CN109790379A

CN109790379A - Composite resin composition and the electronic component as made of composite resin composition forming

Info

Publication number: CN109790379A
Application number: CN201780058316.8A
Authority: CN
Inventors: 深津博树; 泷智弘
Original assignee: Polyplastics Co Ltd
Current assignee: Polyplastics Co Ltd
Priority date: 2016-10-07
Filing date: 2017-09-26
Publication date: 2019-05-21
Anticipated expiration: 2037-09-26
Also published as: WO2018066416A1; JP6345376B1; TW201827483A; CN109790379B; KR102058121B1; TWI711644B; KR20190026037A; JPWO2018066416A1

Abstract

The electronic component that the present invention provided and can obtain excellent heat resistance, inhibited the composite resin composition of the electronic component of buckling deformation and blistering generation and shaped by the composite resin composition.Composite resin composition of the invention includes: (A) liquid-crystalline polymer, (B) fibrous filler and (C) plate filler, above-mentioned (A) liquid-crystalline polymer is that following Component units (I)~(VI) comprising specified amount shows optically anisotropic Wholly aromatic polyester amide as required constituent and in melting, and the weight average fiber length of aforementioned (B) fibrous filler is 250 μm or more.

Description

Composite resin composition and the electronics as made of composite resin composition forming Component

Technical field

The present invention relates to composite resin composition and the electronic components as made of composite resin composition forming.

Background technique

Liquid-crystalline polymer is the excellent thermoplastic resins such as dimensional accuracy, mobility.Due to having the feature that, one Liquid-crystalline polymer is used as the material of various electronic components since straight.

Especially with the high performance of electronic equipment in recent years, the high heat resistance of connector is had also appeared (based on installation The productivity of technology improves), densification (multiple-core) and the requirement for minimizing such epoch, start with above-mentioned liquid crystal Property polymer feature and using the liquid-crystalline polymer composition strengthened by glass fibre as connector material.

But in recent years, connector is pushed further into light and shortization, caused by the wall thickness deficiency because of formed products Rigidity is insufficient, the internal stress because of caused by the insertion of metal terminal, and buckling deformation occurs after forming and in Reflow Soldering heating, It leads to the problem of bad with the solder of substrate.That is, in the existing reinforcing carried out merely with glass fibre, in order to improve rigidity And when increasing the additive amount of glass fibre, there are resin not thin-walled portion fill or because forming when pressure due to be embedded in terminal The problem of deforming.

In order to solve the problems, such as such buckling deformation, manufacturing process is studied, also, is examined in terms of material Consider, proposes the specific plate filler of compounding.That is, for the feelings of most of common connectors (electronic component) in the market Condition can be controlled the dimensional accuracy of product, be stuck up by gate location and design as the setting holding symmetry in forming Song by using the low warpage material proposed in the past, can obtain the few product of buckling deformation in turn.

But the complication of the shape with electronic component in recent years, it is desirable that XY axial plane, the YZ relative to formed products are provided Any axial plane of axial plane and XZ axial plane not no asymmetric electronic parts of symmetry.As the asymmetric electronic parts, can arrange DDR-DIMM connector etc. is enumerated to make with the memory module connector of locking mechanism (there is fixed claw at both ends) For typical example.Especially laptop memory module connector has the locking mechanism for installation, and has and use In the notch of position alignment, therefore, become extremely complex shape.

The case where for such asymmetric electronic parts, with the XY axial plane, YZ axial plane and XZ axial plane relative to formed products Any axial plane have the common connector (symmetrical electron component) of symmetry different, do not have symmetry, therefore, from Set out in terms of shape method progress buckling deformation improve on there are boundaries.In addition, for the Asymmetric Electric having a complex shape The case where subassembly, the orientation of resin and filler in formed products becomes complicated, but also needs higher mobility, and warpage becomes The inhibition of shape is more difficult.

As the technology for solving such problems, For example, Patent Document 1 discloses a kind of Asymmetric Electric sub-portions Part, the liquid-crystalline polymer group as made of being compounded specific fibrous filler and specific plate filler with specific quantity Object forming is closed, any axial plane relative to the XY axial plane of formed products, YZ axial plane and XZ axial plane is without symmetry.

Existing technical literature

Patent document

Patent document 1: International Publication No. 2008/023839

Summary of the invention

Problems to be solved by the invention

But since the nearest integrated rate with asymmetric electronic parts the associated change in shape such as increases, especially saves The reasons such as distance, the reduction of product height, increase of number of poles away between, liquid-crystalline polymer group disclosed in above-mentioned patent document 1 It closes the existing liquid-crystalline polymer composition such as object and there is the case where can not coping with completely.That is, existing liquid-crystalline polymer group Heat resistance and the mobility for closing object are insufficient, are difficult to obtain using such liquid-crystalline polymer composition and inhibit buckling deformation Asymmetric electronic parts.

In addition, liquid-crystalline polymer composition may lead to the problem of blistering.That is, the liquid crystal as liquid-crystalline polymer The high high-temp stability of property polyesteramide is good, therefore, is typically used to the material for needing to carry out the heat treatment under high temperature.But It is to be placed on formed products in the air of high temperature for a long time and when in liquid, it may occur that generated on surface and be referred to as the thin of blistering It is small the problem of heaving.Caused by the phenomenon is following: the decomposition gas that liquid crystalline polyester amide generates when in a molten state Deng enter formed products inside, later carry out high temperature heat treatment when the gas expansion, the formed products table that heating has been softened Face jacks up, and the part jacked up is presented in the form blistered.Blistering generation also can by the melting extrusion of material from Gas vent sufficiently deaerates, is detained for a long time in forming not in forming machine etc. to reduce.But condition and range is very narrow, it is right It is insufficient for obtaining the formed products for inhibiting blistering to occur, the i.e. formed products with resistance to foaming.For essence Ground solves blistering, it is desirable that improves the quality of liquid crystalline polyester amide itself, and well known liquid crystalline polyester amide, uses it Method for solve the problems, such as blistering occur for be insufficient.

Invention that present invention has been made in view of the above circumstances, it is intended that excellent heat resistance can be obtained, inhibit by providing It the composite resin composition of the electronic component that buckling deformation and blistering occur and is shaped by the composite resin composition Electronic component.

The solution to the problem

The inventors of the present invention's discovery, by filling out the liquid-crystalline polymer of specific Component units for including specified amount, threadiness Agent and the combination of plate filler, and 250 μm of weight average fiber length for making fibrous filler or more are filled, are able to solve The problem of stating.Specifically, the present invention provides following scheme.

(1) a kind of composite resin composition, it includes (A) liquid-crystalline polymer, (B) fibrous filler and (C) plates Filler,

Aforementioned (A) liquid-crystalline polymer be comprising following Component units (I)~(VI) as required constituent and Optically anisotropic Wholly aromatic polyester amide is shown when melting, wherein

Relative to whole Component units, the content of Component units (I) is 50~70 moles of %,

Relative to whole Component units, the content of Component units (II) is more than and less than 4.5 moles % of 0.5 mole of %,

Relative to whole Component units, the content of Component units (III) is 10.25~22.25 moles of %,

Relative to whole Component units, the content of Component units (IV) is more than and less than 4.5 moles % of 0.5 mole of %,

Relative to whole Component units, the content of Component units (V) is 5.75~23.75 moles of %,

Relative to whole Component units, the content of Component units (VI) is 1~7 mole of %,

Relative to whole Component units, the total contents of Component units (II) and Component units (IV) be 1 mole of % or more and Less than 5 moles %,

Relative to whole Component units, Component units (I)~(VI) total content is 100 moles of %,

Relative to the summation of Component units (V) and Component units (VI), the molar ratio of Component units (VI) is 0.04~ 0.37,

The weight average fiber length of aforementioned (B) fibrous filler is 250 μm or more,

Aforementioned (A) liquid-crystalline polymer relative to composite resin composition generally 37.5~82.5 mass %,

Aforementioned (B) fibrous filler relative to composite resin composition generally 2.5~17.5 mass %,

Aforementioned (C) plate filler relative to composite resin composition generally 15~45 mass %,

The total amount of aforementioned (B) fibrous filler and aforementioned (C) plate filler is relative to composite resin composition entirety For 17.5~62.5 mass %.

