CN113015765A - Liquid crystalline resin composition and connector of molded article comprising same - Google Patents
Liquid crystalline resin composition and connector of molded article comprising same Download PDFInfo
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- CN113015765A CN113015765A CN201980074882.7A CN201980074882A CN113015765A CN 113015765 A CN113015765 A CN 113015765A CN 201980074882 A CN201980074882 A CN 201980074882A CN 113015765 A CN113015765 A CN 113015765A
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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
- C08K7/10—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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- 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
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Abstract
Providing: a liquid crystalline resin composition having excellent fluidity and capable of producing a connector having excellent heat resistance and mechanical strength and suppressed warping deformation, and a connector comprising a molded article of the liquid crystalline resin composition. The liquid crystalline resin composition comprises (A) a liquid crystalline resin, (B) fibrous wollastonite and (C) mica, wherein the aspect ratio of the (B) fibrous wollastonite is 8 or more, the content of the (A) liquid crystalline resin is 62.5 to 72.5 mass%, the content of the (B) fibrous wollastonite is 2.5 to 15 mass%, the content of the (C) mica is 17.5 to 30 mass%, and the total content of the (B) fibrous wollastonite and the (C) mica is 27.5 to 37.5 mass%, based on the whole liquid crystalline resin composition.
Description
Technical Field
The present invention relates to a liquid crystalline resin composition and a connector of a molded article including the liquid crystalline resin composition.
Background
The liquid crystalline resin is a thermoplastic resin having excellent dimensional accuracy, flowability, and the like. Because of such characteristics, liquid crystalline resins have been used as materials for various electronic components.
In particular, with the recent miniaturization and thinning of optoelectronic devices, there are electronic components (connectors and the like) constituting the optoelectronic devices with a reduced thickness and a reduced pitch. For example, patent document 1 discloses a connector molded from a liquid crystalline resin composition reinforced with mica and glass fibers. Such connectors are used as board-to-board connectors, connectors for flexible printed boards for connecting flexible printed boards (FPCs) and Flexible Flat Cables (FFCs), and the like, which require heat resistance, suppression of warpage, fluidity, dimensional stability, and the like.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2006-37061
Disclosure of Invention
Problems to be solved by the invention
However, when a connector is molded from a conventional liquid crystalline resin composition, the composition is insufficient in heat resistance, mechanical strength, suppression of warpage, and fluidity, and is poor in processability, and therefore it is difficult to manufacture a low-thickness narrow-pitch connector that meets the demand for a low thickness and a narrow pitch.
The present invention has been made in view of the above circumstances, and an object thereof is to provide: a liquid crystalline resin composition having excellent fluidity and capable of producing a connector having excellent heat resistance and mechanical strength and suppressed warping deformation, and a connector comprising a molded article of the liquid crystalline resin composition.
Means for solving the problems
The inventors of the present invention found that: the above problems can be solved by combining the liquid crystalline resin, the fibrous wollastonite and the mica at predetermined contents and setting the aspect ratio of the fibrous wollastonite to a predetermined range. Specifically, the present invention provides the following.
(1) A liquid crystalline resin composition comprising: (A) liquid crystalline resin, (B) fibrous wollastonite, and (C) mica,
the aspect ratio of the fibrous wollastonite (B) is 8 or more,
the liquid crystalline resin composition is a liquid crystalline resin composition,
the content of the liquid crystalline resin (A) is 62.5 to 72.5 mass%,
The fibrous wollastonite (B) is contained in an amount of 2.5 to 15 mass%,
The content of the mica (C) is 17.5 to 30 mass%,
The total content of the fibrous wollastonite (B) and the mica (C) is 27.5 to 37.5% by mass.
(2) The liquid crystalline resin composition according to (1), which is used for a connector having a product overall length of less than 30mm and a product height of less than 5 mm.
(3) A connector comprising a molded article of the liquid crystalline resin composition according to (1) or (2), wherein the total length of the product is less than 30mm and the height of the product is less than 5 mm.
(4) The connector according to (3), which is a low thickness narrow pitch connector.
(5) The connector according to (3) or (4), wherein the pitch distance is 0.5mm or less,
The total length of the product is more than 3.5mm and less than 30mm,
The height of the product is less than 1.5mm,
the connector is a low-thickness narrow-pitch connector as a board-to-board connector or a connector for a flexible printed board.
ADVANTAGEOUS EFFECTS OF INVENTION
By the present invention, there are provided: a liquid crystalline resin composition having excellent fluidity and capable of producing a connector having excellent heat resistance and mechanical strength and suppressed warping deformation, and a connector comprising a molded article of the liquid crystalline resin composition.
Drawings
Fig. 1 is a diagram showing an FPC connector formed in the embodiment. The units of the numerical values in the figures are mm.
Fig. 2 is a view showing a measurement position in the measurement of the warpage of the FPC connector performed in the example.
Detailed Description
Hereinafter, embodiments of the present invention will be specifically described.
