CN109844028A - Relay liquid crystalline resin composition is installed and relay is installed using its surface in surface - Google Patents
Relay liquid crystalline resin composition is installed and relay is installed using its surface in surface Download PDFInfo
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- CN109844028A CN109844028A CN201780064384.5A CN201780064384A CN109844028A CN 109844028 A CN109844028 A CN 109844028A CN 201780064384 A CN201780064384 A CN 201780064384A CN 109844028 A CN109844028 A CN 109844028A
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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
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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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
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H45/00—Details of relays
- H01H45/02—Bases; Casings; Covers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
Abstract
It provides surface relay liquid crystalline resin composition is installed and relay is installed using its surface installation relay component and surface, the surface installation relay is suppressed with liquid crystalline resin composition offer excellent heat resistance, the generation of blistering and the disengaging of filler, can use the molded product that bonding agent is bonded with high-adhesive-strength.Surface installation relay of the invention includes (A) liquid-crystalline polymer and (B) fibrous filler with liquid crystalline resin composition, above-mentioned (A) liquid-crystalline polymer is that following structural units (I)~(VI) comprising specified amount is used as required constituent, and optically anisotropic Wholly aromatic polyester amide is shown in melting, the weight average fiber length of above-mentioned (B) fibrous filler is 50~170 μm, the containing ratio for the component that 20~200 μm of fibre length is 70 mass % or more, above-mentioned surface installation relay is to have pedestal and from said base terminal outstanding, so that above-mentioned terminal is welded in the surface installation relay of printed base plate.
Description
Technical field
Relay is installed the present invention relates to surface installation relay liquid crystalline resin composition and using its surface.
Background technique
With the development of electronic industry, the also steady-state growth of the output of relay also spreads communication equipment, OA using field
Equipment, household appliance, automatic vending machine etc..In the past, as the relay for being installed on printed base plate and using, it is known to insertion peace
The relay of dress type (through-hole type).Insertion installation relay has from relay main body vertically terminal outstanding, firstly, should
Terminal is inserted into the hole of printed base plate, is thus placed in the one side of printed base plate.Then, in the another side of above-mentioned printed base plate
Above-mentioned terminal is welded, thus insertion installation relay is fixed in printed base plate in a manner of conductive.
In recent years, as the new relay for being installed on printed base plate and using, surface installing type (surface is developed
Mounted type) relay (such as patent document 1).Surface is installed in relay, is vertically protruded by relay main body
Terminal bend to right angle so that welding surface is parallel with relay main body.Therefore, relay is installed for surface, is not
The providing holes in printed base plate, but load above-mentioned terminal on the pad being arranged on the conductive pattern on printed base plate surface and lead to
It crosses carry out solder reflow process and is fixed on printed base plate in a manner of conductive.
Existing technical literature
Patent document
Patent document 1: No. 3463310 bulletins of Japanese Patent No.
Summary of the invention
Problems to be solved by the invention
As described above, relay is installed on surface is fixed on printed base plate by solder reflow process, therefore it is required that structure
At the molded product of surface installation relay, there is excellent heat resistance such as pedestal, shell, bobbin and be resistant to solder
Reflow process.In addition, surface installation relay is also required also to be able to maintain air-tightness after solder reflow process.Therefore,
It is required that above-mentioned molded product, particularly pedestal can be bonded with high-adhesive-strength by bonding agent with shell.
Then, liquid-crystalline polymer composition attracts attention since heat resistance, dimensional accuracy, mobility etc. are excellent.But
It is that there may be blister liquid-crystalline polymer composition.That is, the liquid crystalline polyester acyl as liquid-crystalline polymer
Amine is often used in the material for needing the heat treatment under high temperature since high high-temp stability is good.But following ask can be caused
Topic: if molded product placed for a long time in the air of high temperature and in liquid, surface, which generates, is referred to as the subtle swollen of blistering
It is swollen.The phenomenon is since decomposition gas generated when liquid crystalline polyester amide is in a molten state etc. is brought into molded product
Inside, then, the gas exapnsion and the upward surface of the molded article softened because of heating when carrying out the heat treatment of high temperature,
The part being pressed upwards occurs in the form blistered.By sufficiently deaerating, forming from venthole when material molten is squeezed out
When not for a long time in molding machine be detained etc., the generation of blistering can also be reduced.But condition and range is very narrow, for obtaining
Inhibit blistering generation molded product, i.e. have resistance to foaming molded product for and it is insufficient.In order to fundamentally solve
The generation of bubble needs to improve the quality of liquid crystalline polyester amide itself, well known liquid crystalline polyester amide, the method pair using it
It is insufficient for solving the problems, such as that blistering generates.In addition, liquid-crystalline polymer composition is also possible to create the problem that
Filler is prominent from the surface of the molded article of the composition, and then is detached from, and generates the dysfunctions such as the poor flow of product.
The present invention is made in view of the situation, it is therefore intended that, installation relay liquid-crystalline resin in surface is provided
Composition, the surface formed by above-mentioned composition installation relay component and the surface installation relay for having above-mentioned component,
Surface installation relay with liquid crystalline resin composition can provide excellent heat resistance, the generation of blistering and the disengaging of filler by
To inhibiting, can use the molded product that bonding agent is bonded with high-adhesive-strength.
The solution to the problem
The present inventors discovery, by by with specified amount include specific structural unit liquid-crystalline polymer and threadiness
The weight average fiber length of fibrous filler is set as 50~170 μm, will have 20 in fibrous filler by filler combination
The containing ratio of the component of~200 μm of fibre length is set as 70 mass % or more, so as to solve the above subject.It is specific and
Speech, the present invention provide scheme as described below.
(1) a kind of liquid crystalline resin composition is the table comprising (A) liquid-crystalline polymer He (B) fibrous filler
Relay liquid crystalline resin composition is installed in face,
Above-mentioned (A) liquid-crystalline polymer be comprising following structural units (I)~(VI) as required constituent and
Optically anisotropic Wholly aromatic polyester amide is shown when melting,
Relative to entire infrastructure unit, the content of structural unit (I) is 50~70 moles of %,
Relative to entire infrastructure unit, the content of structural unit (II) is more than and less than 4.5 moles % of 0.5 mole of %,
Relative to entire infrastructure unit, the content of structural unit (III) is 10.25~22.25 moles of %,
Relative to entire infrastructure unit, the content of structural unit (IV) is more than and less than 4.5 moles % of 0.5 mole of %,
Relative to entire infrastructure unit, the content of structural unit (V) is 5.75~23.75 moles of %,
Relative to entire infrastructure unit, the content of structural unit (VI) is 1~7 mole of %,
Relative to entire infrastructure unit, total content of structural unit (II) and structural unit (IV) are 1 mole of % or more
And less than 5 moles %,
Relative to entire infrastructure unit, the total content of structural unit (I)~(VI) is 100 moles of %,
Structural unit (VI) relative to total molar ratio of structural unit (V) and structural unit (VI) be 0.04~
0.37,
The weight average fiber length of above-mentioned (B) fibrous filler is 50~170 μm,
In above-mentioned (B) fibrous filler, the containing ratio of the component with 20~200 μm of fibre length is 70 matter
% or more is measured,
Above-mentioned (A) liquid-crystalline polymer relative to liquid crystalline resin composition generally 50~70 mass %,
Above-mentioned (B) fibrous filler relative to liquid crystalline resin composition generally 30~50 mass %,
Above-mentioned surface installation relay be have pedestal and from said base terminal outstanding, above-mentioned terminal is welded in
The surface of printed base plate is installed by relay.
