CN109790378A - Composite resin composition and the connector as made of composite resin composition forming - Google Patents
Composite resin composition and the connector as made of composite resin composition forming Download PDFInfo
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- CN109790378A CN109790378A CN201780058271.4A CN201780058271A CN109790378A CN 109790378 A CN109790378 A CN 109790378A CN 201780058271 A CN201780058271 A CN 201780058271A CN 109790378 A CN109790378 A CN 109790378A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
- H01R12/70—Coupling devices
- H01R12/71—Coupling devices for rigid printing circuits or like structures
- H01R12/72—Coupling devices for rigid printing circuits or like structures coupling with the edge of the rigid printed circuits or like structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/46—Bases; Cases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
- Connector Housings Or Holding Contact Members (AREA)
Abstract
The present invention provides and can be realized excellent heat resistance, inhibits the manufacture of the connector of buckling deformation and blistering generation, good fluidity composite resin composition, and the connector as made of composite resin composition forming.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 200 μm or less.
Description
Technical field
The present invention relates to composite resin composition and the connectors 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 miniaturization and slimming of electronic equipment in recent years, exist to the electronic component for constituting electronic equipment
The low thickness of (connector etc.) and the demand of narrow pitch.For example, Patent Document 1 discloses one kind by utilizing mica and glass
Connector made of the liquid-crystalline polymer composition forming that glass fiber is strengthened.Such connector is used as requiring resistance to
Hot, buckling deformation inhibition, mobility, dimensional stability etc., Substrate-substrate connector and for by flexible printing base
The flexible printing board connector etc. that plate (FPC) is connect with flexible flat cable (FFC).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-37061 bulletin
Summary of the invention
Problems to be solved by the invention
But when being intended to shape connector by existing liquid-crystalline polymer composition, the heat resistance of composition, buckling deformation
Inhibition and mobility is insufficient and poor in processability, accordingly, it is difficult to manufacture opposite with the demand to low thickness and narrow pitch
The low thickness narrow pitch connector answered.
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.
The present invention has been made in view of such circumstances invention, it is intended that provide can be realized excellent heat resistance,
It inhibits buckling deformation and the manufacture for the connector occurred that blisters, good fluidity composite resin composition and is answered by this
Connector made of the forming of resin composition.
The solution to the problem
The inventors of the present invention's discovery, by the liquid-crystalline polymer, the threadiness that combine the specific Component units comprising specified amount
Filler and plate filler, and make 200 μm of the weight average fiber length of fibrous filler hereinafter, being able to solve above-mentioned
Problem.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) plate
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,
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 content 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 be 200 μm hereinafter,
For aforementioned (A) liquid-crystalline polymer relative to composite resin composition generally 35~82.5 mass %, aforementioned (B) is fine
Shape filler is tieed up relative to composite resin composition generally 1.5~17.5 mass %, aforementioned (C) plate filler is relative to multiple
Resin composition generally 12.5~47.5 mass %,
The total amount of aforementioned (B) fibrous filler and aforementioned (C) plate filler is relative to composite resin composition entirety
For 17.5~65 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 that grinding is fine
Dimension.
(4) composite resin composition according to any one of (1)~(3), wherein aforementioned (C) plate filler is
Selected from one or more of the group being made of talcum and mica.
(5) a kind of connector, the composite resin composition as described in any one of (1)~(4) shape, and product is complete
Long to be less than 30mm, product height is less than 5mm.
(6) connector according to (5) is low thickness narrow pitch connector.
(7) connector according to (5) or (6), wherein between pitch distance be 0.5mm hereinafter,
Product overall length is 3.5mm or more,
Product height be 4.0mm hereinafter,
The connector is the low thickness narrow pitch as Substrate-substrate connector or flexible printing board connector
Connector.
The effect of invention
In accordance with the invention it is possible to provide the connector for being able to achieve excellent heat resistance, buckling deformation and blistering being inhibited to occur
Manufacture, the composite resin composition of good fluidity, and the connector as made of composite resin composition forming.