(2) composite resin composition according to (1), wherein Component units (III) always rub with Component units (IV) Your number is 1~1.1 times of the total mole number of Component units (V) and Component units (VI), alternatively, Component units (V) and composition are single The total mole number of first (VI) is 1~1.1 times of the total mole number of Component units (III) and Component units (IV).

(3) composite resin composition according to (1) or (2), wherein aforementioned (B) fibrous filler is glass fibers Dimension.

(4) composite resin composition according to any one of (1)~(3), wherein above-mentioned (C) plate filler is Talcum.

(5) a kind of electronic component, the composite resin composition as described in any one of (1)~(4) shape, product Overall length is 30mm or more, and product height is 5mm or more.

(6) electronic component according to (5), for appointing relative to the XY axial plane of formed products, YZ axial plane and XZ axial plane It anticipates axial plane not no asymmetric electronic parts of symmetry.

(7) electronic component according to (5) or (6), distance 0.6mm or less, product overall length 60.0mm between pitch Above, the extremely above memory module connector of product height 10.0mm or less, number of poles 200.

The effect of invention

In accordance with the invention it is possible to provide the ministry of electronics industry that can be obtained excellent heat resistance, buckling deformation and blistering is inhibited to occur The composite resin composition of part and the electronic component shaped by the composite resin composition.

Detailed description of the invention

Fig. 1 is the figure for indicating the DDR-DIMM connector shaped in embodiment.It should be noted that A indicates gate location.

Fig. 2 is the figure to locate in the warpage measurement for indicate the DDR-DIMM connector carried out in embodiment.

Specific embodiment

Hereinafter, embodiments of the present invention are specifically described.

[composite resin composition]

Composite resin composition of the invention is filled out comprising respectively specified amount, specific liquid-crystalline polymer, threadiness Agent and plate filler are filled, the weight average fiber length of fibrous filler is 250 μm or more.Hereinafter, to the present invention is constituted The ingredient of composite resin composition be illustrated.

(liquid-crystalline polymer)

Include the liquid-crystalline polymer as above-mentioned Wholly aromatic polyester amide in composite resin composition of the invention.On The fusing point for stating Wholly aromatic polyester amide is low, therefore, can reduce processing temperature, inhibits to generate when melting and decomposes gas.It is tied Fruit is soaked being able to suppress comprising formed products obtained from the forming of the composite resin composition of above-mentioned Wholly aromatic polyester amide Raw, resistance to foaming improves.Liquid-crystalline polymer can be used alone or two or more is applied in combination.

Wholly aromatic polyester amide of the invention includes following Component units (I), following Component units (II), following compositions Unit (III), following Component units (IV), following Component units (V) and following Component units (VI).

Component units (I) are by 4-HBA (hereinafter also referred to " HBA ".) derivative.Wholly aromatic polyester of the invention In amide, relative to whole Component units, the Component units (I) comprising 50~70 moles of %.The content of Component units (I) is less than 50 moles of % or when more than 70 moles of %, at least one of low melting point and heat resistance are easy to become inadequate.From taking into account eutectic It reveals with from the perspective of heat resistance, the content of Component units (I) is preferably 54~67 moles of %, more preferably 58~64 rubs You are %.

Component units (II) are by 6-Hydroxy-2-naphthoic acid (hereinafter also referred to " HNA ".) derivative.All aromatic of the invention Component units (II) in polyesteramide, relative to whole Component units, comprising 0.5 mole of % more than and less than 4.5 moles of %. The content of Component units (II) is less than 0.5 mole of % or when being 4.5 moles of % or more, at least the one of low melting point and heat resistance Person is easy to become inadequate.From the viewpoint of taking into account low melting point and heat resistance, the content of Component units (II) is preferably 0.75~3.75 mole of %, more preferably 1~3 mole of %.

Component units (III) are by 1,4- benzene dicarboxylic acid (hereinafter also referred to " TA ".) derivative.Wholly aromatic polyester of the invention In amide, relative to whole Component units, the Component units (III) comprising 10.25~22.25 moles of %.Component units (III) Content less than 10.25 moles of % or more than 22.25 moles of % when, at least one of low melting point and heat resistance are easy to become It is insufficient.From the viewpoint of taking into account low melting point and heat resistance, the content of Component units (III) is preferably 12.963~ 20.75 moles of %, more preferably 15.675~19.25 moles of %.

Component units (IV) are by 1,3- benzene dicarboxylic acid (hereinafter also referred to " IA ".) derivative.Wholly aromatic polyester of the invention Component units (IV) in amide, relative to whole Component units, comprising 0.5 mole of % more than and less than 4.5 moles of %.It constitutes The content of unit (IV) is less than 0.5 mole of % or when being 4.5 moles of % or more, at least one appearance of low melting point and heat resistance Easily become inadequate.From the viewpoint of taking into account low melting point and heat resistance, the content of Component units (IV) is preferably 0.5~ 3.75 moles of %, more preferably 0.5~3 mole of %.

Component units (V) are by 4,4 '-dihydroxybiphenyls (hereinafter also referred to " BP ".) derivative.All aromatic of the invention is poly- In esteramides, relative to whole Component units, the Component units (V) comprising 5.75~23.75 moles of %.Component units (V) When content is less than 5.75 moles of % or more than 23.75 moles of %, at least one of low melting point and heat resistance are easy to become not fill Point.From the viewpoint of taking into account low melting point and heat resistance, the content of Component units (V) be preferably 8.5~20.375 moles of %, More preferably 11.25~17 moles of % (for example, 11.675~17 moles of %).

Component units (VI) are by n-acetyl-p-aminophenol (hereinafter also referred to " APAP ".) derivative.Full virtue of the invention In fragrant adoption esteramides, relative to whole Component units, the Component units (VI) comprising 1~7 mole of %.Component units (VI) When content is less than 1 mole of % or more than 7 moles of %, at least one of low melting point and heat resistance are easy to become inadequate.From simultaneous From the perspective of caring for low melting point and heat resistance, the content of Component units (VI) be preferably 1.5~7 moles of %, more preferably 2~ 7 moles of %.

In Wholly aromatic polyester amide of the invention, relative to whole Component units, comprising total 1 mole of % or more and small In the Component units (II) and Component units (IV) of 5 moles of %.In above-mentioned Wholly aromatic polyester amide, by with above range The Component units (II) of the bendability with naphthalene skeleton and the Component units (IV) of the bendability with benzene skeleton coexist in total amount, low Fusing point and taking into account for heat resistance are easy to become abundant.When above-mentioned total content is less than 1 mole of %, the ratio of the Component units of bendability Example becomes very few, and therefore, low melting point is easy to become inadequate.When above-mentioned total content is 5 moles of % or more, the composition of bendability The ratio of unit becomes excessively, and therefore, heat resistance is easy to become inadequate.Go out from the viewpoint for taking into account low melting point and heat resistance Hair, above-mentioned total content are preferably 1.75~4.75 moles of %, more preferably 2.5~4.5 moles of %.

In Wholly aromatic polyester amide of the invention, relative to the summation of Component units (V) and Component units (VI), constitute The molar ratio of unit (VI) is 0.04~0.37.When above-mentioned molar ratio is less than 0.04, the ratio of the Component units with biphenyl backbone Example becomes more, and therefore, the crystallinity of Wholly aromatic polyester amide is lower, and low melting point and taking into account for heat resistance are easy to become not fill Point.In addition, the key not of the same race other than ester bond increases when above-mentioned molar ratio is more than 0.37, and therefore, the knot of Wholly aromatic polyester amide Crystalline substance is lower, and low melting point and taking into account for heat resistance are easy to become inadequate.Go out from the viewpoint for taking into account low melting point and heat resistance Hair, above-mentioned molar ratio are preferably 0.07~0.36, more preferably 0.11~0.35.