(2) liquid crystalline resin composition according to (1), wherein the conjunction of structural unit (III) and structural unit (IV)
Meter molal quantity is 1~1.1 times of total molal quantity of structural unit (V) and structural unit (VI) or structural unit (V) and knot
Total molal quantity of structure unit (VI) is 1~1.1 times of total molal quantity of structural unit (III) and structural unit (IV).
(3) liquid crystalline resin composition according to (1) or (2), wherein above-mentioned (B) fibrous filler is grinding
Fiber.
(4) relay component is installed on a kind of surface, and the composition as described in any one of (1)~(3) is formed.
(5) relay is installed on a kind of surface, has component described in (4).
The effect of invention
According to the present invention it is possible to provide surface installation relay liquid crystalline resin composition, formed by above-mentioned composition
Surface installation relay component and have the surface installation relay of above-mentioned component, relay liquid is installed on the surface
Crystalline substance resin combination provides excellent heat resistance, the generation of blistering and the disengaging of filler are suppressed, can using bonding agent with
The molded product that high-adhesive-strength is bonded.
Detailed description of the invention
Fig. 1: Fig. 1 (a) is the perspective view for schematically showing the embodiment of installation relay in surface of the invention, Fig. 1
(b) be the partial sectional view for showing the AA section of (a) of Fig. 1.
Fig. 2: Fig. 2 (a) and (b) of Fig. 2 are to schematically show the embodiment of installation relay in surface of the invention
It is installed on the side view of the state of printed base plate.
Fig. 3: Fig. 3 (a) is the figure for illustrating the manufacturing method of the sample for evaluating adhesive strength, and (b) of Fig. 3 is
For illustrating to evaluate the figure of the method for adhesive strength.
Specific embodiment
Embodiments of the present invention are specifically described below.
[surface being installed by relay liquid crystalline resin composition]
Surface installation relay of the invention includes respectively specific liquid crystal liquid crystal property with specified amount with liquid crystalline resin composition
Polymer and fibrous filler, the weight average fiber length of fibrous filler is 50~170 μm, in fibrous filler,
The containing ratio of component with 20~200 μm of fibre length is 70 mass % or more, and above-mentioned surface installation relay is to have
Pedestal and from said base terminal outstanding, make above-mentioned terminal be welded in printed base plate surface install relay.It is right below
The ingredient for constituting liquid crystalline resin composition of the invention is illustrated.
(liquid-crystalline polymer)
It is included as the liquid-crystalline polymer of above-mentioned Wholly aromatic polyester amide in liquid crystalline resin composition of the invention.On
The fusing point for stating Wholly aromatic polyester amide is low, therefore can reduce processing temperature, inhibits the generation of decomposition gas when melting.Its
As a result, the blistering comprising molded product obtained from the molding of the liquid crystalline resin composition of above-mentioned Wholly aromatic polyester amide is produced
Life is suppressed, and resistance to foaming improves.Liquid-crystalline polymer can be used alone or combine two or more use.
Wholly aromatic polyester amide in the present invention includes following structural units (I), following structural units (II), Xia Shujie
Structure unit (III), following structural units (IV), following structural units (V) and following structural units (VI).
Structural unit (I) is by 4-HBA (hereinafter also referred to " HBA ".) derived from.Full fragrance in the present invention
Adoption esteramides includes structural unit (I) 50~70 moles of % relative to entire infrastructure unit.The content of structural unit (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
From the perspective of low melting point and heat resistance, the content of structural unit (I) is preferably 54~67 moles of %, more preferably 58~64
Mole %.
Structural unit (II) is by 6-Hydroxy-2-naphthoic acid (hereinafter also referred to " HNA ".) derived from.It is complete in the present invention
Aromatic polyester amide includes more than and less than 4.5 moles % of structural unit (II) 0.5 mole of % relative to entire infrastructure unit.
The content of structural unit (II) is less than 0.5 mole of % or when being 4.5 moles of % or more, in low melting point and heat resistance at least
One is easy to become inadequate.From the viewpoint of taking into account low melting point and heat resistance, the content of structural unit (II) is preferably
0.75~3.75 mole of %, more preferably 1~3 mole of %.
Structural unit (III) is by 1,4- phenylene dicarboxylic acids (hereinafter also referred to " TA ".) derived from.It is complete in the present invention
Aromatic polyester amide includes structural unit (III) 10.25~22.25 moles of % relative to entire infrastructure unit.Structural unit
(III) when content is less than 10.25 moles of % or more than 22.25 moles of %, at least one of low melting point and heat resistance
It is easy to become inadequate.From the viewpoint of taking into account low melting point and heat resistance, the content of structural unit (III) is preferably
12.963~20.75 moles of %, more preferably 15.675~19.25 moles of %.
Structural unit (IV) is by 1,3- phenylene dicarboxylic acids (hereinafter also referred to " IA ".) derived from.It is complete in the present invention
Aromatic polyester amide includes more than and less than 4.5 moles % of structural unit (IV) 0.5 mole of % relative to entire infrastructure unit.
The content of structural unit (IV) is less than 0.5 mole of % or when being 4.5 moles of % or more, in low melting point and heat resistance at least
One is easy to become inadequate.From the viewpoint of taking into account low melting point and heat resistance, the content of structural unit (IV) is preferably
0.5~3.75 mole of %, more preferably 0.5~3 mole of %.
Structural unit (V) is by 4,4 '-dihydroxybiphenyls (hereinafter also referred to " BP ".) derived from.Full virtue in the present invention
It include structural unit (V) 5.75~23.75 moles of % relative to entire infrastructure unit in fragrant adoption esteramides.Structural unit (V)
Content less than 5.75 moles of % or more than 23.75 moles of % when, at least one of low melting point and heat resistance be easy become
It obtains insufficient.From the viewpoint of taking into account low melting point and heat resistance, the content of structural unit (V) is preferably 8.5~20.375
Mole %, more preferably 11.25~17 moles of % (such as 11.675~17 moles of %).