[ liquid Crystal resin composition ]
The liquid crystalline resin composition of the present invention contains predetermined amounts of a liquid crystalline resin, fibrous wollastonite, and mica, and the aspect ratio of the fibrous wollastonite is 8 or more. The components constituting the liquid crystalline resin composition of the present invention will be described below.
[ (A) liquid crystalline resin ]
The liquid crystalline resin (a) used in the present invention is a melt-processable polymer having a property of forming an optically anisotropic melt phase. The properties of the anisotropic molten phase can be confirmed by a commonly used polarization examination method using a cross polarizer. More specifically, the anisotropic molten phase can be confirmed by observing a molten sample placed on a Leitz heating stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope. When the liquid crystal resin applicable to the present invention is tested between crossed polarizers, the polarized light is normally transmitted even in a molten static state, and optical anisotropy is displayed.
The type of the liquid crystalline resin (a) is not particularly limited, but an aromatic polyester and/or an aromatic polyester amide is preferable. In addition, a polyester partially containing an aromatic polyester and/or an aromatic polyester amide in the same molecular chain is also within this range. When the liquid crystalline resin (A) is dissolved in pentafluorophenol at a concentration of 0.1 mass% at 60 ℃, it is preferably used that the liquid crystalline resin (A) has a logarithmic viscosity (I.V.) of preferably at least about 2.0dl/g, more preferably 2.0 to 10.0 dl/g.
As the aromatic polyester or aromatic polyester amide applicable to the liquid crystalline resin (a) of the present invention, an aromatic polyester or aromatic polyester amide having a repeating unit derived from an aromatic hydroxycarboxylic acid as a constituent is particularly preferable.
More specifically, there may be mentioned:
(1) a polyester mainly comprising 1 or 2 or more repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof;
(2) a polyester mainly comprising 1 or 2 or more repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof and 1 or 2 or more repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a derivative thereof;
(3) a polyester mainly comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof, (b) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a derivative thereof, and (c) at least 1 or 2 or more kinds of repeating units derived from an aromatic diol, an alicyclic diol, an aliphatic diol, or a derivative thereof;
(4) a polyesteramide mainly comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof, (b) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxylamine, an aromatic diamine, or a derivative thereof, and (c) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a derivative thereof;
(5) polyester amides mainly comprising (a) 1 or 2 or more kinds of repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof, (b) 1 or 2 or more kinds of repeating units derived from aromatic hydroxylamines, aromatic diamines, and derivatives thereof, (c) 1 or 2 or more kinds of repeating units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and (d) at least 1 or 2 or more kinds of repeating units derived from aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof, and the like. If necessary, a molecular weight modifier may be further used in combination with the above-mentioned components.
Preferred examples of the specific compound constituting the liquid crystalline resin (a) applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; aromatic diols such as 2, 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4' -dihydroxybiphenyl, hydroquinone, resorcinol, a compound represented by the following general formula (I), and a compound represented by the following general formula (II); aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4' -diphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); aromatic amines such as p-aminophenol and p-phenylenediamine.
(X: is selected from the group consisting of alkylene (C)1～C4) Alkylene, alkylidene, O-, -SO-, -SO2-, -S-, and-CO-groups)
(Y is selected from the group consisting of- (CH)2)n- (n-1-4) and-O (CH)2)nAnd (1-4) O- (n). )
The most preferable liquid crystalline resin (a) applicable to the present invention is a wholly aromatic polyester amide containing the following constituent units (I) to (VI) as essential constituent components:
the content of the constituent unit (I) is 50 to 70 mol% based on the total constituent units,
the content of the constituent unit (II) is 0.5 mol% or more and less than 4.5 mol% based on the whole constituent units,
the content of the constituent unit (III) is 10.25 to 22.25 mol% based on the total constituent units,
the content of the constituent unit (IV) is 0.5 mol% or more and less than 4.5 mol% based on the whole constituent units,
the content of the constituent unit (V) is 5.75 to 23.75 mol% based on the total constituent units,
the content of the constituent unit (VI) is 1 to 7 mol% based on the whole constituent units,
the total content of the constituent unit (II) and the constituent unit (IV) is 1 mol% or more and less than 5 mol% based on the total constituent units,
the total content of the constituent units (I) to (VI) is 100 mol% based on the total constituent units,
the molar ratio of the constituent unit (VI) to the total of the constituent unit (V) and the constituent unit (VI) is 0.04 to 0.37, and the liquid crystalline resin (A) exhibits optical anisotropy when molten.
(I)
(II)
(III)
(IV)
(V)
(VI)
The liquid crystalline resin (a) used in the present invention can be produced by a known method from the above-mentioned monomer compound (or mixture of monomers) by a direct polymerization method or an ester exchange method, and usually a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like, or a combination of 2 or more of these is used, and preferably a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is used. The above-mentioned compounds having an ester-forming ability may be used in the polymerization in their original form, or may be modified from a precursor to a derivative having the ester-forming ability in a stage prior to the polymerization. In the polymerization, various catalysts can be used, and typical examples thereof include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, cobalt (III) tris (2, 4-pentanedionate), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of the catalyst used is usually about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers. The polymer produced by these polymerization methods can be further increased in molecular weight by a solid-phase polymerization method in which heating is performed in a reduced pressure or an inert gas, if necessary.