From the viewpoint of taking into account low melting point and heat resistance, it is preferred that Component units (III) and Component units (IV) Total mole number (hereinafter also referred to " molal quantity 1A ".) be the total mole number of Component units (V) and Component units (VI) (below Referred to as " molal quantity 2A ".) 1~1.1 times, alternatively, the total mole number of Component units (V) and Component units (VI) are Component units (III) with 1~1.1 times of the total mole number of Component units (IV).It is further preferred that molal quantity 1A be molal quantity 2A 1.02~ 1.06 times, alternatively, molal quantity 2A is 1.02~1.06 times of molal quantity 1A.It may further be preferable that molal quantity 1A is molal quantity 1.024~1.056 times of 2A, alternatively, molal quantity 2A is 1.024~1.056 times of molal quantity 1A.

As described above, in Wholly aromatic polyester amide of the invention, relative to whole Component units, respectively specifically to measure Summation containing (I) as specific Component units~(VI) and Component units (II) and Component units (IV), also, phase For the summation of Component units (V) and Component units (VI), the molar ratio of Component units (VI) is therefore, low in specific range Fusing point and heat resistance are taken into account more sufficiently.It should be noted that in Wholly aromatic polyester amide of the invention, relative to complete Portion's Component units, Component units (I)~(VI) comprising amounting to 100 moles of %.

As the index for indicating above-mentioned heat resistance, temperature of deflection under load (hereinafter also referred to " DTUL " can be enumerated.).DTUL When being 260 DEG C or more, heat resistance has the tendency that getting higher, and is preferred.DTUL is with following polyesteramide resin composition Value obtained from state is measured, the polyesteramide resin composition are by aforementioned 60 mass % of Wholly aromatic polyester amide With 11 μm of avarage fiber diameter, 75 μm of average fiber length 40 mass % of milled fibre in aforementioned Wholly aromatic polyester amide Obtained from carrying out melting mixing at+20 DEG C of fusing point, DTUL can be based on ISO75-1, and 2 are measured.From taking into account low melting point From the perspective of heat resistance, DTUL is preferably 265 DEG C or more and 310 DEG C or less, more preferably 267~300 DEG C.

Hereinafter, being illustrated to the manufacturing method of Wholly aromatic polyester amide of the invention.All aromatic of the invention is poly- Esteramides is polymerize using direct polymerization method, ester-interchange method etc..When polymerization, melt phase polycondensation, solution polymerization process, slurry are used Combination of more than two kinds in polymerization, solid phase polymerization method etc. or these methods is, it is preferable to use melt phase polycondensation or melt polymerization The combination of method and solid phase polymerization method.

In the present invention, in polymerization, the acylating agent for polymerized monomer can be used, end is lived as chloride derivative The monomer of property.As acylating agent, fatty acid anhydrides such as acetic anhydride etc. can be enumerated.

In these polymerizations, various catalyst can be used, as representative catalyst, can enumerate: dialkyl tin Oxide, diaryltin oxide, titanium dioxide, alkoxytitanium silicates, titanium refine species, fatty acid metal salts, BF₃It The lewis acid etc. of class, preferred fat acid metal salt.The gross mass that the usage amount of catalyst is typically based on monomer is about 0.001 ~1 mass %, particularly preferably about 0.003~0.2 mass %.

In addition, carrying out polymerisation in solution or when slurry polymerization, as solvent, atoleine, high-fire resistance synthetic oil, non-is used Active mineral oil etc..

As reaction condition, for example, 200~380 DEG C of reaction temperature, eventually arrive at 0.1~760Torr of pressure (that is, 13 ~101,080Pa).Especially in frit reaction, for example, 260~380 DEG C of reaction temperature, preferably 300~360 DEG C, it is final It reaches 1~100Torr of pressure (that is, 133~13,300Pa), be preferably 1~50Torr (that is, 133~6,670Pa).

Reaction whole starting monomers (HBA, HNA, TA, IA, BP and APAP), acylating agent and catalyst can be added same So that reaction is started (stage manner) in one reaction vessel, the hydroxyl of starting monomer HBA, HNA, BP and APAP can also be used After acylating agent is acylated, (second order segmented mode) is reacted with the carboxyl of TA and IA.

Melt polymerization starts to depressurize after reaching predetermined temperature in the reaction system, is gathered after reaching defined degree of decompression It closes.After the torque of blender reaches specified value, non-active gas is imported, becomes defined from decompression state experience normal pressure and adds Then pressure condition is discharged from reaction system by Wholly aromatic polyester amide.

The Wholly aromatic polyester amide manufactured by above-mentioned polymerization passes through further under normal pressure or decompression x, non- The solid phase heated in active gases can be realized the increase of molecular weight.The preferred condition of solid-phase polymerization is 230~350 DEG C of reaction temperature, preferably 260~330 DEG C, eventually arrive at 10~760Torr of pressure (that is, 1,330~101, 080Pa)。

The manufacturing method of Wholly aromatic polyester amide of the invention preferably comprises following process: in depositing for fatty acid metal salts Under, by 4-HBA, 6-Hydroxy-2-naphthoic acid, 4,4 '-dihydroxybiphenyls and n-acetyl-p-aminophenol rouge Fat acid anhydrides is acylated, then with Isosorbide-5-Nitrae-benzene dicarboxylic acid and 1,3- benzene dicarboxylic acid carry out transesterification,

Relative to comprising 4-HBA, 6-Hydroxy-2-naphthoic acid, 1,4- benzene dicarboxylic acid, 1,3- benzene dicarboxylic acid, 4, Whole monomers of 4 '-dihydroxybiphenyls and n-acetyl-p-aminophenol,

The usage amount of 4-HBA is 50~70 moles of %, from the viewpoint of taking into account low melting point and heat resistance, Preferably 54~67 moles of %, more preferably 58~64 moles of %,

The usage amount of 6-Hydroxy-2-naphthoic acid is more than and less than 4.5 moles % of 0.5 mole of %, from taking into account low melting point From the perspective of heat resistance, preferably 0.75~3.75 mole of %, more preferably 1~3 mole of %,

Isosorbide-5-Nitrae-benzene dicarboxylic acid usage amount is 10.25~22.25 moles of %, from the viewpoint for taking into account low melting point and heat resistance It sets out, preferably 12.963~20.75 moles of %, more preferably 15.675~19.25 moles of %,

The usage amount of 1,3- benzene dicarboxylic acid is more than and less than 4.5 moles % of 0.5 mole of %, from taking into account low melting point and resistance to From the perspective of hot, preferably 0.5~3.75 mole of %, more preferably 0.5~3 mole of %,

The usage amount of 4,4 '-dihydroxybiphenyls is 5.75~23.75 moles of %, from the sight for taking into account low melting point and heat resistance Point sets out, preferably 8.5~20.375 moles of %, more preferably 11.25~17 moles of % (such as 11.675~17 moles of %),

The usage amount of n-acetyl-p-aminophenol is 1~7 mole of %, from the viewpoint for taking into account low melting point and heat resistance It sets out, preferably 1.5~7 moles of %, more preferably 2~7 moles of %,

6-Hydroxy-2-naphthoic acid and 1, total dosage of 3- benzene dicarboxylic acid are more than and less than 5 moles % of 1 mole of %, from simultaneous From the perspective of caring for low melting point and heat resistance, preferably 1.75~4.75 moles of %, more preferably 2.5~4.5 moles of %,

4-HBA, 6-Hydroxy-2-naphthoic acid, 1,4- benzene dicarboxylic acid, 1,3- benzene dicarboxylic acid, 4,4 '-dihydroxy connection Total dosage of benzene and n-acetyl-p-aminophenol is preferably 100 moles of %,