Structural unit (VI) is by n-acetyl p-aminophenol (hereinafter also referred to " APAP ".) derived from.In the present invention
Wholly aromatic polyester amide in, relative to entire infrastructure unit include structural unit (VI) 1~7 mole of %.Structural unit
(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 not
Sufficiently.From the viewpoint of taking into account low melting point and heat resistance, the content of structural unit (VI) is preferably 1.5~7 moles of %, more
Preferably 2~7 moles of %.
Wholly aromatic polyester amide in the present invention includes to add up to 1 mole of % or more and small relative to entire infrastructure unit
In the structural unit (II) and structural unit (IV) of 5 moles of %.By making in above-mentioned Wholly aromatic polyester amide with above range
Total amount and deposit the bendability with naphthalene skeleton structural unit (II) and the bendability with benzene skeleton structural unit
(IV), it thus becomes easy and sufficiently takes into account low melting point and heat resistance.When above-mentioned total content is less than 1 mole of %, bendability
The ratio of structural unit becomes very few, therefore low melting point is easy to become inadequate.Above-mentioned total content is 5 moles of % or more
When, the ratio of the structural unit of bendability becomes excessively, therefore heat resistance is easy to become inadequate.From taking into account low melting point and resistance to
From the perspective of hot, above-mentioned total content is preferably 1.75~4.75 moles of %, more preferably 2.5~4.5 moles of %.
In Wholly aromatic polyester amide in the present invention, structural unit (VI) is relative to structural unit (V) and structure list
Total molar ratio of first (VI) is 0.04~0.37.When above-mentioned molar ratio is less than 0.04, the structural unit with biphenyl backbone
Ratio become it is more, therefore Wholly aromatic polyester amide crystallinity reduction, low melting point and taking into account for heat resistance are easy to become not
Sufficiently.In addition, the xenogenesis key other than ester bond increases, therefore the knot of Wholly aromatic polyester amide when above-mentioned molar ratio is more than 0.37
Crystalline substance reduces, 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, the conjunction of preferred structure unit (III) and structural unit (IV)
It counts molal quantity (hereinafter also referred to " molal quantity 1A ".) be total molal quantity of structural unit (V) and structural unit (VI) (below
Referred to as " molal quantity 2A ".) 1~1.1 times or molal quantity 2A be 1~1.1 times of molal quantity 1A.More preferable molal quantity 1A is
1.02~1.06 times or molal quantity 2A of molal quantity 2A are 1.02~1.06 times of molal quantity 1A.Even more preferably mole
It is 1.024~1.056 times of molal quantity 1A that number 1A, which is 1.024~1.056 times or molal quantity 2A of molal quantity 2A,.
As described above, the Wholly aromatic polyester amide in the present invention contains work relative to entire infrastructure unit with specific amount
For (I)~(VI) and structural unit (II) of specific structural unit and total, and the structural unit of structural unit (IV)
(VI) total molar ratio relative to structural unit (V) and structural unit (VI) is specific range, therefore is sufficiently taken into account low
Fusing point and heat resistance.Contain it should be noted that Wholly aromatic polyester amide of the invention adds up to relative to entire infrastructure unit
There is structural unit (I)~(VI) of 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 is
At 260 DEG C or more, has the tendency that heat resistance raising, therefore preferably.DTUL is in the state of following liquid crystalline resin composition
The value of measurement can be measured based on ISO75-1,2, wherein the liquid crystalline resin composition is to gather above-mentioned all aromatic
11 μm of 60 mass % of esteramides and avarage fiber diameter, 75 μm of average fiber length 40 mass % of milled fibre in above-mentioned full virtue
At+20 DEG C of fusing point of fragrant adoption esteramides obtained from melting mixing.From the viewpoint of taking into account low melting point and heat resistance,
DTUL is preferably 265 DEG C or more and 310 DEG C or less, more preferably 267~300 DEG C.
Then, the manufacturing method of the Wholly aromatic polyester amide in the present invention is illustrated.Full fragrance in the present invention
Direct polymerization method, ester-interchange method etc. can be used to be polymerize for adoption esteramides.It is poly- using melt phase polycondensation, solution when polymerization
Combination of more than two kinds in legal, slurry polymerisation process, solid phase polymerization method etc. or these methods is, it is preferable to use melt phase polycondensation
Or the combination of melt phase polycondensation and solid phase polymerization method.
In the present invention, polymerization when the acylating agent for polymerized monomer can be used, by end in the form of chloride derivative
The monomer of activation.As acylating agent, fatty acid anhydrides such as acetic anhydride etc. can be enumerated.
When polymerizeing these, various catalyst can be used, as representative catalyst, dialkyl group oxidation can be enumerated
Tin, diaryl tin oxide, titanium dioxide, alkoxytitanium silicates, Titanium alkoxides class, fatty acid metal salts, BF3Etc Louis
This hydrochlorate etc., preferred fat acid metal salt.The dosage of catalyst based on the gross mass of monomer be typically about 0.001~1 mass %,
Particularly preferred about 0.003~0.2 mass %.
In addition, as solvent, atoleine, high-fire resistance can be used to close when carrying out polymerisation in solution or slurry polymerisation
At oil, inert mineral oil etc..
As reaction condition, for example, reaction temperature be 200~380 DEG C, eventually arrive at pressure and be 0.1~760Torr (that is,
13~101,080Pa).In particular, such as reaction temperature is 260~380 DEG C, is preferably 300~360 DEG C, most in frit reaction
Zhongdao is 1~100Torr (that is, 133~13,300Pa), is preferably 1~50Torr (that is, 133~6,670Pa) up to pressure.
It, can be by whole starting monomers (HBA, HNA, TA, IA, BP and APAP), acylating agent and catalyst about reaction
It puts into same reaction vessel and starts to react (stage manner), starting monomer HBA, HNA, BP and APAP can also be made
After hydroxyl is acylated by acylating agent, (two stage method) is reacted with the carboxyl of TA and IA.
About melt polymerization, after reaching predetermined temperature in the reaction system, starts to depressurize, reach regulation degree of decompression and carry out
Melt polymerization.After the torque of blender reaches specified value, imports non-active gas and reach from decompression state via normal pressure
Wholly aromatic polyester amide is discharged from reaction system in defined pressurized state.
Using above-mentioned polymerization manufacture Wholly aromatic polyester amide can by further under normal pressure or decompression,
The solid phase heated in non-active gas realizes the increase of molecular weight.The optimum condition of solid-phase polymerization is reaction temperature
It spends 230~350 DEG C, preferably 260~330 DEG C and eventually arrives at 10~760Torr of pressure (that is, 1,330~101,080Pa).