Detailed description of the invention
Fig. 1 is the figure for indicating the FPC connector shaped in embodiment.It should be noted that the unit of the numerical value in figure is
mm。
Fig. 2 is the figure to locate for indicating the warpage measurement of the FPC 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 200 μm or less.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 mole %, 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 5 moles of %, Component units (II) and Component units (IV).In above-mentioned Wholly aromatic polyester amide, by with above range
Total amount the Component units (II) of the bendability with naphthalene skeleton and the Component units (IV) of the bendability with benzene skeleton coexist,
Low melting 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 Component units of bendability
Ratio 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 structure of bendability
Become excessively at the ratio of unit, 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, relative to whole Component units, containing is specific structure in Wholly aromatic polyester amide of the invention
It is specifically measured at the specific amount of (I)~(VI) of unit and Component units (II) and the summation of 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 to polymerized monomer can be used, as chloride derivative by end active
The monomer of change.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 dosage of catalyst be typically based on the gross mass of monomer be 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 or reduced pressure, non-live
The solid phase heated in property gas, can be realized the increase of molecular weight.The preferred condition of solid-phase polymerization is anti-
Answer 230~350 DEG C of 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 includes 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 dosage of 4-HBA is 50~70 moles of %, excellent from the viewpoint of taking into account low melting point and heat resistance
54~67 moles of %, more preferably 58~64 moles of % are selected as,
The dosage of 6-Hydroxy-2-naphthoic acid be more than and less than 4.5 moles % of 0.5 mole of %, from take into account low melting point and
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 dosage is 10.25~22.25 moles of %, is gone out from the viewpoint for taking into account low melting point and heat resistance
Hair, preferably 12.963~20.75 moles of %, more preferably 15.675~19.25 moles of %,
The dosage 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 heat-resisting
Property from the perspective of, preferably 0.5~3.75 mole of %, more preferably 0.5~3 mole of %,
The dosage of 4,4 '-dihydroxybiphenyls is 5.75~23.75 moles of %, from the viewpoint for taking into account low melting point and heat resistance
It sets out, preferably 8.5~20.375 moles of %, more preferably 11.25~17 moles of % (such as 11.675~17 moles of %),
The dosage of n-acetyl-p-aminophenol is 1~7 mole of %, is gone out from the viewpoint for taking into account low melting point and heat resistance
Hair, 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 dosage 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 dosage of aforementioned fatty acids acid anhydride be preferably 4-HBA, 6-Hydroxy-2-naphthoic acid, 4,4 '-dihydroxybiphenyls,
And 1.02~1.04 times of total hydroxyl equivalent of n-acetyl-p-aminophenol.More preferable above-mentioned fatty acid metal salts are acetic 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 always rub
That number (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, when being inserted between cross-polarization piece, light can be made to penetrate.Sample is that optics is each
When anisotropy, 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 35~82.5 mass %.The content of liquid-crystalline polymer is integrally small relative to composite resin composition
When 35 mass %, the mobility of composite resin composition is easy to deteriorate, in addition, the connector obtained by composite resin composition
The buckling deformation of equal formed products may become larger, therefore not preferably.The content of liquid-crystalline polymer is combined relative to compound resin
Object integrally more than 82.5 mass % when, the bending elastic modulus of the formed products such as connector obtained by composite resin composition and resistance to
Anti-thread breakage reduction, therefore not preferably.Composite resin composition of the invention is preferably in composite resin composition relative to compound
Resin combination integrally includes the above-mentioned liquid-crystalline polymer of 47~75 mass %, more preferably includes 60~65 mass %.
(fibrous filler)
Composite resin composition of the invention includes above-mentioned liquid-crystalline polymer and fibrous filler, fibrous filler
Weight average fiber length be 200 μm hereinafter, therefore, by the high temperature of formed products obtained from composite resin composition forming
Rigidity and mobility are excellent, inhibit buckling deformation.Fibrous filler can be used alone or two or more is applied in combination.
It as fibrous filler of the invention, is not particularly limited, it is fine that glass fibre, milled fibre, carbon fiber, asbestos can be enumerated
Dimension, silicon dioxide fibre, silica alumina fiber, Zirconium oxide fibre, boron nitride fiber, silicon nitride fiber, boron fibre,
Potassium titanate fibre etc..Since the high temperature rigid of the formed products obtained by composite resin composition is easy to improve, as this hair
Bright fibrous filler, preferably milled fibre.