Relative to total dosage of 4,4 '-dihydroxybiphenyls and n-acetyl-p-aminophenol, N- acetyl group-p-aminophenyl The molar ratio of the usage amount of phenol is 0.04~0.37, from the viewpoint of taking into account low melting point and heat resistance, preferably 0.07~ 0.36, it is more preferably 0.11~0.35,

The usage amount of aforementioned fatty acids acid anhydride is preferably 4-HBA, 6-Hydroxy-2-naphthoic acid, 4,4 '-dihydroxy connection 1.02~1.04 times of benzene and total hydroxyl equivalent of n-acetyl-p-aminophenol.More preferable above-mentioned fatty acid metal salts are second Acid metal salt, above-mentioned fatty acid anhydride are acetic anhydride.In addition, it is further preferred that Isosorbide-5-Nitrae-benzene dicarboxylic acid and 1,3- benzene dicarboxylic acid it is total Molal quantity (hereinafter also referred to " molal quantity 1B ".) be 4,4 '-dihydroxybiphenyls and n-acetyl-p-aminophenol total mole number (hereinafter also referred to " molal quantity 2B ".) 1~1.1 times, alternatively, 4,4 '-dihydroxybiphenyls and n-acetyl-p-aminophenol Total mole number is 1~1.1 times of the total mole number of 1,4- benzene dicarboxylic acid and 1,3- benzene dicarboxylic acid.It may further be preferable that mole Number 1B is 1.02~1.06 times of molal quantity 2B, alternatively, molal quantity 2B is 1.02~1.06 times of molal quantity 1B.It is particularly preferred It is that molal quantity 1B is 1.024~1.056 times of molal quantity 2B, alternatively, molal quantity 2B is the 1.024~1.056 of molal quantity 1B Times.

Hereinafter, being illustrated to the property of Wholly aromatic polyester amide.Wholly aromatic polyester amide of the invention is melting When show optical anisotropy.Show that optical anisotropy means Wholly aromatic polyester amide of the invention in melting For liquid-crystalline polymer.

In the present invention, Wholly aromatic polyester amide is that liquid-crystalline polymer has both thermostabilization for Wholly aromatic polyester amide It is indispensable element for property and workability.The Wholly aromatic polyester acyl being made of above-mentioned Component units (I)~(VI) Amine is according to the difference of the sequence distribution in constituent and polymer, and there is also the substances for not forming anisotropy melting behaviors, originally The polymer of invention is limited to show optically anisotropic Wholly aromatic polyester amide in melting.

Melting anisotropic property can be confirmed by the usual polarized light detection checking method using cross-polarization piece. More specifically, melting anisotropic confirmation can implement as got off: using Olympus Co., Ltd's petrographic microscope, Make the sample melting being placed on Linkam company heating microscope carrier, is observed under nitrogen atmosphere with 150 times of multiplying power, it is thus real It applies.Liquid-crystalline polymer is optical anisotropy, light can be made to penetrate when being inserted between cross-polarization piece.Sample be optics respectively to When anisotropic, even for example melting static liquid status, polarised light can also be penetrated.

Sticky reduction can significantly occur when the liquid-crystalline polymer of nematic is more than fusing point, therefore, in general, fusing point or its Above temperature display liquid crystal liquid crystal property becomes the index of processability.Preferably fusing point is as high as possible from the viewpoint of heat resistance, still, Whens heat deterioration, the heating efficiency of forming machine etc. when considering the melt-processed of polymer, being 360 DEG C or less is preferred standard. It should be noted that more preferably 300~360 DEG C, further preferably 340~358 DEG C.

It is of the invention in high 10~30 DEG C of the temperature of fusing point than Wholly aromatic polyester amide and shear velocity 1000/ second Under aforementioned Wholly aromatic polyester amide melt viscosity be preferably 500Pas or less, more preferably 0.5~300Pas, into One step is preferably 1~100Pas.Above-mentioned melt viscosity within the above range when, aforementioned Wholly aromatic polyester amide its own, Or the composition containing aforementioned Wholly aromatic polyester amide its forming when it is easy to ensure that mobility, stuffing pressure were not easy Degree.It should be noted that melt viscosity refers to the melt viscosity based on ISO11443 measurement in this specification.

As the index for indicating above-mentioned heat resistance, fusing point and the difference of DTUL can be also enumerated.It is resistance to when the difference is 90 DEG C or less It is hot to there is the tendency got higher, it is preferred.From the viewpoint of taking into account low melting point and heat resistance, above-mentioned difference preferably greater than 0 DEG C and for 85 DEG C or less (such as 50 DEG C or more and 85 DEG C or less), be more preferably 55~79 DEG C.

Composite resin composition of the invention integrally includes relative to composite resin composition in composite resin composition The above-mentioned liquid-crystalline polymer of 37.5~82.5 mass %.The content of liquid-crystalline polymer is relative to composite resin composition entirety When less than 37.5 mass %, the mobility of composite resin composition is easy to deteriorate, in addition, the electricity obtained by composite resin composition The buckling deformation of the formed products such as subassembly may become larger, therefore not preferably.The content of liquid-crystalline polymer is relative to compound tree Oil/fat composition integrally more than 82.5 mass % when, the elasticity of flexure of the formed products such as electronic component obtained by composite resin composition Modulus and resistance to anti-thread breakage reduction, therefore not preferably.The composite resin composition of the invention phase preferably in composite resin composition Integrally include the above-mentioned liquid-crystalline polymer of 44~75 mass % for composite resin composition, more preferably includes 60~65 matter Measure %.

(fibrous filler)

Composite resin composition of the invention includes above-mentioned liquid-crystalline polymer and fibrous filler, fibrous filler Weight average fiber length be 250 μm or more, therefore, by the composite resin composition forming obtained from formed products high temperature Excellent rigidity inhibits buckling deformation.Fibrous filler can be used alone or two or more is applied in combination.As this hair Bright fibrous filler, is not particularly limited, and can enumerate glass fibre, milled fibre, carbon fiber, asbestos fibre, dioxy SiClx fiber, silica alumina fiber, Zirconium oxide fibre, boron nitride fiber, silicon nitride fiber, boron fibre, potassium titanate Fiber etc..Since the high temperature rigid of the formed products obtained by composite resin composition is easy to improve, as fibre of the invention Tie up shape filler, preferably glass fibre.

In composite resin composition of the invention, the weight average fiber length of fibrous filler is 250 μm or more, excellent It is selected as 350 μm or more, more preferably 450 μm or more.When above-mentioned weight average fiber length is less than 250 μm, by compound resin group The high temperature rigid for closing the formed products that object obtains is difficult to become sufficiently, and the buckling deformation of formed products may become larger, therefore not preferably.Make It for the upper limit of above-mentioned weight average fiber length, is not particularly limited, preferably 700 μm or less, more preferably 500 μm or less. When above-mentioned weight average fiber length is 600 μm or less, the mobility of composite resin composition becomes good, and the warpage of formed products becomes Shape is not easy to become larger, therefore preferably.It should be noted that in this specification, the weight average fiber length of fibrous filler is Refer to, composite resin composition is heated to be ashed for 2 hours at 600 DEG C obtain ash residue, which is dispersed In 5 mass % Aqueous Solutions of Polyethylene Glycol, dispersion liquid is obtained, obtained from being measured using image determiner to the dispersion liquid Weight average fiber length.

In addition, the fibre diameter of fibrous filler of the invention is not particularly limited, usually using 5~15 μm or so Fibre diameter.