The manufacturing method of Wholly aromatic polyester amide in the present invention preferably includes following processes: in fatty acid metal salts
In the presence of, by 4-HBA, 6-Hydroxy-2-naphthoic acid, 4,4 '-dihydroxybiphenyls and n-acetyl p-aminophenol are used
Fatty acid anhydride is acylated, then with Isosorbide-5-Nitrae-phenylene dicarboxylic acids and 1,3- phenylene dicarboxylic acids carry out transesterification,
Preferably: relative to including 4-HBA, 6-Hydroxy-2-naphthoic acid, 1,4- phenylene dicarboxylic acids, 1,3-
Whole monomers of phenylene dicarboxylic acids, 4,4 '-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-phenylene dicarboxylic acids dosage is 10.25~22.25 moles of %, from the sight for taking into account low melting point and heat resistance
Point sets out, preferably 12.963~20.75 moles of %, more preferably 15.675~19.25 moles of %,
The dosage of 1,3- phenylene dicarboxylic acids 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 0.5~3.75 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 %,
Total dosage of 6-Hydroxy-2-naphthoic acid and 1,3- phenylene dicarboxylic acids is that 1 mole of % rubs more than and less than 5
You are %, from the viewpoint of taking into account low melting point and heat resistance, preferably 1.75~4.75 moles of %, more preferably 2.5~4.5
Mole %,
4-HBA, 6-Hydroxy-2-naphthoic acid, 1,4- phenylene dicarboxylic acids, 1,3- phenylene dicarboxylic acids, 4,4 '-
Total dosage of dihydroxybiphenyl and n-acetyl p-aminophenol is 100 moles of %,
It is preferred that the dosage of n-acetyl p-aminophenol is relative to 4,4 '-dihydroxybiphenyls and n-acetyl p-aminophenol
Total dosage molar ratio be 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 above-mentioned fatty 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, the conjunction of more preferably Isosorbide-5-Nitrae-phenylene dicarboxylic acids and 1,3- phenylene dicarboxylic acids
It counts molal quantity (hereinafter also referred to " molal quantity 1B ".) it is that 4,4 '-dihydroxybiphenyls and the total of n-acetyl p-aminophenol rub
That number (hereinafter also referred to " molal quantity 2B ".) 1~1.1 times or molal quantity 2B be 1~1.1 times of molal quantity 1B.Further
It is 1.02~1.06 times of molal quantity 1B that more preferable molal quantity 1B, which is 1.02~1.06 times or molal quantity 2B of molal quantity 2B,.
Particularly preferred molal quantity 1B be that 1.024~1.056 times or molal quantity 2B of molal quantity 2B are molal quantity 1B 1.024~
1.056 again.
Then, the property of Wholly aromatic polyester amide is illustrated.Wholly aromatic polyester amide in the present invention is molten
Optical anisotropy is shown when melting.Show that optical anisotropy refers in melting: the Wholly aromatic polyester amide in the present invention
For liquid-crystalline polymer.
In the present invention, Wholly aromatic polyester amide is that liquid-crystalline polymer has both heat surely for Wholly aromatic polyester amide
Qualitative and workability is indispensable element.The Wholly aromatic polyester amide being made of above structure unit (I)~(VI)
According to the sequence distribution in constituent and polymer there is also the type for not forming anisotropy melting behaviors, but it is of the invention poly-
Conjunction object, which is defined in, shows optically anisotropic Wholly aromatic polyester amide in melting.
Melting anisotropic property can be confirmed by the usual polarisation inspection method using cross-polarization piece.More
Specifically, melting anisotropic confirmation can be implemented as follows: using Olympus Corp's petrographic microscope, by Linkam
The sample melting loaded in corporation thermal station, is observed with 150 times of multiplying power in a nitrogen atmosphere, is thus implemented.Liquid crystal liquid crystal property
Polymer is optically anisotropy, makes light transmission when being inserted between cross-polarization piece.When sample is optical anisotropy,
Even such as melting static liquid status and can also make polarizing transmission.
The liquid-crystalline polymer of nematic can generate significant viscosity more than fusing point and reduce, thus usually in fusing point or
Show that liquid crystal liquid crystal property this point becomes the index of processability at a temperature of more than fusing point.From the viewpoint of heat resistance, preferably fusing point
It is as high as possible, it is contemplated that the heating efficiency etc. of heat deterioration, molding machine when the melt-processed of polymer, 360 DEG C the following are preferred
Standard.It should be noted that more preferably 300~360 DEG C, it is even more preferably 340~358 DEG C.
10~30 DEG C of temperature higher than the fusing point of the Wholly aromatic polyester amide in the present invention and under shear velocity 1000/ second
The melt viscosity of above-mentioned Wholly aromatic polyester amide be preferably 500Pas hereinafter, more preferably 0.5~300Pas, into one
Step is more preferably 1~100Pas.Above-mentioned melt viscosity within the above range when, above-mentioned Wholly aromatic polyester amide itself or
Person contains the composition of above-mentioned Wholly aromatic polyester amide in its molding it is easy to ensure that mobility, stuffing pressure are not easy to become
Degree.It should be noted that in the present specification, melt viscosity refers to the melt viscosity based on ISO11443 measurement.
As the index for indicating above-mentioned heat resistance, fusing point and the difference of DTUL can be also enumerated.Have if the difference is 90 DEG C or less
The tendency that heat resistance improves.From the viewpoint of taking into account low melting point and heat resistance, it is above-mentioned difference preferably more than 0 DEG C and 85 DEG C with
Under (such as 50 DEG C or more and 85 DEG C or less), more preferably 55~79 DEG C.
Liquid crystalline resin composition of the invention is whole relative to liquid crystalline resin composition in liquid crystalline resin composition
Body includes the above-mentioned liquid-crystalline polymer of 50~70 mass %.The content of liquid-crystalline polymer is relative to liquid crystalline resin composition
When entirety is less than 50 mass %, the mobility of liquid crystalline resin composition is easy to deteriorate, and in addition has by liquid crystalline resin composition
The worry that the buckling deformation of the molded products such as obtained surface installation relay component becomes larger, therefore not preferably.Liquid crystal liquid crystal property polymerization
The content of object be relative to liquid crystalline resin composition integrally more than 70 mass % when, the table that is obtained by liquid crystalline resin composition
The bending modulus of molded products and the resistance to anti-thread breakage reductions such as relay component are installed in face, therefore not preferably.Liquid crystal liquid crystal property of the invention
Resin combination integrally includes 55~65 mass % relative to liquid crystalline resin composition preferably in liquid crystalline resin composition
Above-mentioned liquid-crystalline polymer, more preferably include 58~62 mass %.
