WO2014050371A1

WO2014050371A1 - Composite resin composition for electronic component and electronic component molded from composite resin composition

Info

Publication number: WO2014050371A1
Application number: PCT/JP2013/072226
Authority: WO
Inventors: 博樹深津; 峰生大竹; 和博龍; 淳一郎杉浦; 吉昭田口
Original assignee: ポリプラスチックス株式会社
Priority date: 2012-09-26
Filing date: 2013-08-20
Publication date: 2014-04-03
Also published as: CN104704049A; SG11201502394YA; MY174277A; JPWO2014050371A1; TW201431949A; KR20150060829A; CN104704049B; TWI502019B; JP5769888B2

Abstract

The objective of the present invention is to provide a composite resin composition for electronic components which has excellent fluidity and an electronic component molded from the composite resin composition. The present invention provides a composite resin composition for electronic components comprising (A) a liquid crystal polymer, (B) milled fiber and (C) a plate-like inorganic filler, wherein (A) the liquid crystal polymer includes, as essential components, (I) a constitutional unit derived from a 4-hydroxybenzoic acid, (II) a constitutional unit derived from a 2-hydroxy-6-naphthoic acid, (III) a constitutional unit derived from a terephthalic acid, (IV) a constitutional unit derived from an isophthalic acid and (V) a constitutional unit derived from a 4,4'-dihydroxybiphenyl.

Description

Composite resin composition for electronic parts, and electronic parts molded from the composite resin composition

The present invention relates to a composite resin composition for electronic parts and an electronic part molded from the composite resin composition. In particular, the present invention relates to a composite resin composition for an asymmetric electronic component, an asymmetric electronic component molded from the composite resin composition, a composite resin composition for a low profile narrow pitch connector, and a low molding molded from the composite resin composition. Related to narrow pitch connectors.

The liquid crystalline polymer is a thermoplastic resin excellent in dimensional accuracy, fluidity and the like. Due to these characteristics, liquid crystalline polymers have been conventionally employed as materials for various electronic components. In manufacturing such an electronic component, the liquid crystal polymer composition is required to have good fluidity. Examples of the electronic component include an asymmetric electronic component, a low profile narrow pitch connector, and a coaxial connector.

Especially for asymmetric electronic components, the following background exists. Due to the demands of the era of higher heat resistance of connectors (improvement of productivity by mounting technology), higher density (multi-core), and miniaturization due to the recent high performance of electronic equipment, the characteristics of the above liquid crystalline polymer Taking advantage of the above, a liquid crystalline polymer composition reinforced with glass fiber has been adopted as a connector material.

In recent years, however, connectors have become lighter, thinner, and smaller, and due to insufficient rigidity due to insufficient thickness of molded parts and internal stress due to metal terminal inserts, warpage deformation occurs after molding and during reflow heating, and soldering to the board There is a problem that becomes defective. That is, in the conventional reinforcement using only glass fibers, there is a problem that if the addition amount of the glass fibers is increased in order to increase the rigidity, the resin is not filled in the thin portion, or the insert terminal is deformed by the pressure during molding.

In order to solve the problem of warp deformation, the molding technique has been devised, and a specific plate-like filler has been proposed in terms of material. In other words, in the case of ordinary connectors (electronic parts) that exist in the market a lot, it is possible to control the dimensional accuracy and warpage of the product by designing the gate position and design so as to maintain symmetry. Further, by using a conventionally proposed low warp material, a product with little warp deformation is obtained.

However, as the shape of electronic components has become more complex in recent years, it has been required to provide an asymmetric electronic component that is not symmetric with respect to any of the XY, YZ, and XZ axial surfaces of the molded product. ing. A typical example of such an asymmetric electronic component is a memory module connector having a latch structure (having fixing claws at both ends) such as a DDR-DIMM connector. In particular, a memory module connector for a notebook personal computer has a latch structure for mounting and a notch for alignment, and thus has a very complicated shape.