In composite resin composition of the invention, the weight average fiber length of fibrous filler is 200 μm or less, excellent
It is selected as 170 μm or less, more preferably 150 μm or less.When above-mentioned weight average fiber length is more than 200 μm, compound resin combination
The mobility of object is not variable, and sufficiently the buckling deformation of formed products may become larger, therefore not preferably.It is fine as above-mentioned weight average
The lower limit for tieing up length, is not particularly limited, preferably 50 μm or more, more preferably 70 μm or more.Above-mentioned weight average fiber is long
When degree is 50 μm or more, the high temperature rigid of the formed products obtained by composite resin composition is easy to become sufficiently, therefore preferably.It needs
Illustrate, in this specification, the weight average fiber length of fibrous filler refers to, by composite resin composition 600
It heats to be ashed for 2 hours at DEG C and obtains ash residue, which is dispersed in 5 mass % Aqueous Solutions of Polyethylene Glycol
In, dispersion liquid is obtained, weight average fiber length obtained from being measured using image determiner to the dispersion liquid.
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 1.5~17.5 mass %.The content of fibrous filler is integrally less than relative to composite resin composition
When 1.5 mass %, the temperature of deflection under load of the formed products such as connector obtained by composite resin composition is low, and high temperature rigid is not filled
Point, therefore not preferably.The content of fibrous filler relative to composite resin composition integrally more than 17.5 mass % when, combination
The mobility of object deteriorates, and the buckling deformation of formed products may become larger, therefore not preferably.Fibrous filler of the invention is preferred
Be included in composite resin composition relative to the whole amount with 4~16 mass % of composite resin composition, more preferably comprising 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 12.5~47.5 mass % relative to composite resin composition.Plate filler
Content relative to composite resin composition integrally less than 12.5 mass % when, the formed products that are obtained by composite resin composition are stuck up
The inhibition of song deformation is insufficient, therefore not preferably.The content of plate filler is integrally more than relative to composite resin composition
When 47.5 mass %, the mobility of composite resin composition deteriorates, and the forming of composite resin composition may become difficult therefore unexcellent
Choosing.Plate filler of the invention is included in compound preferably with respect to the whole amount with 20~37 mass % of composite resin composition
It more preferably include 25~35 mass % in resin combination.
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, is preferably selected from a kind or more of talcum and mica, more preferable talcum.In addition, to the no spy of the average grain diameter of plate filler
It does not limit, it is preferably smaller if considering the mobility in thinner wall section.On the other hand, in order to make by composite resin composition
The buckling deformation of the formed products such as obtained connector is smaller, needs to maintain certain size.Specifically, it is preferable that 1~100 μm,
More preferable 5~50 μm.
(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 connector shaped by the 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 connector shaped by the 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 addition, 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 connector shaped by the 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 excellent from the aspect of, price good from form and aspect is low
Select 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 connector 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 connector 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 17.5~65 mass %.Above-mentioned total amount 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 the connector obtained by composite resin composition is rigidly insufficient, in addition, warpage
Deformation may become larger, therefore not preferably.Above-mentioned total amount relative to composite resin composition integrally more than 65 mass % when, it is compound
The mobility of resin combination deteriorates, the buckling deformation of formed products may become larger, therefore not preferably.Above-mentioned total amount is preferably opposite
In composite resin composition generally 25~53 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 200 μm of weight average fiber length for making fibrous filler or less, 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, connector, the especially small-sized and with complex shape component such as low thickness narrow pitch connector can be preferably shaped to
Deng.The degree of mobility is judged by the minimum pressure to fill of connector.That is, by the injection of FPC connector shown in Fig. 1
The minimum injection fillers pressure that good formed products can be obtained when forming is defined as minimum pressure to fill.Minimum pressure to fill is got over
It is low, 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
Consider from the following aspect below) it is preferable that connector, especially low thickness narrow pitch connector forming when, it is ensured that it is multiple
The mobility of resin composition, and stuffing pressure will not become over.
(connector)
By shaping composite resin composition of the invention, connector of the invention can be obtained.As of the invention
Connector is not particularly limited, such as can enumerate the connector that product overall length is less than 5mm less than 30mm, product height.As
Product overall length is less than 30mm, product height is less than the connector of 5mm, is not particularly limited, such as can enumerate: the narrow section of low thickness
Away from connector, coaxial connector, Micro SIM connector, Micro SD connector etc..Wherein, low thickness narrow pitch connector
It is suitable.It as low thickness narrow pitch connector, is not particularly limited, such as can enumerate: Substrate-substrate connector (
It is known as " BtoB connector "), flexible printing board connector will be (for will be flexible printing substrate (FPC) and flexible
Flat cable (FFC) connection, also known as " FPC connector ") etc..Wherein, distance is 0.5mm or less, produces between pitch
Product overall length is 3.5mm or more, product height is 4.0mm or less, is connected as Substrate-substrate connector or flexible printing substrate
It is suitable for connecing the low thickness narrow pitch connector of device.