The melt viscosity of the liquid crystalline resin (a) obtained by the above-described method is not particularly limited. Melt viscosity at forming temperature can generally be used at a shear rate of 1000 seconds-1Is measured to be 3 pas or more and 500 pas or less. However, when the viscosity itself is too high, the fluidity is very poor, and therefore, it is not preferable. The liquid crystalline resin (a) may be a mixture of 2 or more liquid crystalline resins.
The liquid crystalline resin composition of the present invention preferably contains (A) a liquid crystalline resin in an amount of 62.5 to 72.5 mass% based on the whole liquid crystalline resin composition. (A) When the content of the liquid crystalline resin is less than 62.5% by mass based on the entire liquid crystalline resin composition, the following may occur: the liquid crystalline resin composition is not preferable because the fluidity of the liquid crystalline resin composition is easily deteriorated and the bending deformation of a molded article such as a connector obtained by using the liquid crystalline resin composition is reduced. (A) If the content of the liquid crystalline resin is more than 72.5% by mass based on the entire liquid crystalline resin composition, the effect of suppressing the flexural modulus and warpage of a molded article such as a connector obtained from the liquid crystalline resin composition is reduced, which is not preferable. The liquid crystalline resin composition of the present invention preferably contains 63.5 to 71.5% by mass, more preferably 65 to 70% by mass of (a) the liquid crystalline resin based on the whole liquid crystalline resin composition.
[ (B) fibrous wollastonite ]
(B) The aspect ratio of the fibrous wollastonite, i.e., the value of the average fiber length/the average fiber diameter, is 8 or more. The aspect ratio is preferably 10to 25, more preferably 15 to 20, from the viewpoint of the flexural modulus, warpage suppressing effect, and the like of a molded article such as a connector obtained from the liquid crystalline resin composition of the present invention.
The fibrous wollastonite (B) is not particularly limited, and for example, a known fibrous wollastonite can be used. (B) The fibrous wollastonite may be used alone or in combination of 2 or more different in aspect ratio, average fiber length, average fiber diameter and the like.
(B) The fibrous wollastonite preferably has an average fiber diameter of 3.0 to 50 μm, and more preferably has an average fiber diameter of 4.5 to 40 μm. When the average fiber diameter is 3.0 μm or more, a molded article such as a connector obtained by using the liquid crystalline resin composition of the present invention can easily secure sufficient mechanical strength and deflection temperature under load. When the average fiber diameter is 50 μm or less, the effect of suppressing fuzz on the surface of the molded article tends to be improved. In the present specification, as the average fiber diameter, the average value of the values obtained by observing fibrous wollastonite with a scanning electron microscope and measuring the fiber diameters of 100 fibrous wollastonite was used.
(B) The fibrous wollastonite preferably has an average fiber length of 30 to 800 μm, and more preferably has an average fiber length of 50 to 600 μm. When the average fiber length is 30 μm or more, a molded article such as a connector obtained from the liquid crystalline resin composition of the present invention can easily secure sufficient mechanical strength and deflection temperature under load. When the average fiber length is 800 μm or less, the effect of suppressing fuzz on the surface of the molded article tends to be improved. In the present specification, as the average fiber length, a solid microscopic image of 10 sheets of fibrous wollastonite was obtained from a PC by a CCD camera, and the fiber length was measured by an image processing method using an image measuring machine for 100 fibrous wollastonite in 1 solid microscopic image, that is, 1000 fibrous wollastonite in total, and the average of the measured values was used.
The liquid crystalline resin composition of the present invention preferably contains (B) fibrous wollastonite in an amount of 2.5 to 15 mass% based on the whole liquid crystalline resin composition. (B) If the fibrous wollastonite content is less than 2.5% by mass based on the entire liquid crystalline resin composition, warpage of a molded article such as a connector obtained from the liquid crystalline resin composition, particularly warpage after reflow soldering may increase, which is not preferable. (B) When the content of the fibrous wollastonite is more than 15% by mass based on the whole liquid crystalline resin composition, the following may occur: the liquid crystalline resin composition is not preferable because the fluidity of the liquid crystalline resin composition is easily deteriorated and the bending deformation of a molded article such as a connector obtained from the liquid crystalline resin composition is reduced. The liquid crystalline resin composition preferably contains the fibrous wollastonite (B) of the present invention in an amount of 3 to 13% by mass, more preferably 5to 10% by mass, based on the whole liquid crystalline resin composition.
[ (C) mica ]
The liquid crystalline resin composition of the present invention contains mica. The liquid crystalline resin composition of the present invention contains mica, and thus has a sufficient flexural modulus and can provide a molded article with suppressed warp deformation. The mica may be used singly or in combination of two or more.
