively base, Preferably carbon number is alkyl, the phenyl of 1～10), p, p ' diphenylene sulfuryl, p, p '-biphenylene, p, p '-two sub- Phenylcarbonyl group, naphthyl etc..

PPS can be only to be made up of the repetitive represented with formula (4) and Ar in formula (4) is only by a kind of sub-virtue The homopolymer (homopolymer) that base is constituted.Additionally, from the viewpoint of processability, thermostability, it can also be Only it is made up of the repetitive represented with formula (4) but Ar in formula (4) is different arlydene of more than two kinds Copolymer.Among these, from processability and excellent heat resistance and from the viewpoint of obtaining easily, the most following PPS, Described PPS have preferably 50 moles more than %, more preferably 70 moles more than %, further preferred 90 moles of % with On the repetitive to phenylene sulfide.

From the viewpoint of suppression corrosivity, PPS is preferably below 1500ppm containing cl concn, more preferably Below 900ppm.The mensuration of cl concn can specify according to Japan of civic organization printed circuit industry meeting (JPCA) JPCA-ES01 (halogen-free copper clad layers amasss plate test method) is measured.This analysis method can utilize at flask burning The reason chromatography of ions is carried out.

For the manufacture method of PPS, it is not particularly limited, it is possible to use known method.Can enumerate such as Make halogen atom substituted aromatic compound (such as paracide etc.) in sulfur and the method being polymerized under sodium carbonates' presence；? At sodium sulfide or NaHS and sodium hydroxide or hydrogen sulfide and sodium hydroxide or amino-alkane acid sodium in polar solvent In the presence of carry out the method be polymerized；Chlorothio phenol is self condensed.Among these, more specifically, preferably exist The sulfone series solvents such as the amide series solvent such as N-Methyl pyrrolidone, dimethyl acetylamide or sulfolane make sodium sulfide and to two The method etc. of chlorobenzene reaction.In order to have branched structure on strand, trichloro-benzenes can be used as required as propping up Chain agent.

PPS can also utilize such as No. 2513188 description of U.S. Patent No., Japanese Patent Publication 44-27671 public affairs Report, Japanese Patent Publication 45-003368 publication, Japanese Patent Publication 52-012240 publication, Japanese Laid-Open Patent Publication No. 61-225217, No. 3274165 description of U.S. Patent No., Japanese Patent Publication 46-027255 publication, Billy Time No. 29437 method described in description, Japanese Unexamined Patent Publication 05-222196 publication etc. of patent obtain.Profit The PPS obtained by such polyreaction is usually linear PPS.

In the present embodiment, it is possible to use the following material (cross-linking type PPS) obtained: after carrying out polyreaction, exist In the presence of oxygen, carry out heat treated with the temperature (such as 200～250 DEG C) below the fusing point of PPS, thus promote oxygen Changing crosslinking, appropriateness improves polymer molecular weight, viscosity.This cross-linking type PPS also comprises the degree of cross linking and controls relatively Low partly cross-links PPS.

The shear rate of PPS is 100 seconds^-1Time the melt viscosity of 300 DEG C be preferably more than 10Pa s.Additionally, It is preferably below 150Pa s, more preferably below 100Pa s, is even more preferably below 80Pa s.Logical Crossing and making melt viscosity is above-mentioned scope, it is possible to maintain the balance of toughness and rigidity with higher level, and can be more effective Overlap is produced during ground suppression molding.

It should be noted that melt viscosity can utilize capillary rheometer to be measured.Such as can use Capilograph (Toyo Seiki makes society of institute system), employing capillary tube (long capillary tube=10mm, capillary diameter= 1mm), in temperature 300 DEG C, shear rate 100 seconds^-1Under conditions of be measured.

For above-mentioned linear PPS, the cross-linking type PPS etc. of the concrete example as PPS, can be used alone a kind, Can also be share two or more., when carrying out the alloying of PPS and polyphenylene oxide, owing to polyphenylene oxide dispersion phase can be made Particle diameter diminish, therefore as the preferably suitable linear PPS of PPS and cross-linking type PPS.

Albefaction in time reducing molding, from the viewpoint of film dirt, the content of oligomer contained in PPS is preferably 0.7 Below quality %.Herein, oligomer contained in PPS refers to the material utilizing dichloromethane to extract from PPS, generally It it is the material of the impurity being considered as PPS.