In the case of such an asymmetric electronic component, unlike a normal connector (symmetric electronic component) having symmetry with respect to any of the XY axis plane, YZ axis plane, and XZ axis plane of the molded product, symmetry Therefore, there is a limit to the improvement of warp deformation from the viewpoint of the molding technique. In addition, in the case of an asymmetric electronic component having a complicated shape, the orientation of the resin and filler in the molded product is complicated, higher fluidity is required, and it is more difficult to suppress warpage deformation.

As a technique for solving such problems, for example, Patent Document 1 is formed from a liquid crystalline polymer composition obtained by blending a specific amount of a specific fibrous filler and a specific plate-like filler. An asymmetric electronic component having no symmetry with respect to any of the XY axis plane, the YZ axis plane, and the XZ axis plane of the product is disclosed.

In particular, the following background exists for low-profile narrow-pitch connectors. With the recent downsizing and thinning of electronic devices, there is a need for lowering the height and narrowing the pitch of electronic components (connectors and the like) constituting the electronic device. For example, Patent Document 2 discloses a connector formed from a liquid crystalline polymer composition reinforced with mica and glass fiber. Such connectors are for board-to-board connectors and flexible printed boards used to connect flexible printed boards (FPCs) and flexible flat cables (FFCs) that require fluidity and dimensional stability. Used as a connector.

International Publication No. 2008/023839 JP 2006-37061 A

However, conventional liquid crystalline polymer compositions are not sufficiently fluid. In particular, the asymmetric electronic component is disclosed in the above-mentioned Patent Document 1 due to a shape change accompanying an increase in the integration rate in the recent asymmetric electronic component, particularly a decrease in pitch distance, a product height, and an increase in the number of poles. It has been found that conventional liquid crystal polymer compositions such as the prepared liquid crystal polymer composition may not be able to cope with them. That is, the conventional liquid crystalline polymer composition has insufficient fluidity, and it has been difficult to obtain an asymmetric electronic component in which warpage deformation is suppressed from such a liquid crystalline polymer composition. In particular, for low-profile narrow pitch connectors, when a connector is formed from a conventional liquid crystalline polymer composition, the flowability of the composition is not sufficient and the processability is poor, resulting in a low profile and narrow pitch. It was difficult to manufacture low-profile narrow-pitch connectors that meet the needs of

The present invention has been made in view of such circumstances, and an object thereof is to provide a composite resin composition for electronic parts having good fluidity, and an electronic part molded from the composite resin composition. In one preferred embodiment of the present invention, a composite resin composition for an asymmetric electronic component that can provide an asymmetric electronic component with good fluidity and reduced warpage deformation, and an asymmetric electronic component molded from the composite resin composition The purpose is to provide. In another preferred embodiment, the present invention provides a composite resin composition having good fluidity and capable of realizing the production of a low profile narrow pitch connector, and a low profile narrow pitch connector molded from the composite resin composition. For the purpose.

The present inventors have found that the above problem can be solved by combining a liquid crystalline polymer containing a predetermined amount of a specific structural unit, glass fibers and / or milled fibers, and a plate-like inorganic filler. Specifically, the present invention provides the following.

(1) A composite resin composition for electronic parts comprising (A) a liquid crystalline polymer, (B) a milled fiber, and (C) a plate-like inorganic filler,
The (A) liquid crystalline polymer has, as essential constituents, the following constituent units: (I) constituent units derived from 4-hydroxybenzoic acid, (II) constituent units derived from 2-hydroxy-6-naphthoic acid, III) a structural unit derived from terephthalic acid, (IV) a structural unit derived from isophthalic acid, and (V) a structural unit derived from 4,4′-dihydroxybiphenyl,
The content of the structural unit (I) with respect to all the structural units is 35 to 75 mol%,
The content of the structural unit (II) with respect to the total structural unit is 2 to 8 mol%,
The content of the structural unit (III) with respect to all the structural units is 4.5 to 30.5 mol%,
The content of the structural unit (IV) with respect to all the structural units is 2 to 8 mol%,
The content of the structural unit (V) with respect to all the structural units is 12.5 to 32.5 mol%,
The total amount of the structural units (II) and (IV) is 4 to 10 mol% with respect to all the structural units,
The content of the liquid crystal polymer (A) is 40 to 80% by mass with respect to the entire composite resin composition,
The content of the (B) milled fiber is 10 to 30% by mass with respect to the entire composite resin composition,
The composite resin composition for electronic parts, wherein the content of the (C) plate-like inorganic filler is 10 to 35% by mass with respect to the entire composite resin composition.