The liquid crystalline resin composition contains 17.5 to 30 mass% of mica based on the whole liquid crystalline resin composition. When the content of mica is less than 17.5% by mass based on the whole liquid crystalline resin composition, the flexural modulus of a molded article obtained from the liquid crystalline resin composition is improved and the suppression of warp deformation is insufficient, which is not preferable. If the content of mica is more than 30% by mass based on the whole liquid crystalline resin composition, the fluidity of the liquid crystalline resin composition is deteriorated, and it may be difficult to mold the liquid crystalline resin composition, which is not preferable. The liquid crystalline resin composition preferably contains 18.5 to 27.5% by mass, more preferably 20 to 25% by mass of mica based on the whole liquid crystalline resin composition.
[ mica ]
Mica refers to a ground silicate mineral containing aluminum, potassium, magnesium, sodium, iron, and the like. Examples of mica that can be used in the present invention include muscovite, phlogopite, biotite, and synthetic mica, and among these, muscovite is preferable in terms of good color and low cost.
In the production of mica, a wet grinding method and a dry grinding method are known as methods for grinding minerals. The wet grinding method is a method in which mica raw stone is coarsely ground by a dry grinder, water is added, the mica raw stone is coarsely ground in a slurry state by wet grinding, and then dehydration and drying are performed. Dry grinding is a common method at a lower cost than wet grinding, but when wet grinding is used, it is easier to grind minerals thinly and finely. In the present invention, it is preferable to use a thin and finely pulverized product because mica having a preferable average particle diameter and thickness, which will be described later, can be obtained. Therefore, mica produced by wet grinding is preferably used in the present invention.
In addition, since the wet grinding method requires a step of dispersing the ground material in water, a coagulating sedimentation agent and/or a precipitation aid is generally added to the ground material in order to improve the dispersion efficiency of the ground material. Examples of the coagulating sedimentation agent and the precipitating assistant usable in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, chloric copperas, polyiron sulfate, polyiron chloride, iron-silica inorganic polymer coagulant, iron chloride-silica inorganic polymer coagulant, and hydrated lime (Ca (OH))2) Caustic soda (NaOH), soda ash (Na)2CO3) And the like. The pH of these coagulants and precipitation aids is either basic or acidic. The mica used in the present invention is preferably subjected to wet grindingWhen the precipitation aid is not used, the coagulation precipitant and/or the precipitation aid is not used. When mica which has not been treated with a coagulating precipitant and/or a precipitation assistant is used, the liquid crystalline resin composition is less likely to undergo decomposition of the polymer, generation of a large amount of gas, reduction in the molecular weight of the polymer, and the like, and thus the performance of the obtained molded article such as a connector can be more favorably maintained.
The mica used in the present invention preferably has an average particle diameter of 10to 100 μm, particularly preferably 20 to 80 μm, as measured by Microtrac laser diffraction method. When the average particle diameter of mica is 10 μm or more, the effect of improving the rigidity of the molded article tends to be sufficient, and therefore, mica is preferable. When the average particle size of mica is 100 μm or less, the rigidity of the molded article can be sufficiently improved and the fusion strength can be sufficiently increased, which is preferable. Further, when the average particle size of mica is 100 μm or less, sufficient fluidity for molding the connector of the present invention or the like can be easily secured.
The thickness of the mica used in the present invention is preferably 0.01 to 1 μm, particularly preferably 0.03 to 0.3 μm, as measured by observation with an electron microscope. When the thickness of mica is 0.01 μm or more, mica is less likely to be broken when the liquid crystalline resin composition is melt-processed, and therefore, the rigidity of the molded article may be easily increased, which is preferable. When the thickness of mica is 1 μm or less, the effect of improving the rigidity of the molded article tends to be sufficient, and therefore, mica is preferable.
Mica usable in the present invention may be surface-treated with a silane coupling agent or the like, and/or granulated with a binder.
The total content of the fibrous wollastonite (B) and the mica (C) in the liquid crystalline resin composition of the present invention is 27.5 to 37.5% by mass based on the whole liquid crystalline resin composition. If the content is less than 27.5% by mass based on the entire liquid crystalline resin composition, the flexural modulus and warpage suppressing effect of a molded article such as a connector obtained from the liquid crystalline resin composition are reduced, which is not preferable. When the content is more than 37.5% by mass based on the entire liquid crystalline resin composition, the following may occur: the liquid crystalline resin composition is not preferable because the fluidity of the liquid crystalline resin composition is easily deteriorated and the bending deformation of a molded article such as a connector obtained from the liquid crystalline resin composition is reduced. The content is preferably 28.0 to 36.5% by mass, more preferably 28.5 to 35% by mass, based on the whole liquid crystalline resin composition.
[ other ingredients ]
In the liquid crystalline resin composition of the present invention, other polymers, other fillers, known substances added to general synthetic resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, release agents, crystallization accelerators, and crystallization nucleating agents may be added as appropriate according to the required performance within a range not to impair the effects of the present invention. The other components may be used singly or in combination of two or more.