The content of oligomer can utilize following method to be measured.The powder 5g of PPS is added to dichloromethane In 80mL, after implementing 6 hours surname extraction, it is cooled to room temperature, the dichloromethane solution as extracting solution is shifted To weighing botle.Then, use the dichloromethane amounting to 60mL, in three times the container extracted is carried out clearly Wash, this cleanout fluid is added in the extracting solution to above-mentioned weighing botle and reclaims.Then, will add with about 80 DEG C Hot extracting solution, makes dichloromethane evaporation remove, reclaims residue.Residue is weighed, by measuring this level of residue, Obtain the ratio of extracted amount based on dichloromethane (that is, oligomer amount present in PPS).

From the viewpoint of reducing the deflection hot environment further, in above-mentioned thermoplastic resin composition The content of PPS (E2) is preferably below 50 mass %, below more preferably 40 mass %.Additionally, from reducing further From the viewpoint of deflection under hot environment, total with polyphenylene oxide (A), phenylethylene resin series (B) and glass fibre (C) When quality is 100 mass %, the content of PPS (E2) is preferably below 60 mass %.

-other materials-

In the range of appearance not significantly reducing mechanical properties, anti-flammability, molded body etc., above-mentioned thermoplastic resin Oil/fat composition can contain stabilizer class, coloring agent, the releasing agents such as antioxidant, UV absorbent, heat stabilizer Deng.

From the viewpoint of each showing sufficient additive effect, with polyphenylene oxide (A), phenylethylene resin series (B), glass When glass fiber (C), the gross mass of organic phosphorus flame retardant (D) are 100 mass %, the content of above-mentioned antioxidant etc. is excellent Elect more than 0.001 mass % as, more than more preferably 0.01 mass %, be even more preferably more than 0.2 mass %, Additionally, from the viewpoint of the physical property keeping above-mentioned thermoplastic resin composition, it is preferably below 3 mass %, more It is preferably below 2 mass %, is even more preferably below 1 mass %.

Not significantly reducing in the range of mechanical properties, resistance to impact, anti-flammability, above-mentioned thermoplastic resin composition can With containing the inanimate matter filler beyond glass fibre (C).

As the inanimate matter filler beyond above-mentioned glass fibre (C), can enumerate but be not limited to such as carbon fiber, cloud Mother, Talcum, sheet glass, glass milled fiber (glass fibre is pulverized the material for powder), chlorite etc..

From rigidity, durability give from the viewpoint of, with polyphenylene oxide (A), phenylethylene resin series (B), glass fibre (C), Inanimate matter filler when the gross mass of organic phosphorus flame retardant (D) is 100 mass %, beyond above-mentioned glass fibre (C) Content be preferably more than 0.5 mass %, more than more preferably 1 mass %, furthermore it is preferred that be below 10 mass %, Below more preferably 8 mass %.

From the viewpoint of metal protection, the polyphenylene oxide (A) in the most above-mentioned thermoplastic resin composition, styrene Be the gross mass of resin (B) and glass fibre (C) be more than 90 mass %, and when being 100 mass % with above-mentioned gross mass Containing polyphenylene oxide (A) 25～75 mass %, phenylethylene resin series (B) 0～5 mass %, glass fibre (C) 20～50 matter Amount %, most preferably polyphenylene oxide (A) 45～75 mass %, phenylethylene resin series (B) 0～5 mass %, glass fibre (C) 25～50 mass %.

From the viewpoint of the fan products formed that the deflection obtained in high temperature environments is less, above-mentioned thermoplastic resin group The gross mass of polyphenylene oxide (A), phenylethylene resin series (B) and glass fibre (C) in compound is preferably more than 85 mass %, More than more preferably 90 mass %.

[manufacture method of thermoplastic resin composition]

Above-mentioned thermoplastic resin composition can by such as by polyphenylene oxide (A), polyphenylene oxide (B), glass fibre (C), have Machine phosphorus flame retardant (D), polyamide series resin (E1), polyphenylene sulfide system resin (E2), other materials melting mixing enter Row manufactures.