(2) The electronic component is an asymmetric electronic component,
The content of the liquid crystal polymer (A) is 47.5 to 65% by mass with respect to the entire composite resin composition,
The content of the (B) milled fiber is 15 to 30% by mass with respect to the entire composite resin composition,
The composite resin composition for electronic components according to (1), wherein the content of the (C) plate-like inorganic filler is 20 to 35% by mass with respect to the entire composite resin composition.

(3) The composite resin composition for electronic components according to (2), wherein the (C) plate-like inorganic filler is at least one selected from the group consisting of talc and mica.

(4) The electronic component is a low profile narrow pitch connector,
The composite resin composition for electronic parts according to (1), wherein the content of the (C) plate-like inorganic filler is 10 to 30% by mass with respect to the entire composite resin composition.

(5) The above (A) liquid crystalline polymer has a [melting point-crystallization temperature] value of 50 to 60 ° C. and conforms to ISO 11443 at a shear rate of 1000 / sec at a temperature 10 to 20 ° C. higher than the melting point. (4) The composite resin composition for electronic parts according to (4), wherein the melt viscosity measured in this way is 5 to 15 Pa · s.

(6) The average fiber length of the (B) milled fiber is 50 to 100 μm, and
(C) The plate-like inorganic filler is a composite resin composition for electronic parts according to (4) or (5), which is at least one selected from the group consisting of talc and mica.

(7) An electronic component molded from the composite resin composition for electronic components according to (1).

(8) The content of the liquid crystal polymer (A) is 47.5 to 65% by mass with respect to the entire composite resin composition,
The content of the (B) milled fiber is 15 to 30% by mass with respect to the entire composite resin composition,
The content of the (C) plate-like inorganic filler is 20 to 35% by mass with respect to the entire composite resin composition,
The electronic component according to (7), which is an asymmetric electronic component having no symmetry with respect to any of the XY axis plane, the YZ axis plane, and the XZ axis plane of the molded product.

(9) The electronic component according to (8), wherein the (C) plate-like inorganic filler is at least one selected from the group consisting of talc and mica.

(10) A connector for a memory module having a pitch distance of 0.8 mm or less, a total product length of 60.0 mm or more, a product height of 6.0 mm or less, and a pole number of 150 or more. The electronic component described.

(11) The electronic component according to (8) or (9), which is a memory card socket having a rail structure and a product height of 3.0 mm or less.

(12) The content of the (C) plate-like inorganic filler is 10 to 30% by mass with respect to the entire composite resin composition,
The distance between pitches is 0.5 mm or less,
The total product length is 4.0mm or more,
The product height is 4.0 mm or less,
The electronic component according to (7), which is a low-profile narrow-pitch connector that is a board-to-board connector or a connector for a flexible printed board.

(13) The above (A) liquid crystalline polymer has a [melting point-crystallization temperature] value of 50 to 60 ° C. and conforms to ISO 11443 at a shear rate of 1000 / sec at a temperature 10 to 20 ° C. higher than the melting point. The electronic component according to (12), which has a melt viscosity measured in the range of 5 to 15 Pa · s.

(14) The average fiber length of the (B) glass fiber and milled fiber is 50 to 100 μm, and
The (C) plate-like inorganic filler is an electronic component according to (12) or (13), which is at least one selected from the group consisting of talc and mica.