As the manufacturing process of connector of the invention is obtained, it is not particularly limited, the connector obtained in order to prevent
Deformation etc., preferably selects the molding condition of no remaining internal stress.In order to reduce stuffing pressure, reduce obtained connector
The barrel temperature of remaining internal stress, forming machine is preferably the temperature of the fusing point of liquid-crystalline polymer or more.
In addition, mold temperature is preferably 70~100 DEG C.When mold temperature is low, compound resin combination in a mold is filled
Object may flow bad therefore not preferred.When mold temperature is high, the problems such as generation of burr may be generated, therefore
Not preferably.For injection speed, preferably it was formed with 150mm/ seconds or more.When injection speed is low, it may only be possible to not filled out
Formed products are filled, may be also the formed products that stuffing pressure is high and remaining internal stress is big even if obtaining fully filled formed products,
It can only obtain the connector of flatness difference.
Connector of the invention inhibits buckling deformation.The degree of the warpage of connector is such as got off judgement.That is, utilizing Fig. 1
Shown in FPC connector, multiple position finding height shown in bullet in Fig. 2, by the maximum from least square plane
Highly with the difference of minimum constructive height as warpage.Connector of the invention inhibits warpage before carrying out IR Reflow Soldering and later
Variation.
In addition, connector 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 the connector obtained by composite resin composition of the invention, for example being commented by high temperature rigid
The excellent heat resistance of valence.High temperature rigid is evaluated by being based on ISO75-1,2 measuring load deflection temperatures.
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 double screw extruder ((strain) Nippon 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 hoisting machinery industry (strain) system " SE100DU ")
It is shaped under molding condition below, obtains measurement test film (4mm × 10mm × 80mm).Using the test film, base is utilized
In ISO75-1,2 method measuring load deflection temperature.It should be noted that using 1.8MPa as bending stress.By result
It is shown 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/sec
[melt viscosity]
(strain) Toyo Seiki is used to make made Capirograph, it is 10~30 DEG C high with the fusing point than liquid-crystalline polymer
Temperature, it is poly- based on ISO11443 measurement liquid crystal liquid crystal property with shear velocity 1000/ second using the throttle orifice of internal diameter 1mm, length 20mm
Close the melt viscosity of object.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]
< Examples 1 to 10,1~6 > of comparative example
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]
Use (strain) Toyo Seiki to make made Capirograph 1B type, the fusing point than liquid-crystalline polymer it is high by 10~
Using the throttle orifice of internal diameter 1mm, length 20mm at a temperature of 30 DEG C, liquid is measured based on ISO11443 with shear velocity 1000/ second
The melt viscosity of crystalline substance polymer.It should be noted that for measuring temperature, liquid-crystalline polymer 1 is 360 DEG C, liquid crystal liquid crystal property is poly-
Conjunction object 2 is 350 DEG C, liquid-crystalline polymer 3 is 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)
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: 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: Japan Electric Glass (strain) ECS03T-786H processed, 10 μm of fibre diameter, length 3mm chopped strand
Milled fibre: (strain) PF70E001 processed, 70 μm of 10 μm of fibre diameter, average fiber length (manufacturing marks are spun in day east
Title 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: loose village's industry (strain) CROWN TALC PP processed, 10 μm of average grain diameter
Mica: (strain) mountain pass mica industry AB-25S, 25 μm of average grain diameter
In addition, extrusion condition when obtaining composite resin composition is as follows.