In above-mentioned thermoplastic resin composition, organic phosphorus flame retardant (D) has the fusing point of 35～60 DEG C, at room temperature In the case of compound for solid or powder body, manufacture thermoplastic resin composition time, extruder material pouring inlet, Feedstock pipeline near machine barrel etc., (D) composition occurs melted, produces set thing, thus produces pipeline blocking, Manufacture may be interrupted.In the manufacture of above-mentioned thermoplastic resin composition, the manufacture that can overcome this problem is preferably used Method.

The manufacture method of above-mentioned thermoplastic resin composition is not limited to following methods, the most such as by organic phosphorus flame retardant (D) mix in advance with part or all of polyphenylene oxide (A), prepare mixture, this mixture is used as thermoplasticity The raw material of resin combination.Herein, for the mixing of the organic phosphorus flame retardant (D) in this mixture Yu polyphenylene oxide (A) Ratio, from the viewpoint of the operability in time producing thermoplastic resin composition, with the matter of organic phosphorus flame retardant (D) Amount is that the Functionality, quality and appealing design of the polyphenylene oxide (A) when 1 elects more than 1 as, more preferably more than 1.5, particularly preferably more than 2, Additionally, from the viewpoint of the complex that reduction produces along with the increase of the manufacture of mixture, it is preferably 7 Hereinafter, more preferably less than 6, particularly preferably less than 5.

Containing in the organic phosphorus flame retardant (D) preparation with the mixture of polyphenylene oxide (A), it is possible to use such as adjustable is stirred Mix the mixer of speed, the Henschel mixer of adjustable rotating blade velocity, can be according to organic phosphorus flame retardant (D) Character (solid, powder body etc.), the suitably condition such as governing speed, temperature, time while preparing mixture, but It is not limited to this.

In the manufacture method of above-mentioned thermoplastic resin composition, from manufacturing thermoplastic resin composition in a large number and stably From the viewpoint of, i.e. from the viewpoint of manufacturing efficiency, suitably use double screw extruder, but be not limited to this.

As double screw extruder, such as ZSK40MC double screw extruder (Germany Werner& can be enumerated Pfleiderer society system, machine barrel number 13, screw diameter 40mm, L/D=50；Have 2 kneading disk L (Left-handed), 6 kneading disk R (Right-handed) and the screw pattern of 4 kneading disk N (Neutral)), it is possible to use it is at cylinder Melt under conditions of temperature 270～330 DEG C, screw rod revolution 150～450rpm, rate of extrusion 40～220kg/h Mixing.Additionally, as double screw extruder, such as TEM58SS double screw extruder (toshiba machine society can be enumerated System, machine barrel number 13, screw diameter 58mm, L/D=53；There are 2 kneading disk L, 14 kneading disk R and 2 The screw pattern of individual kneading disk N), it is possible to use its temperature cylinder 270～330 DEG C, screw rod revolution 150～ 500rpm, the condition of rate of extrusion 200～600kg/h carry out melting mixing.

Herein, " L " of above-mentioned L/D is " the spiro rod machine tube length " of extruder, and above-mentioned " D " is " spiro rod machine tube Diameter ".

The screw diameter of double screw extruder is preferably 25～90mm, more preferably 40～70mm.

In the case of using double screw extruder to manufacture above-mentioned thermoplastic resin composition, from giving material thermal resistance and machine From the viewpoint of tool physical property, preferably polyphenylene oxide (A), phenylethylene resin series (B) and organic phosphorus flame retardant (D) are from extruder Most upstream portion supply mouth (its top feed mouth) supply, the glass fibre (C) supply mouth in the middle part of extruder (enter by side Material mouth) supply.

[fan products formed]

The fan products formed of present embodiment can obtain by being shaped above-mentioned thermoplastic resin composition.Make For forming method, can enumerate such as compression forming, injection moulding, calendering formation, extrusion molding, hollow molding, The methods such as inflation molding, thermoforming, blow molding.

The maximum gauge of the fan products formed of present embodiment is preferably more than 30mm, more preferably more than 40mm, Furthermore it is preferred that be below 200mm, more preferably below 160mm, it is even more preferably below 120mm. By making maximum gauge be below 200mm, it is possible to seek to apply the miniaturization of the electronic equipment of fan products formed.