The other filler is a filler other than fibrous wollastonite having an aspect ratio of 8 or more, mica, and carbon black, and examples thereof include fibrous fillers other than fibrous wollastonite having an aspect ratio of 8 or more (for example, fibrous wollastonite having an aspect ratio of less than 8, ground fibers), and plate-like fillers other than mica (for example, talc). Among them, from the viewpoint of improving the mechanical strength of the molded article, suppressing warpage, and the like, the liquid crystalline resin composition of the present invention preferably does not contain fibrous wollastonite having an aspect ratio of less than 8, milled fibers, and talc.
The method for producing the liquid crystalline resin composition of the present invention is not particularly limited as long as the components in the liquid crystalline resin composition can be uniformly mixed, and can be appropriately selected from conventionally known methods for producing resin compositions. For example, a method in which the respective components are melt-kneaded and extruded using a melt-kneading apparatus such as a single-screw or twin-screw extruder, and the obtained liquid crystalline resin composition is processed into a desired form such as powder, sheet, pellet, or the like can be mentioned.
The liquid crystalline resin composition of the present invention has excellent fluidity, and therefore, the minimum filling pressure during molding is not likely to become excessively high, and it can be preferably molded into a connector, particularly a small-sized and complicated-shaped member such as a low-thickness narrow-pitch connector. The degree of fluidity is judged by the minimum fill pressure of the connector. That is, when the FPC connector shown in fig. 1 is injection molded, the minimum injection filling pressure at which a good molded body can be obtained is specified as the minimum filling pressure. The lower the minimum filling pressure, the more excellent the flowability was evaluated.
The melt viscosity of the liquid crystalline resin composition measured according to ISO11443 at a temperature 10to 30 ℃ higher than the melting point of the liquid crystalline resin and a shear rate of 1000/sec is preferably 1X 105 pas or less, more preferably 5 pas or more and 1X 102 pas or less. The melt viscosity was 1X 105When Pa · s or less, fluidity of the liquid crystalline resin composition is easily ensured and filling pressure does not become excessively high at the time of molding of a connector, particularly a low-thickness narrow-pitch connector.
(connector)
The connector of the present invention can be obtained by molding the liquid crystalline resin composition of the present invention. The connector of the present invention is not particularly limited, and examples thereof include connectors having a product overall length of less than 30mm and a product height of less than 5 mm. The connector having a product overall length of less than 30mm and a product height of less than 5mm is not particularly limited, and examples thereof include a low-thickness narrow-pitch connector, a coaxial connector, a Micro SIM connector, and a Micro SD connector. Among them, a low thickness narrow pitch connector is desirable. The low-thickness narrow-pitch connector is not particularly limited, and examples thereof include a substrate-to-substrate connector (also known as a "BtoB connector"), a connector for a flexible printed circuit board (used for connecting a flexible printed circuit board (FPC) and a Flexible Flat Cable (FFC), also known as an "FPC connector"), and the like. Among them, a low-thickness narrow-pitch connector having an inter-pitch distance of 0.5mm or less, a product overall length of 3.5mm or more and less than 30mm, and a product height of 1.5mm or less is preferable as a board-to-board connector or a connector for a flexible printed board.
The method of molding the connector of the present invention is not particularly limited, and molding conditions without residual internal stress are preferably selected to prevent deformation of the connector. In order to reduce the filling pressure and reduce the residual internal stress of the obtained connector, the barrel temperature of the molding machine is preferably a temperature equal to or higher than the melting point of the liquid crystalline resin.
In addition, the temperature of the mold is preferably 70-100 ℃. When the mold temperature is low, the liquid crystalline resin composition filled in the mold may have flow defects, which is not preferable. When the mold temperature is high, a problem such as generation of burrs may occur, which is not preferable. The injection rate is preferably 150 mm/sec or more. When the injection speed is low, only an unfilled molded body may be obtained, and even if a completely filled molded body is obtained, the molded body may have a high filling pressure and a large residual internal stress, and only a connector having poor flatness may be obtained.
The connector of the present invention is suppressed in warp deformation. The degree of warpage of the connector is determined as follows. That is, using the FPC connector shown in fig. 1, the height is measured at a plurality of positions shown by black dots in fig. 2, and the difference between the maximum height and the minimum height from the least square plane is taken as the warpage. The connector of the present invention suppresses the change of warpage before and after performing IR reflow soldering.
The connector of the present invention is excellent in heat resistance, for example, heat resistance evaluated by high-temperature rigidity. The high temperature stiffness can be evaluated by measuring the deflection temperature under load according to ISO75-1, 2.
The connector of the present invention is excellent in mechanical strength. The mechanical strength was evaluated by measuring the flexural strength, flexural deformation, and flexural modulus in accordance with the flexural test of ASTM D790.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
< examples 1 to 5 and comparative examples 1 to 7>
In the following examples and comparative examples, liquid crystalline resins LCP1 and LCP2 were produced as follows. At this time, the melting point and the melt viscosity of the pellets were measured under the following conditions.