According to the present invention, there are provided a composite resin composition for electronic parts having good fluidity, and an electronic part molded from the composite resin composition. In a preferred embodiment of the present invention, a composite resin composition for an asymmetric electronic component capable of obtaining an asymmetric electronic component having good fluidity and suppressing warpage deformation, and an asymmetric electronic component molded from the composite resin composition Is provided. In a preferred embodiment of the present invention, there are provided a composite resin composition having good fluidity and capable of producing a low profile narrow pitch connector, and a low profile narrow pitch connector molded from the composite resin composition. .

It is a figure which shows the DDR-DIMM connector shape | molded in the Example. A indicates the gate position. It is a figure which shows the measuring point in the measurement of the curvature of the DDR-DIMM connector performed in the Example. It is a figure which shows the low profile narrow pitch connector (connector for flexible printed circuit boards) shape | molded in the Example. In addition, the unit of the numerical value in a figure is mm.

Hereinafter, embodiments of the present invention will be specifically described.

[Composite resin composition]
The composite resin composition in the present invention contains a predetermined amount of a specific liquid crystalline polymer, glass fibers and / or milled fibers, and a plate-like inorganic filler. Hereinafter, the components constituting the composite resin composition in the present invention will be described.

(Liquid crystal polymer)
The liquid crystalline polymer in the present invention contains, as essential constituents, the following constituent units: (I) constituent units derived from 4-hydroxybenzoic acid (also referred to as “HBA”), (II) 2-hydroxy-6-naphthoic acid A structural unit derived from (also referred to as “HNA”), (III) a structural unit derived from terephthalic acid (also referred to as “TA”), (IV) a structural unit derived from isophthalic acid (also referred to as “IA”), and (V) Contains structural units derived from 4,4′-dihydroxybiphenyl (also referred to as “BP”).

The liquid crystalline polymer in the present invention contains the above structural units at a specific ratio. That is, the content of the structural unit (I) is 35 to 75 mol% (preferably 40 to 65 mol%) with respect to all the structural units. The content of the structural unit (II) is 2 to 8 mol% (preferably 3 to 7 mol%) with respect to all the structural units. The content of the structural unit (III) is 4.5 to 30.5 mol% (preferably 13 to 26 mol%) based on all the structural units. The content of the structural unit (IV) is 2 to 8 mol% (preferably 3 to 7 mol%) with respect to all the structural units. The content of the structural unit (V) is 12.5 to 32.5 mol% (preferably 15.5 to 29 mol%) with respect to all the structural units. The total amount of the structural units (II) and (IV) is 4 to 10 mol% (preferably 5 to 10 mol%) with respect to the total structural units.

When the content of the constituent unit (I) is less than 35 mol% or more than 75 mol% with respect to all the constituent units, the melting point of the liquid crystalline polymer is remarkably increased, and asymmetric electronic components, low-profile narrow pitch connectors, and When manufacturing a molded article such as an electronic component including a coaxial connector, the liquid crystalline polymer is solidified in the reactor, and it may not be possible to manufacture a liquid crystalline polymer having a desired molecular weight.

When the content of the constituent unit (II) is less than 2 mol% with respect to all constituent units, when manufacturing molded articles such as electronic parts including asymmetric electronic parts, low profile narrow pitch connectors, and coaxial connectors This is not preferable because cracks may occur in the molded product. Further, if the content of the structural unit (II) is more than 8 mol% with respect to all the structural units, the heat resistance of the liquid crystalline polymer is lowered, which is not preferable.

When the content of the structural unit of (III) is less than 4.5 mol% or more than 30.5 mol% with respect to all the structural units, the melting point of the liquid crystalline polymer becomes remarkably high, and the asymmetric electronic component, low profile When manufacturing molded products such as electronic components including pitch connectors and coaxial connectors, the liquid crystalline polymer is solidified in the reactor, and it may not be possible to produce a liquid crystalline polymer having a desired molecular weight. .