Composite resin composition of the invention integrally includes relative to composite resin composition in composite resin composition The fibrous filler of 2.5~17.5 mass %.The content of fibrous filler is integrally less than relative to composite resin composition When 2.5 mass %, the temperature of deflection under load of the formed products such as electronic component obtained by composite resin composition is low, and high temperature rigid is not Sufficiently, therefore it is not preferred.The content of fibrous filler relative to composite resin composition integrally more than 17.5 mass % when, it is multiple The mobility of resin composition deteriorates, and the buckling deformation of formed products may become larger, therefore not preferably.Threadiness of the invention Filler is included in composite resin composition preferably with respect to the whole amount with 4~16 mass % of composite resin composition, more Preferably comprise 5~15 mass %.

(plate filler)

It also include plate filler in composite resin composition of the invention.By in composite resin composition of the invention In include plate filler, the formed products for the buckling deformation that can be inhibited.Plate filler can be used alone or group It closes and uses two or more.

It integrally include the plate filler of 15~45 mass % relative to composite resin composition.The content of plate filler Relative to composite resin composition integrally less than 15 mass % when, the formed products such as electronic component obtained by composite resin composition Buckling deformation may become larger, therefore not preferably.The content of plate filler is integrally more than relative to composite resin composition When 45 mass %, the mobility of composite resin composition may deteriorate, therefore not preferably.Plate filler of the invention is preferred It is included in composite resin composition relative to the whole amount with 20~40 mass % of composite resin composition, more preferably includes 25 ~35 mass %.

As plate filler of the invention, talcum, mica, glass flake, various metal foils etc. can be enumerated, never The mobility of composite resin composition is set to deteriorate, inhibit the aspect of the buckling deformation of the formed products obtained by composite resin composition Consider, preferably talc.In addition, the average grain diameter of plate filler is not particularly limited, if considering the mobility in thinner wall section, It is then preferably smaller.On the other hand, in order to become the warpage of the formed products such as the electronic component obtained by composite resin composition Shape is smaller, needs to maintain certain size.Specifically, it is preferable that 1~100 μm, it is 5~50 μm more preferable.

(talcum)

As the talcum that can be used in the present invention, it is preferred that relative to all solids component amount of the talcum, Fe₂O₃、Al₂O₃And the total content of CaO is 2.5 mass % hereinafter, Fe₂O₃And Al₂O₃Total content be more than 1.0 mass % and for 2.0 Quality % hereinafter, also, CaO content less than 0.5 mass %.That is, the talcum that can be used in the present invention is in addition to as its master The SiO of ingredient₂And other than MgO, Fe can also be contained₂O₃、Al₂O₃And it is at least one kind of in CaO, and contained with above-mentioned content range There is each ingredient.

In above-mentioned talcum, Fe₂O₃、Al₂O₃And the total content of CaO be 2.5 mass % or less when, composite resin composition The heat resistance of the formed products such as shaping processability and the electronic component shaped by composite resin composition is not easy to deteriorate.Fe₂O₃、 Al₂O₃And the total content of CaO is preferably 1.0 mass % or more and 2.0 mass % or less.

In addition, in above-mentioned talcum, Fe₂O₃And Al₂O₃Total content be more than that the talcum of 1.0 mass % is easy to get.In addition, In above-mentioned talcum, Fe₂O₃And Al₂O₃Total content be 2.0 mass % or less when, the shaping processability of composite resin composition and The heat resistance of the formed products such as the electronic component shaped by composite resin composition is not easy to deteriorate.Fe₂O₃And Al₂O₃Always contain Amount is preferably greater than 1.0 mass % and is 1.7 mass % or less.

In turn, in above-mentioned talcum, when the content of CaO is less than 0.5 mass %, the shaping processability of composite resin composition and The heat resistance of the formed products such as the electronic component shaped by composite resin composition is not easy to deteriorate.The content of CaO is preferably 0.01 mass % or more and 0.4 mass % or less.

Talcum of the invention utilizes the quality criteria of laser diffractometry measurement or the cumulative mean partial size (D of volume reference₅₀) Preferably 4.0~20.0 μ from the viewpoint of the mobility of the buckling deformation and maintenance composite resin composition that prevent formed products M, 10~18 μm are more preferably.

(mica)

Mica is the crushed material of the silicate mineral comprising aluminium, potassium, magnesium, sodium, iron etc..As what be can be used in the present invention Mica can enumerate muscovite, phlogopite, biotite, artificial mica etc., wherein from the aspect of good from form and aspect, low-cost It is preferred that muscovite.

In addition, in the manufacture of mica, as the method for crushing mineral, it is known that case of wet attrition method and dry grinding method. Case of wet attrition method is following method: after mica original stone is carried out coarse crushing using Dry-crusher, water is added with pulp-like State carries out main crushing by case of wet attrition, is followed by dehydrated, is dry.Compared with case of wet attrition method, dry grinding method be it is low at This common method, still, when using case of wet attrition method, it is easier to mineral are thin and carefully crush.For being had There is the reasons why mica of aftermentioned preferred average grain diameter and thickness, present invention preferably uses thin and thin crushed materials.Therefore, this hair , it is preferable to use the mica manufactured by case of wet attrition method in bright.

In addition, the process for needing to be dispersed in water pulverized object is therefore, pulverized in order to improve in case of wet attrition method The dispersion efficiency of object, in general, coagulative precipitation agent and/or precipitation aid is added in pulverized object.It can make as in the present invention Coagulative precipitation agent and precipitation aid can enumerate polyaluminium chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, chlorinated copperas (chlorinated copperas), polyiron sulfate, poly-iron chloride, iron-silica inorganic polymer coagulant, iron chloride- Silica inorganic polymer coagulant, calcium hydroxide (Ca (OH)₂), caustic soda (NaOH), soda ash (Na₂CO₃) etc..These are solidifying Poly- precipitating reagent and the pH of precipitation aid are alkalinity or acidity.Mica used in the present invention does not preferably make when carrying out case of wet attrition With coagulative precipitation agent and/or precipitation aid.When using the mica not handled using coagulative precipitation agent and/or precipitation aid, Polymer in composite resin composition is not susceptible to decompose, the molecule for being not likely to produce a large amount of gas, being not susceptible to polymer Therefore amount reduction etc. is easy the performance of the formed products such as the electronic component maintained better.

The mica that can be used in the present invention preferably pass through average grain diameter that Microtrac laser diffractometry measures be 10~ 100 μm, particularly preferred average grain diameter is 20~80 μm.The average grain diameter of mica be 10 μm or more when, to formed products rigidity Improved effect is easy to become sufficiently, therefore preferably.When the average grain diameter of mica is 100 μm or less, the raising of the rigidity of formed products It is easy to become sufficiently, fusion intensity is also easy to become sufficiently, therefore preferably.In turn, the average grain diameter of mica is 100 μm or less When, it is easy to ensure that the sufficient mobility for the forming of electronic component of the invention etc..

Thickness for the mica that can be used in the present invention preferably passes through the thickness of the observation practical measurement of electron microscope Degree is 0.01~1 μm, is particularly preferably 0.03~0.3 μm.Mica with a thickness of 0.01 μm or more when, in composite resin composition Melt-processed when mica be not easily broken, therefore, the rigidity of formed products may be easy to improve, thus preferably.Mica with a thickness of 1 μm or less when, the improved effect of the rigidity of formed products is easy to become sufficiently, therefore preferably.

The mica that can be used in the present invention can use silane coupling agent etc. and be surface-treated, and/or, it can also Graininess is formed to be granulated with bonding agent.

In composite resin composition of the invention, the total amount of fibrous filler and plate filler is relative to compound resin Composition generally 17.5~62.5 mass %.Above-mentioned total amount is relative to composite resin composition integrally less than 17.5 mass % When, the temperature of deflection under load low and high temperature of the formed products such as electronic component obtained by composite resin composition is rigidly insufficient, this Outside, buckling deformation may become larger, therefore not preferably.Above-mentioned total amount is relative to composite resin composition integrally more than 62.5 matter When measuring %, the mobility of composite resin composition deteriorates, the buckling deformation of formed products may become larger, therefore not preferably.It is above-mentioned Total amount is preferably with respect to composite resin composition generally 25~56 mass %, more preferably 35~40 mass %.