[ measurement of melting Point ]
An endothermic peak temperature (Tm1) observed when a liquid crystal resin was measured under a temperature raising condition of 20 ℃/min from room temperature was observed using a DSC manufactured by TA Instruments, and then, the temperature was held at (Tm1+40) ° C for 2 minutes, and after the temperature was once cooled to room temperature under a temperature lowering condition of 20 ℃/min, the temperature of the endothermic peak observed when the temperature was measured again under a temperature raising condition of 20 ℃/min was measured.
[ measurement of melt viscosity ]
The melt viscosity of the liquid crystalline resin was measured according to ISO11443 using CAPILOGRAPH 1B model manufactured by Toyo Seiki Seisaku-Sho K.K., at a shear rate of 1000/sec using an orifice having an inner diameter of 1mm and a length of 20mm at a temperature of 10to 30 ℃ higher than the melting point of the liquid crystalline resin. The measurement temperature of LCP1 was 360 ℃ and the measurement temperature of LCP2 was 380 ℃.
(method for producing LCP 1)
The following raw material monomers, fatty acid metal salt catalyst and acylating agent were charged into a polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen gas inlet, and pressure-reducing/outflow line, and nitrogen substitution was started.
(I) 4-hydroxybenzoic acid: 1385g (60 mol%) (HBA)
(II) 6-hydroxy-2-naphthoic acid: 88g (2.8 mol%) (HNA)
(III) terephthalic acid: 504g (18.15 mol%) (TA)
(IV) isophthalic acid: 19g (0.7 mol%) (IA)
(V)4, 4' -dihydroxybiphenyl: 415g (13.35 mol%) (BP)
(VI) N-acetyl-p-aminophenol: 126g (5 mol%) (APAP)
Potassium acetate catalyst: 120mg of
Acetic anhydride: 1662g
After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Then, the temperature was raised to 360 ℃ over a further 5.5 hours, and then the pressure was reduced to 10Torr (1330 Pa) over a further 20 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced, the pressure was increased from a reduced pressure to a normal pressure, and the polymer was discharged from the lower part of the polymerization vessel to granulate the strand and form it into pellets. The obtained pellets had a melting point of 345 ℃ and a melt viscosity of 10 pas.
(method for producing LCP 2)
The following raw material monomers, fatty acid metal salt catalyst and acylating agent were charged into a polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen gas inlet, and pressure-reducing/outflow line, and nitrogen substitution was started.
(I) 4-hydroxybenzoic acid: 1040g (48 mol%) (HBA)
(II) 6-hydroxy-2-naphthoic acid: 89g (3 mol%) (HNA)
(III) terephthalic acid: 547g (21 mol%) (TA)
(IV) isophthalic acid: 91g (3.5 mol%) (IA)
(V)4, 4' -dihydroxybiphenyl: 716g (24.5 mol%) (BP)
Potassium acetate catalyst: 110mg
Acetic anhydride: 1644g
After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Then, the temperature was raised to 360 ℃ over a further 5.5 hours, and then the pressure was reduced to 5Torr (i.e., 667Pa) over a further 20 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, the pressure was increased from a reduced pressure to a normal pressure, and the polymer was discharged from the lower part of the polymerization vessel to granulate the strand and form it into pellets. The obtained pellets had a melting point of 355 ℃ and a melt viscosity of 10 pas.
(Components other than the liquid crystalline resin)
Fibrous fillers
1, wollastonite: NYGLOS 8(NYCO Materials, Inc., aspect ratio 17, average fiber length 136 μm, average fiber diameter 8 μm)
Wollastonite 2: NYAD 325(NYCO Materials, Inc., aspect ratio 5, average fiber length 50 μm, average fiber diameter 5 μm)
Grinding the fibers: PF70E001 manufactured by Nindon textile Co., Ltd., fiber diameter of 10 μm, and average fiber length of 70 μm (manufacturer's nominal value)
Platy Filler
Mica; AB-25S, manufactured by Kabushiki Kaisha Kogyo, and having an average particle diameter of 25 μm
Talc; CROWNTALC PP, manufactured by Sonmura industries, Inc., having an average particle diameter of 10 μm
Each of the liquid crystalline resins obtained above was mixed with the components other than the liquid crystalline resin using a twin-screw extruder to obtain a liquid crystalline resin composition. The amounts of the respective components are shown in tables 1 and 2. In the following, "%" relating to the amount of blending in the table represents mass%. The extrusion conditions for obtaining the liquid crystalline resin composition are as follows.
[ extrusion conditions ]
[ examples 1 to 4, comparative examples 1 to 7 ]
The temperature of the cylinder provided at the main feed port was set to 250 ℃ and the temperatures of all the other cylinders were set to 360 ℃. The liquid crystalline resin is supplied from the main inlet. The filler was supplied from a side inlet.
[ example 5 ]
The temperature of the cylinder provided at the main feed port was set to 250 ℃ and the temperatures of all the other cylinders were set to 370 ℃. The liquid crystalline resin is supplied from the main inlet. The filler was supplied from a side inlet.