When the content of the constituent unit of (IV) is less than 2 mol% with respect to all constituent units, when manufacturing molded articles such as electronic parts including asymmetric electronic parts, low profile narrow pitch connectors, and coaxial connectors This is not preferable because cracks may occur in the molded product. In addition, the melting point of the liquid crystalline polymer becomes extremely high, and the liquid crystalline polymer is solidified in the reactor when a molded product such as an asymmetric electronic component, a low-profile narrow pitch connector, and an electronic component including a coaxial connector is manufactured. Since it may become impossible to manufacture the liquid crystalline polymer of molecular weight, it is not preferable.

In addition, if the content of the structural unit (IV) is more than 8 mol% with respect to all the structural units, the heat resistance of the liquid crystalline polymer is lowered, which is not preferable.

When the content of the structural unit (V) is less than 12.5 mol% or more than 32.5 mol% with respect to all the structural units, the melting point of the liquid crystalline polymer is remarkably increased, and the asymmetric electronic component liquid crystalline polymer is Solidifying in a reactor to produce a liquid crystalline polymer having a desired molecular weight is not preferable because it becomes impossible to produce a molded product such as a low-profile narrow pitch connector and an electronic component including a coaxial connector.

When the total amount of the structural units (II) and (IV) is less than 4 mol% with respect to all the structural units, the crystallization heat amount of the liquid crystalline polymer can be 2.5 J / g or more. In this case, when a molded product such as an asymmetric electronic component, a low-profile narrow-pitch connector, and an electronic component including a coaxial connector is manufactured, there is a possibility that the molded product may be cracked. A preferable value for the heat of crystallization of the liquid crystalline polymer is 2.3 J / g or less, and more preferably 2.0 J / g or less. The crystallization heat quantity indicates the crystallization state of the liquid crystalline polymer, and is a value obtained by differential calorimetry. Specifically, after observing the endothermic peak temperature (Tm1) observed when the liquid crystalline polymer is measured from room temperature at a temperature rising condition of 20 ° C./min, the liquid crystal polymer is held at a temperature of Tm1 + 40 ° C. for 2 minutes, and then 20 ° C. It refers to the calorific value of the exothermic peak obtained from the peak of the exothermic peak temperature observed when measured under the temperature lowering condition per minute.

Further, if the total amount of the structural units (II) and (IV) is more than 10 mol% with respect to all the structural units, the heat resistance of the liquid crystalline polymer is lowered, which is not preferable.

In addition, the well-known other structural unit can also be introduce | transduced into the liquid crystalline polymer in this invention in the range which does not inhibit the objective of this invention.

The liquid crystalline polymer in the present invention can be obtained by polymerizing the above structural units by a direct polymerization method, a transesterification method, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method or the like.

In the polymerization of the above structural unit, in addition to the above structural unit, an acylating agent for the above structural unit or a monomer whose terminal is activated as an acid chloride derivative can be used in combination. Examples of the acylating agent include acid anhydrides such as acetic anhydride.

In the polymerization of the above structural units, various catalysts can be used, for example, dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, alkali metal salts of carboxylic acids, alkaline earths. Metal salts, Lewis acid salts (BF _{3 and the} like) and the like. The amount of the catalyst used may be about 0.001 to 1% by mass, preferably about 0.003 to 0.2% by mass, based on the total amount of the above structural units.

The conditions for the polymerization reaction are not particularly limited as long as the polymerization of the above structural units proceeds. For example, the reaction temperature is 200 to 380 ° C., the final ultimate pressure is 0.1 to 760 Torr (that is, 13 to 101,080 Pa). ).

The polymerization reaction may be a method (one-stage system) in which all the raw material monomers, acylating agent and catalyst are charged in the same reaction vessel to start the reaction, and corresponds to each structural unit of (I), (II) and (V). After acylating the raw material monomers, that is, the structural unit derived from 4-hydroxybenzoic acid, the structural unit derived from 2-hydroxy-6-naphthoic acid, and the hydroxyl group of 4,4′-dihydroxybiphenyl with an acylating agent, A raw material monomer corresponding to each structural unit of (III) and (IV), that is, a method of reacting with carboxyl groups of terephthalic acid and isophthalic acid (two-stage method) may be used.