The fan products formed of present embodiment is preferably used as the communications such as electronic equipment, mobile telephone base station such as server and sets The cooling of power-supply device standby, vehicle-mounted (lithium ion battery of such as electric motor car, hybrid electric vehicle etc., Ni-MH battery etc.) Fan etc..

If electronics miniaturization, then thermal capacitance is easily trapped in electronic equipment internal.The fan products formed of present embodiment makes Fan products formed is manufactured, even if therefore at height with the thermoplastic resin composition that E2 '/E1 ', E2 '/ρ is particular range Under heat, high speed rotating, it is not easy to deform, it is possible to be applied to easily be detained inside the miniaturized electronics of heat.This Outward, even if under high heat, high speed rotating, cooling effectiveness is the highest.

Embodiment

Hereinafter enumerating specific embodiment and comparative example, the present invention will be described.The invention is not restricted to this.

The raw material of the fan products formed of embodiment and comparative example and the assay method of physical property are as follows.

[raw material]

-polyphenylene oxide (A)-

PPE-1: reduced viscosity η (using chloroform solvent 30 DEG C of mensuration) is the poly-(2,6-dimethyl-1,4-of 0.52dl/g Phenylene) ether

PPE-2: reduced viscosity η (using chloroform solvent 30 DEG C of mensuration) is the poly-(2,6-dimethyl-1,4-of 0.40dl/g Phenylene) ether

PPE-3: reduced viscosity η (using chloroform solvent 30 DEG C of mensuration) is the poly-(2,6-dimethyl-1,4-of 0.31dl/g Phenylene) ether

-polystyrene (B)-

GPPS-1: General Purpose Polystyrenre (trade name: Styron660 (registered trade mark), Dow Chemical company system)

-glass fibre (C)-

GF-1: average fiber footpath 10 μm that processes through amino silane compounds surface, fibre cutting length 3mm Glass fibre (trade name: EC10 3MM 910 (registered trade mark), NSG Vetrotex society system)

GF-2: average fiber footpath 13 μm that processes through amino silane compounds surface, fibre cutting length 3mm Glass fibre (trade name: ECS03T-249 (registered trade mark), NEG society system)

-organic phosphorus flame retardant (D)-

FR-1: triphenyl phosphate (aromatic phosphoric ester flame retardant, trade name: TPP (registered trade mark), big eight chemistry Society's system)

FR-2: bisphenol-A double (diphenyl phosphoester) (aromatic phosphoric ester flame retardant, trade name: CR-741 (registration Trade mark), big eight chemistry society systems)

(phosphonitrile flame retardant, trade name: Rabbitle (registered trade mark) FP-110, volt are shown in system to FR-3: phosphonitrile acid phenenyl ester Yao Suo society system)

-polyamide series resin (E1)-

PA9T-1: polyamide (according to the method described in the embodiment of Japanese Unexamined Patent Publication 2000-212433 publication, will As the p-phthalic acid 3272.96g (19.7 moles) of dicarboxylic acid component, 1,9-nonamethylene diamine as diamine component 2532.64g (16.0 moles) and 2-methyl isophthalic acid, 8-octamethylenediamine 633.16g (4.0 moles), benzoic acid as end-capping reagent 73.26g (0.60 mole), ortho phosphorous acid sodium-hydrate 6.5g (being 0.1 mass % relative to raw material) and distilled water 6 liters Add to the autoclave of internal volume 20 liters, carry out nitrogen displacement.Stir 30 minutes at 100 DEG C, with 2 hours by interior Portion's temperature is warming up to 210 DEG C.Now, autoclave boosts to 22kg/cm².Keep this state sustained response after 1 hour, It is warming up to 230 DEG C, afterwards, keeps the temperature at 230 DEG C 2 hours, slowly extract water vapour out, pressure is protected Hold at 22kg/cm²While making it react.Then, with 30 minutes, pressure is down to 10kg/cm², react 1 further Hour, obtaining intrinsic viscosity [η] is the prepolymer of 0.25dl/g.By its 100 DEG C, decompression under be dried 12 hours, It is ground into the size of below 2mm.By it 230 DEG C, solid phase 10 hours under 0.1mmHg, obtain polyamide Granular polymer.Temperature cylinder is used to be set as that the granular polymer obtained is made by the double screw extruder of 330 DEG C Granular PA9T-1.Fusing point: 304 DEG C, intrinsic viscosity [η]: 1.20dl/g, ending ratio: 90%, terminal amino group Concentration: 10 μm ol/g, terminal carboxyl group: 60 μm ol/g, phosphorus element content: 300ppm)