(fibrous filler)
Liquid crystalline resin composition of the invention includes above-mentioned liquid-crystalline polymer and fibrous filler, fibrous filler
The weight average fiber length of agent is 50~170 μm, has containing for the component of 20~200 μm of fibre length in fibrous filler
Have rate be 70 mass % or more, therefore by the liquid crystalline resin composition molding obtained from molded product excellent heat resistance, rise
The generation of bubble and the disengaging of filler be suppressed, can use bonding agent is bonded with high-adhesive-strength.Fibrous filler
It can be used alone or combine two or more use.As the fibrous filler in the present invention, it is not particularly limited, it can
Enumerate glass fibre, milled fibre, carbon fiber, asbestos fibre, silicon dioxide fibre, silica alumina fiber, oxidation
Zirconium fiber, boron nitride fiber, silicon nitride fiber, boron fibre, potassium titanate fibre etc..In order to make to be obtained by liquid crystalline resin composition
The mutual adhesive strength of molded product be maintained it is higher and be easy inhibit filler be detached from from above-mentioned molded product, as the present invention
In fibrous filler, preferred milled fibre.
In liquid crystalline resin composition of the invention, the weight average fiber length of fibrous filler is 50~170 μm, excellent
It is selected as 70~150 μm, more preferably 80~140 μm, is even more preferably 100~140 μm.Above-mentioned weight average fiber length is less than
At 50 μm, the high temperature rigid of the molded product obtained by liquid crystalline resin composition is difficult to become sufficiently, there is the buckling deformation of molded product
The worry to become larger, therefore not preferably.When above-mentioned weight average fiber length is more than 170 μm, it is difficult to inhibit filler from obtained liquid crystal
Property resin combination molded product be detached from, therefore not preferably.When above-mentioned weight average fiber length is in the range of 50~170 μm, make
The surface roughness (Ra) of the molded product of obtained liquid crystalline resin composition moderately improves, and is easy above-mentioned molded product each other
Adhesive strength be maintained higher in suitable range.It should be noted that in the present specification, the weight of fibrous filler
Equal fibre length refers to the value measured as follows: liquid crystalline resin composition being heated 2 hours at 600 DEG C and is ashed, is ashed
Residue disperses 5 mass % Aqueous Solutions of Polyethylene Glycol for the ash residue and obtains dispersion liquid, which is surveyed with image
Determine the weight average fiber length that device determines.
In order to inhibit filler to be detached from from the molded product of liquid crystalline resin composition and keep the welding of above-mentioned molded product strong
It keeps balancing to the mechanical strength heights such as degree, high temperature rigid, there is 20~200 μm of fibre length in fibrous filler
The containing ratio of component is 70 mass % or more, preferably 75 mass % or more, more preferably 80 mass % or more.Above-mentioned containing ratio
The upper limit be not particularly limited, be 100 mass % or less, or 95 mass % or less.It should be noted that in this explanation
In book, above-mentioned containing ratio measures as follows: liquid crystalline resin composition being heated 2 hours at 600 DEG C and is ashed, obtains being ashed residual
Slag makes the ash residue be scattered in 5 mass % Aqueous Solutions of Polyethylene Glycol and obtain dispersion liquid, by being surveyed for the dispersion liquid with image
The fiber length distribution that device determines is determined to measure.
In addition, the fibre diameter of the fibrous filler in the present invention is not particularly limited, it is 5 usually using fibre diameter
~15 μm or so of fibrous filler.
Liquid crystalline resin composition of the invention is whole relative to liquid crystalline resin composition in liquid crystalline resin composition
Body includes the fibrous filler of 30~50 mass %.The content of fibrous filler is relative to liquid crystalline resin composition entirety
When less than 30 mass %, the load deflection of the molded products such as surface installation relay component obtained by liquid crystalline resin composition
Temperature low and high temperature is rigidly insufficient, therefore not preferably.The content of fibrous filler is relative to liquid crystalline resin composition entirety
When more than 50 mass %, there is the mobility of liquid crystalline resin composition to deteriorate, the worry that the buckling deformation of molded product becomes larger, therefore
Not preferably.Fibrous filler in the present invention is integrally excellent relative to liquid crystalline resin composition in liquid crystalline resin composition
Choosing includes 35~45 mass %, more preferably includes 38~42 mass %.
(other ingredients)
In liquid crystalline resin composition of the invention, it can also be compounded plate filler, nucleation in addition to the above ingredients
The pigment such as agent, carbon black, inorganic firing pigment, antioxidant, stabilizer, plasticizer, lubricant, release agent, fire retardant and known
One or more of inorganic filler.
As long as the manufacturing method of liquid crystalline resin composition of the invention can make the ingredient in liquid crystalline resin composition
It is uniformly mixed, makes 50~170 μm of the weight average fiber length of fibrous filler, make that there are 20~200 μ in fibrous filler
The containing ratio of the component of the fibre length of m is that 70 mass % or more are not particularly limited, can be from previously known resin group
Closing is suitable for selection in the manufacturing method of object.It can be mentioned, for example following methods: using the melting such as single screw rod or double screw extruder
After each components fuse is kneaded and is squeezed out by kneading device, obtained liquid crystalline resin composition is processed into powder, scale, pellet
Etc. desired form.
The mobility of liquid crystalline resin composition of the invention is excellent, therefore minimum pressure to fill when molding is not easy to become
Excessively, surface installation relay component etc. can be preferably moulded as.
In high 10~30 DEG C of the temperature of fusing point than liquid-crystalline polymer and under shear velocity 1000/ second, it is based on
The melt viscosity of the liquid crystalline resin composition of ISO11443 measurement is 1 × 105Pas or less (more preferably 5Pas or more
And 1 × 102Pas or less), this ensures the stream of liquid crystalline resin composition in the molding of surface installation relay component
Dynamic property, the aspect for avoiding stuffing pressure excessive are preferred.
(relay component is installed on surface and relay is installed on surface)
By forming liquid crystalline resin composition of the invention, relay portion is installed on available surface of the invention
Part.Excellent heat resistance, the generation of blistering and the disengaging of filler of surface installation relay component of the invention be suppressed, can
To be bonded using bonding agent with high-adhesive-strength.Surface installation relay of the invention has above-mentioned component, and therefore (1) is resistance to
It is hot excellent, solder reflow process can be resistant to；It (2) especially can be Nian Jie strong with height using bonding agent with shell by pedestal
Degree bonding, can also keep air-tightness after solder reflow process, and the generation of (3) blistering and the disengaging of filler are suppressed,
It is not likely to produce the dysfunctions such as poor flow.
Surface installation relay component of the invention and surface installation relay of the invention are illustrated.Fig. 1's
It (a) is the perspective view for schematically showing the embodiment of installation relay in surface of the invention, (b) of Fig. 1 shows Fig. 1
(a) partial sectional view of AA section.Surface installation relay 1 has pedestal 2, shell 3, coil block 4,5 and of armature component
Terminal 6.
Pedestal 2 has from the terminal 6 outstanding of pedestal 2.Peripheral part in the upper surface of pedestal 2 configures shell 3.In pedestal 2
The central portion of upper surface configure in order coil block 4 and armature component 5.