Some liquid crystalline polymers containing the structural units (I) to (V) do not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the liquid crystalline polymer. The liquid crystalline polymer in the present invention is preferably a liquid crystalline polymer that forms an anisotropic molten phase, that is, a liquid crystalline polymer that exhibits optical anisotropy when melted, in that it has processability.

The property of melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. Specifically, for melting anisotropy, a polarizing microscope (manufactured by Olympus Co., Ltd.) is used, a sample placed on a hot stage (manufactured by Linkham Co., Ltd.) is melted, and the magnification is 150 times under a nitrogen atmosphere. This can be confirmed by observation. Liquid crystalline polymers that exhibit optical anisotropy when melted are optically anisotropic and transmit light when inserted between crossed polarizers. When the sample is optically anisotropic, for example, polarized light is transmitted even in a molten stationary liquid state.

Further, the melt viscosity of the liquid crystalline polymer measured in accordance with ISO 11443 at a temperature 10 to 20 ° C. higher than the melting point and at a shear rate of 1000 / second is more preferably 1 × 10 ⁵ Pa · s or less (more preferably ⁵ Pa · s or more). And 1 × 10 ² Pa · s or less) at the time of molding an electronic component, particularly at the time of molding a portion having a complicated shape such as a latch structure or a notch in an asymmetric electronic component. This is preferable in that the fluidity of the resin is ensured and the filling pressure does not become excessive.

Further, the liquid crystalline polymer in the present invention has a value of [melting point−crystallization temperature], which is a value obtained by subtracting the crystallization temperature from the melting point, and a temperature of 10 to 20 ° C. higher than the melting point. The melt viscosity measured according to ISO 11443 at a shear rate of 1000 / sec is preferably 5 to 15 Pa · s. According to such a liquid crystalline polymer, the fluidity of the composite resin composition can be secured at the time of molding an electronic component, particularly at the time of molding a low profile narrow pitch connector, etc., and therefore the filling pressure becomes an excessive value. This can be suppressed.

The composite resin composition in the present invention contains the liquid crystalline polymer in the composite resin composition in an amount of 40 to 80% by mass with respect to the total composite resin composition. If the content of the liquid crystalline polymer is less than 40% by mass with respect to the entire composite resin composition, the fluidity is deteriorated, which is not preferable. When the content of the liquid crystalline polymer is more than 80% by mass with respect to the entire composite resin composition, an asymmetric electronic component obtained from the composite resin composition, a low-profile narrow pitch connector, an electronic component including a coaxial connector, etc. This is not preferable because the flexural modulus and crack resistance of the molded product are lowered. The composite resin composition in the present invention preferably contains the liquid crystalline polymer in the composite resin composition in an amount of 50 to 70% by mass based on the entire composite resin composition.

In particular, when the composite resin composition of the present invention is for an asymmetric electronic component, the liquid crystal polymer is contained in the composite resin composition in an amount of 47.5 to 65% by mass with respect to the entire composite resin composition. Is preferred. When the content of the liquid crystalline polymer is 47.5% by mass or more based on the entire composite resin composition, the fluidity of the composite resin composition tends to be good, and the asymmetric electronic component obtained from the composite resin composition It is preferable because warpage deformation of a molded product such as the above is difficult to increase. When the content of the liquid crystalline polymer is 65% by mass or less with respect to the entire composite resin composition, the bending elastic modulus and crack resistance of molded products such as asymmetric electronic parts obtained from the composite resin composition are unlikely to decrease. Therefore, it is preferable. In particular, when the composite resin composition of the present invention is for an asymmetric electronic component, it is more preferable that the liquid crystalline polymer is contained in the composite resin composition in an amount of 50 to 55% by mass with respect to the total composite resin composition. preferable.

(Milled fiber)
Since the composite resin composition in the present invention contains the above-mentioned liquid crystalline polymer and milled fiber, a molded product obtained by molding the composite resin composition is excellent in high-temperature rigidity.