(other ingredients)

In composite resin composition of the invention, in addition to the above ingredients, nucleating agent, carbon black, inorganic can also be compounded The pigment such as sintering fuel, antioxidant, stabilizer, plasticizer, lubricant, release agent, fire retardant and well known inorganic filler One or more of.

As long as the manufacturing method of composite resin composition of the invention can uniformly mix the ingredient in composite resin composition It closes, and 250 μm of weight average fiber length for making fibrous filler or more, there is no particular limitation, can be from present It is suitable for selection in the manufacturing method for the resin combination known.Such as it can enumerate: molten using single screw rod or double screw extruder etc. Melt kneading device to each ingredient progress melting mixing and after squeezing out, obtained composite resin composition is processed into powder, squama The method of the desired form such as piece, pellet.

The mobility of composite resin composition of the invention is excellent, and therefore, minimum pressure to fill when forming is not easy to become Excessively, the such tool of electronic component, the asymmetric electronic parts especially with locking mechanism, notch etc. can be preferably shaped to There is the component etc. of complicated shape.The degree of mobility is judged by the minimum pressure to fill of connector.That is, will be in Fig. 1 institute The minimum injection fillers pressure that good formed products can be obtained when the injection moulding of the DDR-DIMM connector shown is defined as minimum Stuffing pressure.Minimum pressure to fill is lower, and it is more excellent to be evaluated as mobility.

High 10~30 DEG C of the fusing point than liquid-crystalline polymer at a temperature of with shear velocity 1000/ second be based on ISO11443 The melt viscosity of the composite resin composition of measurement is 1 × 10⁵Pas or less (more preferable 5Pas or more and 1 × 10²Pa·s Considered from the following aspect below) it is preferable that when the forming of part with complex shape in electronic component, especially non- When there is the formings of the part of complicated shapes such as locking mechanism, notch in symmetrical electron component, it is ensured that composite resin composition Mobility, and stuffing pressure will not become over.

(electronic component)

By shaping composite resin composition of the invention, electronic component of the invention can be obtained.As the present invention Electronic component, be not particularly limited, such as the ministry of electronics industry of product overall length 30mm or more, product height 5mm or more can be enumerated Part.In electronic component of the invention, asymmetric electronic parts refer to the XY axial plane, YZ axial plane and XZ axial plane relative to formed products Any axial plane not no electronic component of symmetry.

The case where for most of common connector (electronic components) in the market, relative to XY axial plane, YZ axial plane and XZ Any axial plane of axial plane has symmetry, can by gate location and design as the setting holding symmetry in forming Control the dimensional accuracy and warpage of product.In contrast, asymmetric electronic parts is complex-shaped, it is difficult to press down in manufacturing process Buckling deformation processed.Electronic component of the invention, especially asymmetric electronic parts are combined by using compound resin of the invention Object is able to suppress buckling deformation.

As the typical example of such electronic component, connector, slot can be enumerated.

As connector, such as memory module connector, interface connector can be enumerated.It is connected as memory module Device, such as DIMM connector can be enumerated；DDR-DIMM connector, DDR2-DIMM connector, DDR-SO-DIMM connector, DDR connectors such as DDR2-SO-DIMM connector, DDR-Micro-DIMM connector, DDR2-Micro-DIMM connector etc..Make For interface connector, such as SATA connector, SAS connector, NGFF connector can be enumerated etc..Wherein, DDR connector, SATA connector, SAS connector and NGFF connector are suitable, the especially thin-walleds of laptop purposes and complex-shaped , distance 0.6mm or less between pitch, product overall length 60.0mm or more, product height 10.0mm or less, 200 grades of number of poles or more Memory module is particularly suitable with connector.Such memory module is fed into connector in peak temperature 230 At~280 DEG C carry out surface installation IR Reflow Soldering process, it is desirable that experience IR Reflow Soldering process before warpage be 0.1mm with Under and Reflow Soldering before and after warpage difference be 0.05mm hereinafter, in accordance with the invention it is possible to meeting such requirement.

In addition, card bus (CardBus), CF card, memory stick, PC card, SD card, SDMo, intelligence can be enumerated as slot The storage card slot of energy card, smart media card etc..

It as the manufacturing process of electronic component of the invention is obtained, is not particularly limited, inhibits warpage to become to obtain The electronic component of shape preferably selects the molding condition of no remaining internal stress.In order to reduce stuffing pressure, reduce obtained electricity The barrel temperature of the remaining internal stress of subassembly, forming machine is preferably the temperature of the fusing point of liquid-crystalline polymer or more.

In addition, preferably 70~100 DEG C of mold temperature.When mold temperature is low, composite resin composition in a mold is filled It may flow bad therefore not preferred.When mold temperature is high, the problems such as generation of burr may be generated, therefore not It is preferred that.For injection speed, preferably it was formed with 150mm/ seconds or more.When injection speed is low, it may only be possible to be not filled by Formed products may be also the formed products that stuffing pressure is high and remaining internal stress is big, only even if obtaining fully filled formed products It can obtain the big electronic component of buckling deformation.

Electronic component of the invention inhibits buckling deformation.The warpage degree of electronic component such as gets off judgement.That is, for figure DDR-DIMM connector shown in 1, multiple position finding height shown in bullet in Fig. 2, will be from least square plane Maximum height and minimum constructive height difference as warpage.Electronic component of the invention inhibits before carrying out IR Reflow Soldering and it The variation of warpage afterwards.

In addition, electronic component of the invention inhibits blistering.The degree that blistering occurs is judged by nucleation temperature. That is, the surface for being clamped in the formed products in the hot press of predetermined temperature after five minutes with visual observation will blister whether there is or not blistering generation Generation number be zero maximum temperature as nucleation temperature.Nucleation temperature is higher, is evaluated as blistering and occurs more to be inhibited.

In addition, the heat resistance of electronic component of the invention, the excellent heat resistance for example evaluated by high temperature rigid.High temperature is rigid Property by being based on ISO75-1,2 measuring load deflection temperatures are evaluated.

Embodiment

Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited thereto.

1 > of < synthesis example

To have blender, reflux column, monomer input port, nitrogen inlet, in decompression/outflow pipeline aggregation container plus Enter starting monomer below, fatty acid metal salt catalyst, acylating agent, starts nitrogen displacement.

(I) 9.7 moles of 4-HBA (58 moles of %) (HBA)

(II) 0.17 mole of 6-Hydroxy-2-naphthoic acid (1 mole of %) (HNA)

(III) 3.2 moles of terephthalic acid (TPA) (19.25 moles of %) (TA)

(IV) 0.25 mole of M-phthalic acid (1.5 moles of %) (IA)

(V) 2.5 moles of 4,4 '-dihydroxybiphenyl (15.25 moles of %) (BP)

(VI) 0.83 mole of n-acetyl-p-aminophenol (5 moles of %) (APAP)

Potassium acetate catalyst 110mg

Acetic anhydride 1734g (1.03 times of total hydroxyl equivalent of HBA and HNA and BP and APAP)

It is added after raw material, the temperature of reaction system is risen to 140 DEG C, is reacted 1 hour at 140 DEG C.Thereafter, it then uses Be warming up to 360 DEG C within 5.5 hours, then, be decompressed to 10Torr (i.e. 1330Pa) with 20 minutes, while make acetic acid, excessive acetic anhydride, Other low boiling point components distillate, Bian Jinhang melt polymerization.After value as defined in reaching in stirring torque, nitrogen is imported, from decompression State undergoes normal pressure and becomes pressurized state, and polymer is discharged from the lower part of aggregation container.

< evaluates >

For the Wholly aromatic polyester amide of synthesis example 1, fusing point, melt viscosity and DTUL are carried out as follows Evaluation.Show the results of the evaluation table 1.