Shell 3 configures in the way of the peripheral part and coil block 4 and armature component 5 of the upper surface of covering pedestal 2.
Coil block 4 and armature component 5 are accommodated in the space interior of the hollow container shaped formed by pedestal 2 and shell 3.
Coil block 4 includes bobbin 41, coil 42 and iron core 43, is configured in the central portion of the upper surface of pedestal 2.Line
Coil 41 has the cylindrical portion penetrated through along long axis direction, is wound with one with a part of terminal 6 in the periphery of bobbin 41
The coil 42 for holding electrical connection, is inserted into cored 43 in the above-mentioned cylindrical portion of bobbin 41.
Armature component 5 has armature interconnecting piece 51 and armature 52 and is configured on coil block 4, and the armature 52 is from rank
Iron interconnecting piece 51 inversely extends each other along the long axis direction of bobbin 41.One end of another part of armature 52 and terminal 6
Electrical connection.If forming electromagnet and being connected with coil 42, the front end of armature 52 is moved to coil block 4 due to magnetic force
Side.As a result, the signal for carrying out the input side of self-contained coil 42 is transferred to the outlet side comprising armature 52.
One end of terminal 6 is electrically connected with coil 42 or armature 52, and the other end is with aftermentioned printed base plate 7 with conductive
Mode connects.Terminal 6 is prominent from pedestal 2 and makes to be welded in printed base plate 7 as described later.
In view of the generation and the disengaging of filler that can form excellent heat resistance, blistering are suppressed, can use bonding
The molded product this point etc. that agent is bonded with high-adhesive-strength, pedestal 2, shell 3, bobbin 41 in preferably above-mentioned component by
Liquid crystalline resin composition of the invention is formed.That is, installing relay component as surface of the invention, it can be mentioned, for example bases
Seat, shell, bobbin etc..
Surface installation relay 1 can for example manufacture as follows: the central portion in the upper surface of pedestal 2 configures in order coil group
Part 4 and armature component 5, then the peripheral part in the upper surface of pedestal 2 configures shell 3, and pedestal 2 and shell 3 are utilized bonding agent
It is bonded and manufactures.
The method that surface installation relay 1 is installed on printed base plate 7 is illustrated.As shown in (a) of Fig. 2, in table
Face install relay 1 in, from surface installation relay 1 vertically terminal 6 outstanding bend to right angle so that welding surface with
It is parallel that relay 1 is installed on surface.Therefore, relay 1 is installed for surface, the providing holes not instead of in printed base plate 7 is printing
Terminal 6 is loaded on the pad (not shown) being arranged on the conductive pattern 8 on 7 surface of brush substrate and carries out solder reflow process, by
This is fixed on printed base plate 7 in a manner of conductive.
It should be noted that being shown in above description as shown in (a) of Fig. 2, by surface installation relay 1 vertically
The case where front end of terminal 6 outstanding bends to right angle to the outside of surface installation relay 1.It on the other hand, can also be such as Fig. 2
(b) shown in, from surface installation relay 1 vertically terminal 6 outstanding front end to surface installation relay 1 interior lateral bend
At right angle.
Embodiment
The present invention is illustrated by the following examples, but the present invention is not limited by these examples.
1 > of < synthesis example
To having blender, reflux column, monomer input port, nitrogen inlet, throw in decompression/outflow pipeline aggregation container
Enter starting monomer below, fatty acid metal salt catalyst, acylating agent, starts to carry out 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, HNA, BP and APAP)
After putting into raw material, the temperature of reaction system is increased to 140 DEG C, is reacted 1 hour at 140 DEG C.Then, then with 5.5
Hour be warming up to 360 DEG C, be then depressurized to 10Torr (i.e. 1330Pa) with 20 minutes, make on one side acetic acid, excessive acetic anhydride, its
Its low boiling point component distillates, and carries out melt polymerization on one side.After stirring torque reaches specified value, nitrogen is imported, from decompression state
Reach pressurized state via normal pressure, 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 by the following method
Evaluation.Show the results of the evaluation table 1.
[fusing point]
Using DSC (TA Instrument corporation), observing from room temperature with 20 DEG C/min of Elevated Temperature Conditions pair
After the endotherm peak temperature (Tm1) observed when polymer is measured, (Tm1+40) DEG C at a temperature of kept for 2 minutes after, with
After 20 DEG C/min of cooling conditions are temporarily cooled to room temperature, observed when measuring the Elevated Temperature Conditions measurement with 20 DEG C/min again
Endothermic peak temperature.
[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 % double screw extruder (the made TEX30 α of Japan, Co., Ltd. steel-making
Type) under+20 DEG C of fusing point of polymer of barrel temperature melting mixing is carried out, obtain liquid crystalline resin composition pellet.
By above-mentioned liquid crystalline resin composition pellet with molding machine (Sumitomo Heavy Industries, Ltd's system " SE100DU ")
It is formed under condition of molding below, obtains measurement test film (4mm × 10mm × 80mm).Use the test film base
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.
(condition of molding)
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, the fusing point than liquid-crystalline polymer it is high by 10~
At a temperature of 30 DEG C, liquid crystal is measured with shear velocity 1000/ second, based on ISO11443 using the aperture of internal diameter 1mm, length 20mm
The melt viscosity of property polymer.It should be noted that the record of measuring temperature such as table 1.
< synthesis example 2~18 compares 1~10 > of synthesis example
The type that makes starting monomer, output-input ratio (mole %) are as shown in table 1~3, in addition to this in the same manner as synthesis example 1
Obtain polymer.In addition, similarly being evaluated with synthesis example 1.Show the results of the evaluation table 1~3.
[table 1]
[table 2]
[table 3]
1~3 > of < embodiment 1 and 2, comparative example
In following Examples and Comparative Examples, liquid-crystalline polymer 1 is liquid-crystalline polymer obtained in synthesis example 16.
In addition, liquid-crystalline polymer 2 manufactures in the following way.
It should be noted that in the present embodiment, the measurement of the fusing point and melt viscosity of pellet is respectively according to following items
Part carries out.
[measurement of fusing point]
Using TA Instrument corporation DSC, observing from room temperature with 20 DEG C/min of Elevated Temperature Conditions to liquid crystal
Property the endotherm peak temperature (Tm1) observed when being measured of polymer after, (Tm1+40) DEG C at a temperature of kept for 2 minutes after,
After being temporarily cooled to room temperature with 20 DEG C/minute of cooling conditions, observed when measuring the Elevated Temperature Conditions measurement with 20 DEG C/min again
Endothermic peak temperature.
[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
It is measured under shear velocity 1000/ second based on ISO11443 at a temperature of 10~30 DEG C using the aperture of internal diameter 1mm, length 20mm
The melt viscosity of liquid-crystalline polymer.It should be noted that liquid-crystalline polymer 1 is 360 DEG C, liquid crystal liquid crystal property about measuring temperature
Polymer 2 is 380 DEG C.