(measurement of melt viscosity of liquid Crystal resin composition)
The melt viscosity of the liquid crystalline resin composition was measured according to ISO11443 using a model CAPILOGRAPH 1B manufactured by Toyo Seiki Seisaku-Sho K.K., at a temperature 10to 30 ℃ higher than the melting point of the liquid crystalline resin, using an orifice having an inner diameter of 1mm and a length of 20mm, and at a shear rate of 1000/sec. The temperature measured for the liquid crystalline resin composition using LCP1 was 360 ℃, and the temperature measured for the liquid crystalline resin composition using LCP2 was 380 ℃. The results are shown in tables 1 and 2.
The physical properties of the connector of the molded article comprising the liquid crystalline resin composition were measured by the following methods. The evaluation results are shown in tables 1 and 2.
(deflection temperature under load)
The liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a molded article, and the deflection temperature under load was measured in accordance with ISO75-1, 2.
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry Co., Ltd, SE100DU
Barrel temperature:
360 ℃ (examples 1 to 4 and comparative examples 1 to 7)
370 deg.C (example 5)
Temperature of the die: 80 deg.C
Injection speed: 33 mm/sec
(bending test)
A liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a 0.8mm thick molded article, and the flexural strength, flexural deformation, and flexural modulus were measured in accordance with ASTM D790.
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry Co., Ltd, SE100DU
Barrel temperature:
360 ℃ (examples 1 to 4 and comparative examples 1 to 7)
370 deg.C (example 5)
Temperature of the die: 80 deg.C
Injection speed: 33 mm/sec
(FPC connector warping)
The liquid crystalline resin composition was injection-molded under the following molding conditions (gate: tunnel gate, gate size:
) As shown in FIG. 1, the total size of 17.6 mm. times.4.00 mm. times.1.16 mm, the pitch distance of 0.5mm, the number of pin holes of 30X 2 pins, and the minimum wall thickness were obtained: 0.12mm FPC connector.
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry Co., Ltd, SE30DUZ
Barrel temperature (indicating temperature from the nozzle side):
360 ℃ -360 ℃ -350 ℃ -340 ℃ (examples 1-4, comparative examples 1-7)
370 ℃ -370 ℃ -360 ℃ -350 ℃ (example 5)
Temperature of the die: 80 deg.C
Injection speed: 200 mm/sec
Maintaining the pressure: 50MPa
Pressure maintaining time: 0.5 second
Cooling time: 10 seconds
Screw rotation speed: 120rpm
Screw back pressure: 1.2MPa
The resulting connector was left on a horizontal table, and the height of the connector was measured by a Quick Vision 404PROCNC image measuring machine manufactured by Mitutoyo Corporation. At this time, the heights are measured at a plurality of positions indicated by black dots in fig. 2, and the difference between the maximum height and the minimum height from the least square plane is defined as the warpage of the FPC connector. The warpage was measured before and after the IR reflow under the following conditions.
[ IR reflow soldering Condition ]
The measuring machine comprises: large-sized desk type reflow soldering apparatus RF-300 (using far infrared heater) manufactured by Japanese pulse technology research
Sample feeding speed: 140 mm/sec
Passing time of the reflow oven: 5 minutes
Temperature conditions in the preheating zone: 150 ℃ C
Temperature conditions of the reflow soldering zone: 190 deg.C
Peak temperature: 251 deg.C
(minimum filling pressure of FPC connector)
The minimum injection filling pressure at which a good molded body can be obtained when the FPC connector of fig. 1 is injection molded was measured as the minimum filling pressure.
[ Table 1]
[ Table 2]
As shown in tables 1 and 2, in the examples, the deflection temperature under load was 245 ℃ or higher, the bending deformation was 2.0% or higher, the bending modulus was 14000MPa or higher, the warpage of the FPC connector before reflow was less than 0.030mm, the warpage of the FPC connector after reflow was less than 0.090mm, and the minimum filling pressure of the FPC connector was less than 75 MPa. Therefore, it was confirmed that the liquid crystalline resin composition of the present invention is excellent in fluidity, and a connector of a molded article comprising the liquid crystalline resin composition is excellent in heat resistance and mechanical strength, and warpage is suppressed.
Claims (5)
1. A liquid crystalline resin composition comprising: (A) liquid crystalline resin, (B) fibrous wollastonite, and (C) mica,
the length-diameter ratio of the fibrous wollastonite in the step (B) is more than 8,
the liquid crystalline resin composition is characterized in that it comprises, based on the whole liquid crystalline resin composition,
the content of the liquid crystalline resin (A) is 62.5-72.5 mass%,
The content of the fibrous wollastonite (B) is 2.5-15 mass%,
The content of the (C) mica is 17.5-30 mass%,
The total content of the fibrous wollastonite (B) and the mica (C) is 27.5 to 37.5 mass%.
2. The liquid crystalline resin composition according to claim 1, which is used for a connector having a product overall length of less than 30mm and a product height of less than 5 mm.
3. A connector comprising a molded article of the liquid crystalline resin composition according to claim 1 or 2, wherein the total length of the product is less than 30mm and the height of the product is less than 5 mm.