[extrusion condition]
(Examples 1 to 10, 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 5,6)
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 370 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)
Use (strain) Toyo Seiki to make made Capirograph 1B type, the fusing point than liquid-crystalline polymer it is high by 10~
It is multiple based on ISO11443 measurement with shear velocity 1000/ second using the throttle orifice of internal diameter 1mm, length 20mm at a temperature of 30 DEG C
The melt viscosity of resin composition.It should be noted that using the compound resin of liquid-crystalline polymer 1 for measuring temperature
Composition is 360 DEG C, the use of the composite resin composition of liquid-crystalline polymer 2 is 350 DEG C, answering using liquid-crystalline polymer 3
Resin composition is 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 (Examples 1 to 10, comparative example 1~3)
350 DEG C (comparative example 4)
370 DEG C (comparative example 5,6)
Mold temperature: 80 DEG C
Injection speed: 33mm/sec
(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 (Examples 1 to 10, comparative example 1~3)
350 DEG C (comparative example 4)
370 DEG C (comparative example 5,6)
Mold temperature: 80 DEG C
Injection speed: 33mm/sec
(nucleation temperature)
By composite resin composition injection moulding under following molding conditions, obtain the 12.5mm with fused portion ×
The formed products of 120mm × 0.8mm.The formed products are divided into two in above-mentioned fused portion, are tested obtained part as 1
Body is clamped in the hot press of predetermined temperature 5 minutes.Thereafter, visually whether research occurs on the surface of above-mentioned test body
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 is 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 (Examples 1 to 10, comparative example 1~3)
350 DEG C (comparative example 4)
370 DEG C (comparative example 5,6)
Mold temperature: 90 DEG C
Injection speed: 33mm/sec
(FPC connector warpage)
Under following molding conditions by composite resin composition injection moulding (cast gate: tunnel gate, gate size:), obtain distance 0.5mm, pin hole between whole size 17.6mm × 4.00mm × 1.16mm as shown in Figure 1, pitch
30 × 2 needle of number, minimum wall thickness (MINI W.): the FPC connector of 0.12mm.
[molding condition]
Forming machine: the industry of Sumitomo hoisting machinery, SE30DUZ
Barrel temperature (indicates the temperature from nozzle side):
360 DEG C -360 DEG C -350 DEG C -340 DEG C (Examples 1 to 10, comparative example 1~3)
350 DEG C -350 DEG C -340 DEG C -330 DEG C (comparative example 4)
370 DEG C -370 DEG C -360 DEG C -350 DEG C (comparative example 5,6)
Mold temperature: 80 DEG C
Injection speed: 200mm/sec
Dwell pressure: 50MPa
Dwell time: 0.5 second
Cooling time: 10 seconds
Screw speed: 120rpm
Screw back pressure: 1.2MPa
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 FPC 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/sec
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
(FPC connector deflection)
It finds out using the difference of the warpage before and after the Reflow Soldering that the above method measures as FPC connector deflection.
(FPC connector minimum pressure to fill)
It measures and obtains the smallest injection fillers pressure of good formed products when by the FPC connector injection moulding of Fig. 1
As minimum pressure to fill.
[table 4]
[table 5]
As shown in table 4 and table 5, the mobility of composite resin composition of the invention is excellent, by the composite resin composition
The excellent heat resistance of connector made of forming inhibits buckling deformation and blistering to occur.
Claims (7)
1. a kind of composite resin composition, it includes: (A) liquid-crystalline polymer, (B) fibrous filler and (C) plate are filled
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,
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 content of Component units (II) and Component units (IV) are 1 mole of % more than and less than 5
Mole %,
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 (B) fibrous filler be 200 μm hereinafter,
(A) liquid-crystalline polymer relative to composite resin composition generally 35~82.5 mass %,
(B) fibrous filler relative to composite resin composition generally 1.5~17.5 mass %,
(C) the plate filler relative to composite resin composition generally 12.5~47.5 mass %,
The total amount of (B) fibrous filler and (C) the plate filler relative to composite resin composition generally
17.5~65 mass %,
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 that grinding is fine
Dimension.
4. composite resin composition described in any one of claim 1 to 3, wherein (C) the plate filler is choosing
One or more of the group of free talcum and mica composition.
5. a kind of connector is shaped by composite resin composition according to any one of claims 1 to 4, product is complete
Long to be less than 30mm, product height is less than 5mm.
6. connector according to claim 5 is low thickness narrow pitch connector.