(manufacturing method of liquid-crystalline polymer 2)
To having blender, reflux column, monomer input port, nitrogen inlet, throw in decompression/outflow pipeline aggregation container
Enter starting monomer below, metallic catalyst, acylating agent, starts to carry out 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
After putting into raw material into aggregation container, the temperature of reaction system is increased to 140 DEG C, it is small that 1 is reacted at 140 DEG C
When.Then, then with 5.5 hours be warming up to 360 DEG C, be then depressurized to 5Torr (that is, 667Pa) with 20 minutes, make on one side acetic acid,
Excessive acetic anhydride, other low boiling point components distillate, and carry out melt polymerization on one side.After stirring torque reaches specified value, import
Nitrogen reaches pressurized state from decompression state via normal pressure, and polymer is discharged from the lower part of aggregation container, strands are granulated and grain
Materialization.The fusing point of obtained pellet is 355 DEG C, melt viscosity 10Pas.
(ingredient other than liquid-crystalline polymer)
Each liquid-crystalline polymer and following ingredients obtained in will be above-mentioned be mixed with double screw extruder, obtain liquid crystal liquid crystal property
Resin combination.The use level of each ingredient is as shown in table 4.It should be noted that hereinafter, " % " in table indicates quality %.
(B) fibrous filler
Glass fibre: Nippon Electric Glass Co., Ltd ECS03T-786H, 10 μm of fibre diameter, length 3mm be chopped
Precursor
Milled fibre 1: 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)
Milled fibre 2: Nippon Electric Glass Co., Ltd EPH-80M, 10.5 μm of fibre diameter, average fiber length 80
μm (manufacturer's nominal value)
It should be noted that above-mentioned manufacturer's nominal value is different from the value in the table 4 of the measured value as composition.
In addition, extruding condition when obtaining liquid crystalline resin composition is as described below.
[extruding condition]
(embodiment 1 and 2, comparative example 1 and 3)
The temperature for being set to the barrel of main feed mouth is set as 250 DEG C, the temperature of other barrels is all set to 360 DEG C.Liquid
Crystalline substance polymer is all supplied from main feed mouth.In addition, filler is supplied from side feed inlet.
(comparative example 2)
The temperature for being set to the barrel of main feed mouth is set as 250 DEG C, the temperature of other barrels is all set to 380 DEG C.Liquid
Crystalline substance polymer is all supplied from main feed mouth.In addition, filler is supplied from side feed inlet.
It should be noted that the weight average fiber length of the fibrous filler in liquid crystalline resin composition is by following
Method measurement.
[measurement of weight average fiber length]
Liquid crystalline resin composition pellet 5g is heated 2 hours at 600 DEG C and is ashed.Ash residue is well-dispersed in 5
It after quality % Aqueous Solutions of Polyethylene Glycol, is transferred in culture dish with dropper, with micro- sem observation fibrous filler.Simultaneously with figure
As the weight average fiber length of analyzer (Co., Ltd. NIRECO LUZEXFS) measurement fibrous filler.
In addition, in liquid crystalline resin composition, in fibrous filler with the component of 20~200 μm of fibre length
Containing ratio pass through following method and measure.
[measurement of the containing ratio of the component with 20~200 μm of fibre length]
Liquid crystalline resin composition pellet 5g is heated 2 hours at 600 DEG C and is ashed.Ash residue is well-dispersed in
It after 5 mass % Aqueous Solutions of Polyethylene Glycol, is transferred in culture dish with dropper, with image determiner (NIRECO corporation
LUZEXFS the fiber length distribution of fibrous filler) is measured.Reading in above-mentioned fiber length distribution has 20~200 μm
Fibre length component ratio, as above-mentioned containing ratio.
(measurement of the melt viscosity of liquid crystalline 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
It is measured using the aperture of internal diameter 1mm, length 20mm with shear velocity 1000/ second, based on ISO11443 at a temperature of 10~30 DEG C
The melt viscosity of liquid crystalline resin composition.It should be noted that having used the liquid of liquid-crystalline polymer 1 about measuring temperature
Crystalline substance resin combination is 360 DEG C, and having used the liquid crystalline resin composition of liquid-crystalline polymer 2 is 380 DEG C.It shows the result in
Table 4.
Physical property based on the molded product that following methods measurement is molded by liquid crystalline resin composition.Each evaluation result is shown
In table 4.
(bend test)
Liquid crystalline resin composition is injection moulded under following conditions of molding, the molded product of 0.8mm thickness is obtained, is based on
ASTM D790 measures bending strength, breaking strain and bending modulus.
[condition of molding]
Molding machine: the industry of Sumitomo hoisting machinery, SE100DU
Barrel temperature: 360 DEG C (embodiment 1 and 2, comparative example 1 and 3)
370 DEG C (comparative example 2)
Mold temperature: 80 DEG C
Injection speed: 33mm/ seconds
(temperature of deflection under load)
Liquid crystalline resin composition is injection moulded under following conditions of molding, obtains molded product, is based on ISO75-1,2 survey
Determine temperature of deflection under load.
[condition of molding]
Molding machine: the industry of Sumitomo hoisting machinery, SE100DU
Barrel temperature: 360 DEG C (embodiment 1 and 2, comparative example 1 and 3)
370 DEG C (comparative example 2)
Mold temperature: 80 DEG C
Injection speed: 33mm/ seconds
(nucleation temperature)
Liquid crystalline resin composition is injection moulded under following conditions of molding, obtain the 12.5mm with weld portion ×
The molded product of 120mm × 0.8mm.Punishing the molded product at fragment obtained from two parts in above-mentioned weld portion as 1
It checks body, is pressed from both sides 5 minutes in the hot press of predetermined temperature.Then, whether the surface for visually investigating above-mentioned inspection body has produced
Bubble.About nucleation temperature, it is set as the maximum temperature that the generation number of blistering is zero.It should be noted that above-mentioned predetermined temperature exists
It is set in the range of 250~300 DEG C with 10 DEG C of intervals.
[condition of molding]
Molding machine: the industry of Sumitomo hoisting machinery, SE100DU
Barrel temperature: 360 DEG C (embodiment 1 and 2, comparative example 1 and 3)
370 DEG C (comparative example 2)
Mold temperature: 90 DEG C
Injection speed: 33mm/ seconds
(filler detachment)
Liquid crystalline resin composition is injection moulded under following conditions of molding, obtain the 12.5mm with weld portion ×
The molded product of 120mm × 0.8mm.For punishing the molded product in above-mentioned weld portion at molded product obtained from two parts,
After carrying out IR Reflow Soldering under the conditions of following, the disengaging situation of fibrous filler material is observed, is evaluated according to benchmark below.
Zero (good): unchanged, the disengaging of fibrous filler is suppressed.