In the composite resin composition of the present invention, the average fiber length of the milled fiber calculated from the fiber length of the milled fiber is preferably 50 to 150 μm. An average fiber length of 50 μm or more is preferable because the high-temperature rigidity of a molded product obtained from the composite resin composition is sufficient. An average fiber length of 150 μm or less is preferable because the fluidity of the composite resin composition becomes good and warpage deformation of the molded product does not easily increase.

In particular, when the composite resin composition of the present invention is for a low profile narrow pitch connector, the average fiber length of the milled fiber calculated from the fiber length of the milled fiber in the composite resin composition of the present invention is 50 to 100 μm. Preferably there is. An average fiber length of 50 μm or more is preferable because the high-temperature rigidity of a molded product obtained from the composite resin composition is sufficient. When the average fiber length is 100 μm or less, the fluidity of the composite resin composition becomes good and it is difficult to mold the composite resin composition, which is preferable.

Further, the fiber diameter of the milled fiber in the present invention is not particularly limited, but generally about 5 to 15 μm is used.

The composite resin composition in the present invention contains 10 to 30% by mass of milled fiber with respect to the entire composite resin composition. When the content of the milled fiber is less than 10% by mass relative to the entire composite resin composition, molding of electronic components including asymmetric electronic components, low profile narrow pitch connectors, and coaxial connectors obtained from the composite resin composition This is not preferable because the weight deflection temperature of the product is low and the high-temperature rigidity is not sufficient. If the content of the milled fiber is more than 30% by mass with respect to the entire composite resin composition, the fluidity of the composition deteriorates, which is not preferable.

The composite resin composition in the present invention preferably contains 15 to 30% by mass of milled fiber with respect to the entire composite resin composition, particularly when used for asymmetric electronic components. When the content of the milled fiber is 15% by mass or more based on the entire composite resin composition, a molded article such as an asymmetric electronic component obtained from the composite resin composition is less likely to have a low deflection temperature, and has high-temperature rigidity. This is preferable because it is sufficient. It is preferable that the content of the milled fiber is 30% by mass or less with respect to the entire composite resin composition because the fluidity of the composite resin composition becomes good and warpage deformation of the molded article is difficult to increase.

(Plate-like inorganic filler)
The composite resin composition in the present invention further includes a plate-like inorganic filler. By including a plate-like inorganic filler in the composite resin composition in the present invention, a molded product in which warpage deformation is suppressed can be obtained.

The plate-like inorganic filler is contained in an amount of 10 to 35% by mass with respect to the entire composite resin composition. If the content of the plate-like inorganic filler is less than 10% by mass with respect to the entire composite resin composition, it is not preferable because warpage deformation of a molded product obtained from the composite resin composition is not sufficient. If the content of the plate-like inorganic filler is more than 35% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition may be deteriorated and it may be difficult to mold the composite resin composition. This is not preferable.

The plate-like inorganic filler is preferably contained in an amount of 20 to 35% by mass with respect to the entire composite resin composition, particularly when the composite resin composition is for an asymmetric electronic component. It is preferable that the content of the plate-like inorganic filler is 20% by mass or more based on the entire composite resin composition because warpage deformation of a molded product such as an asymmetric electronic component obtained from the composite resin composition is difficult to increase. It is preferable that the content of the plate-like inorganic filler is 35% by mass or less with respect to the entire composite resin composition because the fluidity of the composite resin composition tends to be good.

The plate-like inorganic filler is preferably contained in an amount of 10 to 30% by mass based on the entire composite resin composition, particularly when the composite resin composition is for a low profile narrow pitch connector. When the content of the plate-like inorganic filler is 10% by mass or more based on the entire composite resin composition, it is possible to sufficiently suppress warpage deformation of a molded product such as a low profile narrow pitch connector obtained from the composite resin composition. It is preferable because it is easy. When the content of the plate-like inorganic filler is 30% by mass or less with respect to the entire composite resin composition, the fluidity of the composite resin composition tends to be good, and it is difficult to form the composite resin composition. preferable.