-polyphenylene sulfide system resin (E2)-

PPS-1: polyphenylene sulfide (DSP (registered trade mark) K-2G, DIC EP Co., Ltd. system)

-other materials-

PBT-1: polybutylene terephthalate (DURANEX PBT (registered trade mark) 2002, WinTechPolymer Co., Ltd.'s system)

FR-4: dialkyl phosphinic acid aluminum (metal phosphinate flame retardant, trade name: EXOLIT OP1230 (registration Trade mark), Clariant Japan society system)

FR-5: brominated Polystyrene (bromide fire retardant, trade name: SAYTEX (registered trade mark) HP-7010, refined treasured Japan's system)

Compatilizer-1: the styrene-t (+)-2,3-Epoxy-1-propanol of the glycidyl methacrylate containing 5 weight % Ester copolymer (weight average molecular weight 110,000)

Compatilizer-2: trade name: CRYSTAL MAN AB (registered trade mark), NOF Corp's system

Antimony trioxide: trade name: PATOX-M (registered trade mark), concentrate Co., Ltd. of Japan system

Muscovitum: trade name: C-1001F (registered trade mark), REPCO society system

[evaluation]

(1) storage modulus

1. measure sample making

The impeller wheel portion of the fan products formed manufactured in embodiment and comparative example is cut, long by hot-pressing 50mm, wide 10mm, the test film of thick 4mm.

2. measure

Use Measurement of Dynamic Viscoelasticity device (trade name " EPLEXOR 500N ", ITS-JAPAN Co., Ltd. system), With following condition, the storage modulus of the storage moduluss of 85 DEG C and 110 DEG C is measured.

(2) UL94 flammability

Use bar shaped matrix band thick for 0.75mm, based on flame retardant test standard UL94, flame retardant level is judged.

(3) fan deflection

As it is shown in figure 5, in Forced Convection Constant Temperature Ovens (DKM600 type, Yamato science Co., Ltd. system), set It is placed on the DC brushless motor 2 (BMS-4020, NAKANISHI system) of aluminium casing 3 interior (in heat insulation shell), The evaluation fan products formed 1 connected by rotary shaft is set, implements rotation test.

First, in the state of temperature 25 DEG C with revolution 1,000rpm makes fan products formed 1 rotate, and uses laser sensing The aluminum shell of the internal diameter φ 120mm of device (Keyence IB-10) METHOD FOR CONTINUOUS DETERMINATION fan most external and simulation actual product The gap length of body 3, when numerical stability, obtains the gap length (L1 (mm)) of itself and aluminium casing 3.

Then, the temperature of thermostat is set as 85 DEG C, when temperature stabilization, the revolution of fan products formed 1 is set It is set to 7,000rpm, uses laser sensor (light projector 4, light-receiving device 5) METHOD FOR CONTINUOUS DETERMINATION fan most external real with simulation The gap length of the aluminium casing 3 of the internal diameter φ 120mm of border goods, when numerical stability, obtains itself and aluminum shell The gap length (L2 (mm)) of body.

The deflection of fan uses following formula to obtain.

" fan deflection: 85 DEG C × 7,000rpm (mm) "=L2-L1

Fan deflection under the conditions of temperature 110 DEG C, revolution 7,000rpm is obtained the most in the same way.

(4) die steel corrosivity

The granular thermoplastic resin group that table 1 is recorded is loaded in ceramic crucible (internal diameter φ 38mm, high 110mm) Compound, in granule, embedment cuts into wide 20mm, long 40mm, the carbon steel S55C sheet of thick 3mm size.To add Enter to have the ceramic crucible of resin particle and carbon steel coupon to stand 5 hours at the electric furnace of 330 DEG C, after taking-up, use exsiccator It is cooled to room temperature.After cooling, in resin material, take out carbon steel coupon, be visually confirmed to be surface free corrosion, will not send out Situation about now corroding is evaluated as "None", it may be found that the situation of corrosion is evaluated as " having ".