× (bad): fibrous filler is detached from.
[condition of molding]
Molding machine: the industry of Sumitomo hoisting machinery, SE100DU
Barrel temperature: 360 DEG C (embodiment 1 and 2, comparative example 1 and 3)
370 DEG C (comparative example 2)
Mold temperature: 90 DEG C
Injection speed: 33mm/ seconds
[IR Reflow Soldering condition]
Measuring machine: the desk-top reflow soldering apparatus RF-300 of the Japanese made large size of pulse technical research (uses FAR INFRARED HEATING
Device)
Sample feed speed: 140mm/ seconds
Reflow soldering passes through the time: 5 minutes
The temperature condition of preheating zone: 150 DEG C
The temperature condition of reflux welding zone: 190 DEG C
Peak temperature: 251 DEG C
(surface roughness (Ra))
Liquid crystalline resin composition is injection moulded under following conditions of molding, obtain test film (ISO test film 1A type,
Thickness 4mm).For the center portion of the molded product, with ultra-deep colour 3D measuring shape microscope VK-9500, (KEYENCE is public
Department's system) measurement surface roughness Ra.
[condition of molding]
Molding machine: the industry of Sumitomo hoisting machinery, SE100DU
Barrel temperature: 360 DEG C (embodiment 1 and 2, comparative example 1 and 3)
370 DEG C (comparative example 2)
Mold temperature: 90 DEG C
Injection speed: 33mm/ seconds
(adhesive strength)
Liquid crystalline resin composition is injection moulded under following conditions of molding, obtain test film (ISO test film 1A type,
Thickness 4mm).The test film is divided into 2 parts, epoxy bonding agent (HENKEL corporation is used as shown in (a) of Fig. 3
LOCTITE 3128NH) fitting (condition of cure: 80 DEG C × 30 minutes).Then, after fitting being set as shown in (b) of Fig. 3
Test film, apply load along the direction of the arrow with cupping machine, by it is peeling-off when load evaluate adhesive strength.
[condition of molding]
Molding machine: the industry of Sumitomo hoisting machinery, SE100DU
Barrel temperature: 360 DEG C (embodiment 1 and 2, comparative example 1 and 3)
370 DEG C (comparative example 2)
Mold temperature: 90 DEG C
Injection speed: 33mm/ seconds
[stretch test conditions]
Testing machine: ORIENTEC, TENSILON RTC-1325A
Test speed: 10mm/ minutes
[table 4]
※ specific components: there is the component of 20~200 μm of fibre length in fibrous filler
As shown in table 4, the molded product formed by surface installation relay of the invention with liquid crystalline resin composition
Excellent heat resistance, the generation of blistering and the disengaging of filler be suppressed, can use bonding agent and glued with high-adhesive-strength
It connects.Therefore, above-mentioned liquid crystalline resin composition can be suitable for surface installation relay component and surface installation relay
Manufacture.
Description of symbols
1 surface is installed by relay
2 pedestals
3 shells
4 coil blocks
41 bobbins
42 coils
43 iron cores
5 armature components
51 armature interconnecting pieces
52 armature
6 terminals
7 printed base plates
8 conductive patterns
Claims (5)
1. a kind of liquid crystalline resin composition, to be installed comprising the surface of (A) liquid-crystalline polymer and (B) fibrous filler
Relay liquid crystalline resin composition,
(A) liquid-crystalline polymer is to be used as required constituent comprising following structural units (I)~(VI) and melting
When show optically anisotropic Wholly aromatic polyester amide,
Relative to entire infrastructure unit, the content of structural unit (I) is 50~70 moles of %,
Relative to entire infrastructure unit, the content of structural unit (II) is more than and less than 4.5 moles % of 0.5 mole of %,
Relative to entire infrastructure unit, the content of structural unit (III) is 10.25~22.25 moles of %,
Relative to entire infrastructure unit, the content of structural unit (IV) is more than and less than 4.5 moles % of 0.5 mole of %,
Relative to entire infrastructure unit, the content of structural unit (V) is 5.75~23.75 moles of %,
Relative to entire infrastructure unit, the content of structural unit (VI) is 1~7 mole of %,
Relative to entire infrastructure unit, total content of structural unit (II) and structural unit (IV) is 1 mole of % or more and small
In 5 moles of %,
Relative to entire infrastructure unit, the total content of structural unit (I)~(VI) is 100 moles of %,
Structural unit (VI) is 0.04~0.37 relative to total molar ratio of structural unit (V) and structural unit (VI),
The weight average fiber length of (B) fibrous filler is 50~170 μm,
In (B) fibrous filler, the containing ratio of the component with 20~200 μm of fibre length be 70 mass % with
On,
(A) liquid-crystalline polymer relative to liquid crystalline resin composition generally 50~70 mass %,
(B) fibrous filler relative to liquid crystalline resin composition generally 30~50 mass %,
Surface installation relay be have pedestal and from pedestal terminal outstanding, make the terminal be welded in printing
Relay is installed on the surface of substrate,
2. liquid crystalline resin composition according to claim 1, wherein structural unit (III) and structural unit (IV)
Total molal quantity be 1~1.1 times of total molal quantity of structural unit (V) and structural unit (VI) or structural unit (V) with
Total molal quantity of structural unit (VI) is 1~1.1 times of total molal quantity of structural unit (III) and structural unit (IV).
3. liquid crystalline resin composition according to claim 1 or 2, wherein (B) fibrous filler is that grinding is fine
Dimension.
4. relay component is installed on a kind of surface, formed by composition according to any one of claims 1 to 3.
5. relay is installed on a kind of surface, has component as claimed in claim 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-248302 | 2016-12-21 | ||
| JP2016248302 | 2016-12-21 | ||
| PCT/JP2017/044424 WO2018116888A1 (en) | 2016-12-21 | 2017-12-11 | Liquid crystalline resin composition for surface-mounted relays and surface-mounted relay using same |
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| KR (1) | KR102020634B1 (en) |
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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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2022071598A (en) | 2020-10-28 | 2022-05-16 | Ｅｎｅｏｓ株式会社 | Method for improving adhesive strength to adhesive of resin molding and composite body having improved adhesive strength |
| CN116806239A (en) * | 2021-02-05 | 2023-09-26 | 宝理塑料株式会社 | Liquid crystal resin composition for fan impeller and fan impeller using same |
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| 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 |
|---|---|
| KR20190034695A (en) | 2019-04-02 |
| JP6416442B1 (en) | 2018-10-31 |
| TWI716655B (en) | 2021-01-21 |
| TW201840714A (en) | 2018-11-16 |
| JPWO2018116888A1 (en) | 2018-12-20 |
| KR102020634B1 (en) | 2019-09-10 |
| CN109844028B (en) | 2020-09-11 |
| WO2018116888A1 (en) | 2018-06-28 |
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