7. connector according to claim 5 or 6, between pitch distance be 0.5mm hereinafter,
Product overall length is 3.5mm or more,
Product height be 4.0mm hereinafter,
The connector is connected as the low thickness narrow pitch of Substrate-substrate connector or flexible printing board connector
Device.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016199062 | 2016-10-07 | ||
| JP2016-199062 | 2016-10-07 | ||
| PCT/JP2017/034795 WO2018066417A1 (en) | 2016-10-07 | 2017-09-26 | Composite resin composition, and connector formed from said composite resin composition |
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| Publication Number | Publication Date |
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| CN109790378A true CN109790378A (en) | 2019-05-21 |
| CN109790378B CN109790378B (en) | 2020-09-11 |
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| CN201780058271.4A Active CN109790378B (en) | 2016-10-07 | 2017-09-26 | Composite resin composition and connector molded from the same |
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|---|---|
| JP (1) | JP6356938B1 (en) |
| KR (1) | KR102052662B1 (en) |
| CN (1) | CN109790378B (en) |
| PH (1) | PH12019500728A1 (en) |
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| WO (1) | WO2018066417A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115551948A (en) * | 2020-05-13 | 2022-12-30 | 宝理塑料株式会社 | Liquid crystalline resin composition for surface mount relay and surface mount relay using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10829634B2 (en) | 2017-12-05 | 2020-11-10 | Ticona Llc | Aromatic polymer composition for use in a camera module |
| WO2020190568A1 (en) | 2019-03-20 | 2020-09-24 | Ticona Llc | Actuator assembly for a camera module |
| JP2022524720A (en) | 2019-03-20 | 2022-05-10 | ティコナ・エルエルシー | Polymer composition for use in camera modules |
| KR102245200B1 (en) | 2019-07-09 | 2021-04-27 | 단국대학교 산학협력단 | Composition for micro connector and micro connector using the same |
| WO2022168706A1 (en) * | 2021-02-05 | 2022-08-11 | ポリプラスチックス株式会社 | Fan impeller liquid crystal resin composition and fan impeller which uses same |
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| WO2016088714A1 (en) * | 2014-12-05 | 2016-06-09 | ポリプラスチックス株式会社 | Composite resin composition and planar connector |
| JP2016124947A (en) * | 2014-12-26 | 2016-07-11 | ポリプラスチックス株式会社 | Production method of molded article and composite resin composition |
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| WO1998056578A1 (en) * | 1997-06-13 | 1998-12-17 | Nippon Petrochemicals Company, Limited | Bonded composite and sealing composition for use in the same |
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| JP2014533325A (en) * | 2011-11-15 | 2014-12-11 | ティコナ・エルエルシー | Low naphthenic liquid crystal polymer composition |
| CN104080836B (en) * | 2012-01-31 | 2016-08-24 | 吉坤日矿日石能源株式会社 | Liquid crystal polyesteramide, liquid crystal polyesteramide resin combination and molded body |
| JP6157779B1 (en) * | 2015-10-21 | 2017-07-05 | ポリプラスチックス株式会社 | Totally aromatic polyester amide and method for producing the same |
-
2017
- 2017-09-26 WO PCT/JP2017/034795 patent/WO2018066417A1/en active Application Filing
- 2017-09-26 CN CN201780058271.4A patent/CN109790378B/en active Active
- 2017-09-26 JP JP2018508240A patent/JP6356938B1/en active Active
- 2017-09-26 KR KR1020197006402A patent/KR102052662B1/en active IP Right Grant
- 2017-09-30 TW TW106133901A patent/TWI721219B/en active
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2019
- 2019-04-03 PH PH12019500728A patent/PH12019500728A1/en unknown
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| US5798432A (en) * | 1996-03-22 | 1998-08-25 | Hoechst Celanese Corp. | Method of making thermotropic liquid crystalline polymers containing hydroquinone |
| CN103459459A (en) * | 2011-04-01 | 2013-12-18 | 宝理塑料株式会社 | Fully aromatic polyester and polyester resin composition |
| CN104704049A (en) * | 2012-09-26 | 2015-06-10 | 宝理塑料株式会社 | Composite resin composition for electronic component and electronic component molded from composite resin composition |
| WO2016088714A1 (en) * | 2014-12-05 | 2016-06-09 | ポリプラスチックス株式会社 | Composite resin composition and planar connector |
| JP2016124947A (en) * | 2014-12-26 | 2016-07-11 | ポリプラスチックス株式会社 | Production method of molded article and composite resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115551948A (en) * | 2020-05-13 | 2022-12-30 | 宝理塑料株式会社 | Liquid crystalline resin composition for surface mount relay and surface mount relay using same |
| CN115551948B (en) * | 2020-05-13 | 2023-04-11 | 宝理塑料株式会社 | Liquid crystalline resin composition for surface mount relay and surface mount relay using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2018066417A1 (en) | 2018-10-04 |
| KR20190028556A (en) | 2019-03-18 |
| CN109790378B (en) | 2020-09-11 |
| KR102052662B1 (en) | 2019-12-05 |
| PH12019500728A1 (en) | 2019-11-11 |
| WO2018066417A1 (en) | 2018-04-12 |
| JP6356938B1 (en) | 2018-07-11 |
| TWI721219B (en) | 2021-03-11 |
| TW201829618A (en) | 2018-08-16 |
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