[embodiment 1]

From double screw extruder (trade name: ZSK40MC, Werner&Pfleiderer society system, machine barrel number 13, screw rod Diameter 40mm, there are 2 kneading disk L, 6 kneading disk R, the screw pattern of 4 kneading disk N) most upstream Portion's (its top feed mouth) supplies (PPE-1) 34 mass parts, mixes with Henschel in advance with the ratio of (FR-1)/(PPE-1)=1/3 Mixture 36 mass parts that conjunction machine stirring mixing (revolution 600rpm, mixing time 1min, interior temperature 23-25 DEG C) obtains, From machine barrel 8 side-fed (GF-1) 30 mass parts at middle part, with temperature cylinder 300 DEG C, screw rod revolution 250rpm, Rate of extrusion 100kg/h carries out melting mixing, obtains thermoplastic resin composition.

Thermoplastic resin composition is measured according to ISO1183 at the proportion ρ of 23 DEG C.

Aerofoil fan (model " 9GV1212P1J01 ", Sanyo Electric Co., Ltd.'s system) is carried out 3D scanning, by wind Fan shape is transformed to cad data.According to the cad data obtained, make the injection moulding mould of fan products formed Tool.The maximum gauge of the fan mould made is 114mm.

Use above-mentioned mould and injection (mo(u)lding) machine (trade name: EC100SX, Toshiba Machinery Co., Ltd.'s system), at table 1 Under the temperature conditions recorded, above-mentioned thermoplastic resin composition is shaped, obtains fan products formed.

It should be noted that in comparative example 3 (PPS material), stand 3 hours in 150 DEG C of baking ovens after molding, carry out Annealing.

[embodiment 2～9, comparative example 1～4]

Making thermoplastic resin composition's to consist of the composition that table 1 is recorded, making forming temperature is the temperature that table 1 is recorded, In addition, carry out similarly to Example 1, obtain fan products formed.

[table 1]

Industrial applicibility

Fan products formed according to the present invention, it is possible to obtain following fan products formed: though its in high temperature environments and Operating with high rotation status, the deformation of fan is also few, and can be high rotary further, and cooling effectiveness is high.

Claims

1. a fan products formed, it is characterised in that it contains thermoplastic resin composition,

Described thermoplastic resin composition in Measurement of Dynamic Viscoelasticity, storage modulus E2 of 110 DEG C ' relative to 85 DEG C / the E1 ' of storage modulus E1 ' ratio (E2 ') be more than 0.90,

2. fan products formed as claimed in claim 1, wherein, the anti-flammability water of described thermoplastic resin composition Putting down as V-0, described flame retardancy level, according to UL94, is implemented with the test film thickness of 0.75mm.

3. fan products formed as claimed in claim 1 or 2, wherein, described thermoplastic resin composition is polyphenyl Ether based resin composition.

4. the fan products formed as according to any one of claims 1 to 3, wherein,

Described thermoplastic resin composition is following polyphenylene ether resin composition: polyphenylene oxide (A), polystyrene tree The gross mass of fat (B) and glass fibre (C) is more than 90 mass %, if described gross mass is 100 mass %, described poly- Phenylate based resin composition contains polyphenylene oxide (A) 45 mass %～75 mass %, phenylethylene resin series (B) 0 mass %～5 Quality %, glass fibre (C) 25 mass %～50 mass %.

5. the fan products formed as according to any one of Claims 1 to 4, wherein, described thermoplastic resin composition Contain organic phosphorus flame retardant (D) further, if polyphenylene oxide (A), phenylethylene resin series (B), glass fibre (C) and have When the gross mass of machine phosphorus flame retardant (D) is 100 mass %, the content of organic phosphorus flame retardant (D) be 5 mass %～ 20 mass %.

6. fan products formed as claimed in claim 5, wherein, if the quality of described organic phosphorus flame retardant (D) is 100 mass %, described organic phosphorus flame retardant (D) is containing the free triphenyl phosphates of choosing more than 70 mass % and phosphonitrile The compound of more than a kind in the group of composition.

7. the fan products formed as according to any one of claim 1～6, its maximum gauge is below 200mm.