4. The connector of claim 3, being a low thickness narrow pitch connector.
5. The connector according to claim 3 or 4, wherein the pitch distance is 0.5mm or less,
The total length of the product is more than 3.5mm and less than 30mm,
The height of the product is less than 1.5mm,
the connector is a low-thickness narrow-pitch connector as a substrate-to-substrate connector or a connector for a flexible printed substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018214698 | 2018-11-15 | ||
| JP2018-214698 | 2018-11-15 | ||
| PCT/JP2019/042849 WO2020100618A1 (en) | 2018-11-15 | 2019-10-31 | Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition |
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| CN113015765A true CN113015765A (en) | 2021-06-22 |
| CN113015765B CN113015765B (en) | 2022-04-26 |
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| JP (1) | JP6841978B2 (en) |
| KR (1) | KR102397208B1 (en) |
| CN (1) | CN113015765B (en) |
| MY (1) | MY187836A (en) |
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| CN115651368A (en) * | 2022-11-08 | 2023-01-31 | 珠海万通特种工程塑料有限公司 | Antistatic liquid crystal polyester composition and preparation method and application thereof |
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| KR102501091B1 (en) * | 2020-05-13 | 2023-02-17 | 포리프라스틱 가부시키가이샤 | Liquid crystalline resin composition for surface mount relay and surface mount relay using the same |
| WO2023054314A1 (en) * | 2021-09-28 | 2023-04-06 | ポリプラスチックス株式会社 | Resin composition |
| KR20230168762A (en) * | 2022-06-08 | 2023-12-15 | 롯데케미칼 주식회사 | Liquid crystalline polymer composition and article produced therefrom |
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| TW538094B (en) * | 2000-04-20 | 2003-06-21 | Ueno Seiyaku Oyo Kenkyujo Kk | Liquid crystal polyester resin composition |
| JP2002294038A (en) * | 2001-03-28 | 2002-10-09 | Sumitomo Chem Co Ltd | Liquid crystal ester resin composition |
| JP2009108179A (en) * | 2007-10-30 | 2009-05-21 | Sumitomo Chemical Co Ltd | Liquid crystalline polyester resin composition and connector comprising the resin composition |
| JP2009108180A (en) * | 2007-10-30 | 2009-05-21 | Sumitomo Chemical Co Ltd | Liquid crystalline polyester resin composition |
| KR101639439B1 (en) * | 2008-12-25 | 2016-07-13 | 스미또모 가가꾸 가부시키가이샤 | Liquid-crystalline polyester resin composition and connector using the same |
| TWI586750B (en) * | 2011-02-28 | 2017-06-11 | 住友化學股份有限公司 | Liquid crystal polyester composition and process for producing the same |
| WO2013129338A1 (en) * | 2012-02-29 | 2013-09-06 | ポリプラスチックス株式会社 | Liquid crystal resin composition for camera modules |
| WO2014027955A1 (en) * | 2012-08-16 | 2014-02-20 | Unisteel Technology International Limited | A novel method of making a novel lcp nanocomposite |
| JP5753144B2 (en) * | 2012-09-21 | 2015-07-22 | ポリプラスチックス株式会社 | Totally aromatic polyester and polyester resin composition, and polyester molded article |
| WO2017110646A1 (en) * | 2015-12-22 | 2017-06-29 | ポリプラスチックス株式会社 | Liquid-crystalline resin composition and insert-molded article |
| KR102244483B1 (en) * | 2016-09-26 | 2021-04-23 | 도레이 카부시키가이샤 | Liquid crystal polyester resin composition, molded article, and method of manufacturing molded article |
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- 2019-10-31 MY MYPI2021002662A patent/MY187836A/en unknown
- 2019-10-31 CN CN201980074882.7A patent/CN113015765B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050182166A1 (en) * | 2003-12-24 | 2005-08-18 | Mitsubishi Chemical Corporation | Reinforced thermoplastic resin composition and molded products thereof |
| CN1727437A (en) * | 2004-07-30 | 2006-02-01 | 汎塑料株式会社 | Liquid crystalline polyester resin composition |
| CN107924039A (en) * | 2015-09-01 | 2018-04-17 | 宝理塑料株式会社 | Camera module use liquid crystalline resin composition and use its camera module |
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| CN115651368A (en) * | 2022-11-08 | 2023-01-31 | 珠海万通特种工程塑料有限公司 | Antistatic liquid crystal polyester composition and preparation method and application thereof |
| CN115651368B (en) * | 2022-11-08 | 2023-12-19 | 珠海万通特种工程塑料有限公司 | Antistatic liquid crystal polyester composition and preparation method and application thereof |
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| MY187836A (en) | 2021-10-26 |
| TW202028365A (en) | 2020-08-01 |
| JPWO2020100618A1 (en) | 2021-02-15 |
| KR20210055782A (en) | 2021-05-17 |
| KR102397208B1 (en) | 2022-05-12 |
| WO2020100618A1 (en) | 2020-05-22 |
| JP6841978B2 (en) | 2021-03-10 |
| CN113015765B (en) | 2022-04-26 |
| PH12021551106A1 (en) | 2021-11-22 |
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