[fusing point]

Using DSC (TA Instruments Inc. manufacture), from room temperature with 20 DEG C/min of Elevated Temperature Conditions to poly- After the observation for closing the endothermic peak temperature (Tm1) that object is observed when being measured, (Tm1+40) DEG C at a temperature of kept for 2 minutes, Then, it is temporarily cooled to room temperature with 20 DEG C/min of cooling conditions, later, measurement is surveyed again with 20 DEG C/min of Elevated Temperature Conditions The temperature of the endothermic peak of time sight.

[DTUL]

By 60 mass % of polymer and glass fibre (Central Glass Co., Ltd. EFH75-01, milled fibre, average fibre Tie up 11 μm of diameter, 75 μm of average fiber length) 40 mass % utilize two axis extruders (Corporation Japan Steel Works TEX30 α Type) under+20 DEG C of fusing point of polymer of barrel temperature melting mixing is carried out, obtain polyesteramide resin composition pellet.

Above-mentioned polyesteramide resin composition pellet is used into forming machine (Sumitomo Heavy Industries, Ltd's system " SE100DU ") it is shaped under molding condition below, obtain measurement test film (4mm × 10mm × 80mm).Use the test Piece, using based on ISO75-1,2 method measuring load deflection temperature.It should be noted that being used as bending stress 1.8MPa.Show the result in table 1.

(molding condition)

Barrel temperature :+15 DEG C of the fusing point of polymer

Mold temperature: 80 DEG C

Back pressure: 2MPa

Injection speed: 33mm/ seconds

[melt viscosity]

Make made Capirograph using Toyo Co., Ltd.'s essence mechanism, with the fusing point than liquid-crystalline polymer it is high by 10~ 30 DEG C of temperature measured liquid crystal based on ISO11443 with shear velocity 1000/ second using the throttle orifice of internal diameter 1mm, length 20mm The melt viscosity of property polymer.It should be noted that measuring temperature is as described in Table 1.

< synthesis example 2~18 compares 1~11 > of synthesis example

The type of starting monomer, feed rate ratio (mole %) are set as shown in table 1~3, in addition to this, with synthesis Example 1 equally operates, and obtains polymer.In addition, similarly evaluated with synthesis example 1.Show the results of the evaluation table 1~3.

[table 1]

[table 2]

[table 3]

< embodiment 1~12, the Comparative Examples 1 to 5 >

In following Examples and Comparative Examples, liquid-crystalline polymer 1 is liquid-crystalline polymer obtained in synthesis example 15. The manufacture in addition, liquid-crystalline polymer 2 and 3 such as gets off.

It should be noted that in the present embodiment, the measurement of the fusing point and melt viscosity of pellet respectively under the following conditions into Row.

[measurement of fusing point]

Using TA Instruments Inc. DSC, from room temperature with 20 DEG C/min of Elevated Temperature Conditions to liquid crystal liquid crystal property After the observation for the endothermic peak temperature (Tm1) observed when polymer is measured, (Tm1+40) DEG C at a temperature of kept for 2 points Then clock is temporarily cooled to room temperature with 20 DEG C/min of cooling conditions, later, measure again with 20 DEG C/min of heating item Part surveys the temperature of the endothermic peak of time sight.

[measurement of melt viscosity]

Make made Capirograph 1B type using Toyo Co., Ltd.'s essence mechanism, it is high in the fusing point than liquid-crystalline polymer Using the throttle orifice of internal diameter 1mm, length 20mm at a temperature of 10~30 DEG C, surveyed with shear velocity 1000/ second based on ISO11443 Determine the melt viscosity of liquid-crystalline polymer.It should be noted that liquid-crystalline polymer 1 is 360 DEG C, liquid crystal for measuring temperature Property polymer 2 be 350 DEG C, liquid-crystalline polymer 3 be 380 DEG C.

(manufacturing method of liquid-crystalline polymer 2)

To have blender, reflux column, monomer input port, nitrogen inlet, in decompression/outflow pipeline aggregation container plus Enter starting monomer below, metallic catalyst, acylating agent, starts nitrogen displacement.

(I) 4-HBA: 1380g (60 moles of %) (HBA)

(II) 6-Hydroxy-2-naphthoic acid: 157g (5 moles of %) (HNA)

(III) terephthalic acid (TPA): 484g (17.5 moles of %) (TA)

(IV) 4,4 '-dihydroxybiphenyl: 388g (12.5 moles of %) (BP)

(V) 4- acetoxyl group amino-phenol: 126g (5 moles of %) (APAP)

Potassium acetate catalyst: 110mg

Acetic anhydride: 1659g

It is added after raw material in aggregation container, the temperature of reaction system is risen to 140 DEG C, it is small that 1 is reacted at 140 DEG C When.Thereafter, then with 4.5 hours be warming up to 340 DEG C, then, be decompressed to 10Torr (that is, 1330Pa) with 15 minutes, while make acetic acid, Excessive acetic anhydride, other low boiling point components distillate, Bian Jinhang melt polymerization.After value as defined in reaching in stirring torque, lead Enter nitrogen, undergo normal pressure from decompression state and become pressurized state, polymer is discharged from the lower part of aggregation container, strands are carried out It is granulated, thus pelletizing batch.The fusing point of obtained pellet is 336 DEG C, melt viscosity 19Pas.

(manufacturing method of liquid-crystalline polymer 3)

(I) 4-HBA: 1040g (48 moles of %) (HBA)

(II) 6-Hydroxy-2-naphthoic acid: 89g (3 moles of %) (HNA)

(III) terephthalic acid (TPA): 547g (21 moles of %) (TA)

(IV) M-phthalic acid: 91g (3.5 moles of %) (IA)

(V) 4,4 '-dihydroxybiphenyl: 716g (24.5 moles of %) (BP)

Potassium acetate catalyst: 110mg

Acetic anhydride: 1644g

It is added after raw material in aggregation container, the temperature of reaction system is risen to 140 DEG C, it is small that 1 is reacted at 140 DEG C When.Thereafter, 360 DEG C then with 5.5 hours are warming up to, then, 5Torr (that is, 667Pa) was decompressed to 20 minutes, while making acetic acid, mistake The acetic anhydride of amount, other low boiling point components distillate side and carry out melt polymerization.After value as defined in reaching in stirring torque, nitrogen is imported Gas, undergoes normal pressure from decompression state and becomes pressurized state, and polymer is discharged from the lower part of aggregation container, makes to strands Grain, thus pelletizing batch.The fusing point of obtained pellet is 355 DEG C, melt viscosity 10Pas.

(ingredient other than liquid-crystalline polymer)

Each liquid-crystalline polymer obtained above is mixed with following compositions using double screw extruder, is obtained compound Resin combination.The compounding amount of each ingredient is as shown in table 4 and table 5.It should be noted that hereinafter, " % " in table indicates matter Measure %.

(B) fibrous filler

Glass fibre 1: Nippon Electric Glass Co., Ltd ECS03T-786H, 10 μm of fibre diameter, length 3mm it is short Cut fiber

Glass fibre 2: Nippon Electric Glass Co., Ltd ECS03T-790DE, 6 μm of fibre diameter, length 3mm it is short Cut fiber

Milled fibre: Co. Ltd. system PF70E001,10 μm of the fibre diameter, (manufacture of 70 μm of average fiber length are spun in day east Quotient's nominal value)

It should be noted that above-mentioned manufacturer's nominal value with 100 μm in the table 4 for the actual measured value in composition not Together.

(C) plate filler

Talcum；10 μm of Ishihara Sangyo Kaisha, Ltd. CROWN TALC PP, average grain diameter

In addition, extrusion condition when obtaining composite resin composition is as follows.

[extrusion condition]

(embodiment 1~12, comparative example 1~3)

The temperature that the barrel of main feed mouth is arranged in is set as 250 DEG C, the temperature of other barrels is set as 360 DEG C.Liquid crystal Property polymer all from main feed mouth supply.In addition, filler is supplied from side to feed inlet.

(comparative example 4)

The temperature that the barrel of main feed mouth is arranged in is set as 250 DEG C, the temperature of other barrels is set as 350 DEG C.Liquid crystal Property polymer all from main feed mouth supply.In addition, filler is supplied from side to feed inlet.

(comparative example 5)

The temperature that the barrel of main feed mouth is arranged in is set as 250 DEG C, the temperature of other barrels is set as 380 DEG C.Liquid crystal Property polymer all from main feed mouth supply.In addition, filler is supplied from side to feed inlet.

It should be noted that the weight average fiber length of the fibrous filler in composite resin composition is by following Method measures.

[measurement of weight average fiber length]

Composite resin composition pellet 5g is heated 2 hours at 600 DEG C and is ashed.It is well dispersed in ash residue After in 5 mass % Aqueous Solutions of Polyethylene Glycol, culture dish is moved to dropper, with micro- sem observation fibrous filler.Meanwhile making With the weight average fiber length of image determiner (Nireco Corporation LUZEXFS) measurement fibrous filler.

(measurement of the melt viscosity of composite resin composition)

Make made Capirograph 1B type using Toyo Co., Ltd.'s essence mechanism, it is high in the fusing point than liquid-crystalline polymer At a temperature of 10~30 DEG C, using the throttle orifice of internal diameter 1mm, length 20mm, surveyed with shear velocity 1000/ second based on ISO11443 Determine the melt viscosity of composite resin composition.It should be noted that using the compound of liquid-crystalline polymer 1 for measuring temperature Resin combination is 360 DEG C, the use of the composite resin composition of liquid-crystalline polymer 2 is 350 DEG C, using liquid-crystalline polymer 3 Composite resin composition be 380 DEG C.Show the result in table 4 and table 5.

Based on following methods, the physical property of the connector shaped by composite resin composition is measured.Each evaluation result is shown In table 4 and table 5.

(bend test)

Under following molding conditions, by composite resin composition injection moulding, the formed products of 0.8mm thickness is obtained, are based on ASTM D790 measures bending strength, breaking strain and bending elastic modulus.

[molding condition]

Forming machine: the industry of Sumitomo hoisting machinery, SE100DU

Barrel temperature:

360 DEG C (embodiment 1~12, comparative example 1~3)

350 DEG C (comparative example 4)

370 DEG C (comparative example 5)

Mold temperature: 80 DEG C

Injection speed: 33mm/ seconds

(temperature of deflection under load)

By composite resin composition injection moulding under following molding conditions, formed products are obtained, are based on ISO75-1,2 measurements Temperature of deflection under load.

[molding condition]

Forming machine: the industry of Sumitomo hoisting machinery, SE100DU

Barrel temperature:

360 DEG C (embodiment 1~12, comparative example 1~3)

350 DEG C (comparative example 4)

370 DEG C (comparative example 5)

Mold temperature: 80 DEG C

Injection speed: 33mm/ seconds

(nucleation temperature)

By composite resin composition injection moulding under following molding conditions, obtain the 12.5mm with weld part × The formed products of 120mm × 0.8mm.The formed products are divided into two in above-mentioned weld part, are tested obtained part as 1 Body is clamped in the hot press of predetermined temperature 5 minutes.Thereafter, visually to study whether the surface of above-mentioned test body is sent out Raw blistering.Nucleation temperature is set as the maximum temperature that the generation number of blistering is zero.It should be noted that above-mentioned predetermined temperature exists 250~300 DEG C of range is set with 10 DEG C for interval.

[molding condition]

Forming machine: the industry of Sumitomo hoisting machinery, SE100DU

Barrel temperature:

360 DEG C (embodiment 1~12, comparative example 1~3)

350 DEG C (comparative example 4)

370 DEG C (comparative example 5)

Mold temperature: 90 DEG C

Injection speed: 33mm/ seconds

(DDR connector warpage)

Following molding conditions by composite resin composition injection moulding (cast gate: tunnel gate, gate size:), obtain distance 0.6mm between as shown in Figure 1, whole size 70.0mm × 26.0mm × 4.0mmt, pitch, The DDR-DIMM connector of pinhole number 100 × 2.

[molding condition]

Forming machine: Sumitomo hoisting machinery industry SE30DUZ

Barrel temperature:

360 DEG C (embodiment 1~12, comparative example 1~3)

350 DEG C (comparative example 4)

370 DEG C (comparative example 5)

Mold temperature: 80 DEG C

Injection speed: 200mm/ seconds

Obtained connector is rested on horizontal desk, utilizes Mitutoyo Corporation Quick The height of Vision 404PROCNC determining image machine measurement connector.At this moment, multiple positions shown in bullet are surveyed in Fig. 2 Fixed height, using the difference of maximum height and minimum constructive height from least square plane as the warpage of DDR connector.It needs to illustrate , warpage is measured before and after the IR Reflow Soldering carried out with following conditions.

[IR Reflow Soldering condition]

Measuring machine: the large-scale desk-top refluxing soft soldering apparatus RF-300 of Japan Pulse Laboratories, Inc. system (makes With far infra-red heater)

Sample conveying speed: 140mm/ seconds

Reflow soldering passes through the time: 5 minutes

The temperature condition of preheating zone: 150 DEG C

Flow back welding zone temperature strip part: 190 DEG C

Peak temperature: 251 DEG C

(DDR connector deflection)

It finds out using the difference of the warpage before and after the Reflow Soldering of above method measurement as DDR connector deflection.

(DDR connector minimum pressure to fill)

Measure the minimum injection fillers that good formed products can be obtained when by the DDR-DIMM connector injection moulding of Fig. 1 Pressure is as minimum pressure to fill.

[table 4]

[table 5]

As shown in table 4 and table 5, the heat resistance of the electronic component shaped by composite resin composition of the invention is excellent It is different, inhibit buckling deformation and blistering occur.

Claims

1. a kind of composite resin composition, it includes the fillings of (A) liquid-crystalline polymer, (B) fibrous filler and (C) plate Agent,

(A) liquid-crystalline polymer is to be used as required constituent comprising following Component units (I)~(VI) and melting When show optically anisotropic Wholly aromatic polyester amide, wherein

Relative to whole Component units, the total content of Component units (II) and Component units (IV) is 1 mole of % more than and less than 5 Mole %,

Relative to the summation of Component units (V) and Component units (VI), the molar ratio of Component units (VI) is 0.04~0.37,

The weight average fiber length of (B) fibrous filler is 250 μm or more,

(A) liquid-crystalline polymer relative to composite resin composition generally 37.5~82.5 mass %,

(B) fibrous filler relative to composite resin composition generally 2.5~17.5 mass %,

(C) the plate filler relative to composite resin composition generally 15~45 mass %,

The total amount of (B) fibrous filler and (C) the plate filler relative to composite resin composition generally 17.5~62.5 mass %,

(I)

(II)

(III)

(IV)

(V)

(VI)

2. composite resin composition according to claim 1, wherein Component units (III) are total with Component units (IV) Molal quantity is 1~1.1 times of the total mole number of Component units (V) and Component units (VI), alternatively, Component units (V) and composition The total mole number of unit (VI) is 1~1.1 times of the total mole number of Component units (III) and Component units (IV).

3. composite resin composition according to claim 1 or 2, wherein (B) fibrous filler is glass fibers Dimension.

4. composite resin composition described in any one of claim 1 to 3, wherein (C) the plate filler is to slide Stone.

5. a kind of electronic component is shaped, product by composite resin composition according to any one of claims 1 to 4 Overall length is 30mm or more, and product height is 5mm or more.

6. electronic component according to claim 5, for relative to the XY axial plane of formed products, YZ axial plane and XZ axial plane Any axial plane not no asymmetric electronic parts of symmetry.

7. electronic component according to claim 5 or 6, between pitch distance 0.6mm or less, product overall length 60.0mm with The extremely above memory module connector of upper, product height 10.0mm or less, number of poles 200.