Examples of the plate-like inorganic filler in the present invention include talc, mica, glass flakes, various metal foils and the like, but a molded product obtained from the composite resin composition without deteriorating the fluidity of the composite resin composition. It is preferable that it is 1 or more types chosen from the group which consists of a talc and a mica at the point of suppressing warp deformation | transformation. Further, the average particle diameter of the plate-like inorganic filler is not particularly limited, but a smaller one is desirable in consideration of fluidity in the thin portion. On the other hand, in order to reduce warping deformation of molded products such as asymmetric electronic parts obtained from composite resin compositions, low-profile narrow-pitch connectors, and electronic parts including coaxial connectors, a certain size must be maintained. desirable. Specifically, it is preferably 1 to 100 μm, more preferably 5 to 50 μm.

〔talc〕
As the talc that can be used in the present invention, the total content of Fe ₂ O ₃ , Al ₂ O ₃ , and CaO is 2.5 mass% or less with respect to the total solid content of the talc, and Fe ₂ O ₃ and The total content of Al ₂ O ₃ is more than 1.0% by mass and 2.0% by mass or less, and the content of CaO is preferably less than 0.5% by mass. That is, the talc that can be used in the present invention contains at least one of Fe ₂ O ₃ , Al ₂ O ₃ , and CaO in addition to the main components SiO ₂ and MgO, and each component has the above content. It may be contained in a range.

In the talc, when the total content of Fe ₂ O ₃ , Al ₂ O ₃ , and CaO is 2.5% by mass or less, the molding processability of the composite resin composition and the asymmetric electron molded from the composite resin composition The heat resistance of molded parts such as electronic parts including parts, low-profile narrow pitch connectors, and coaxial connectors is unlikely to deteriorate. The total content of Fe ₂ O ₃ , Al ₂ O ₃ , and CaO is preferably 1.0% by mass or more and 2.0% by mass or less.

Of the talc, talc having a total content of Fe ₂ O ₃ and Al ₂ O ₃ of more than 1.0% by mass is easily available. Further, in the talc, when the total content of Fe ₂ O ₃ and Al ₂ O ₃ is 2.0% by mass or less, the molding processability of the composite resin composition and the asymmetric electronic component molded from the composite resin composition In addition, the heat resistance of molded products such as electronic parts including low-profile narrow-pitch connectors and coaxial connectors is unlikely to deteriorate. The total content of Fe ₂ O ₃ and Al ₂ O ₃ is preferably more than 1.0 mass% and not more than 1.7 mass%.

Further, in the above talc, when the CaO content is less than 0.5% by mass, the molding processability of the composite resin composition, the asymmetric electronic component molded from the composite resin composition, the low profile narrow pitch connector, and the coaxial The heat resistance of molded products such as electronic parts including connectors is unlikely to deteriorate. The content of CaO is preferably 0.01% by mass or more and 0.4% by mass or less.

The mass average or volume-based cumulative average particle diameter (D ₅₀ ) of talc in the present invention measured by laser diffraction method is 4 from the viewpoint of preventing warpage deformation of the molded product and maintaining fluidity of the composite resin composition. It is preferably from 0 to 20.0 μm, more preferably from 10 to 18 μm.

[Mica]
Mica is a pulverized product of 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 artificial mica. Of these, muscovite is preferable in terms of good hue and low price.

Further, in the production of mica, wet pulverization and dry pulverization are known as methods for pulverizing minerals. The wet pulverization method is a method in which raw mica is roughly pulverized with a dry pulverizer, then water is added and main pulverization is performed by wet pulverization in a slurry state, followed by dehydration and drying. Compared with the wet pulverization method, the dry pulverization method is a general method at a low cost. However, when the wet pulverization method is used, it is easier to pulverize the mineral thinly and finely. In the present invention, it is preferable to use a thin and fine pulverized product because mica having a preferable average particle diameter and thickness described later can be obtained. Therefore, in the present invention, it is preferable to use mica produced by a wet pulverization method.

In addition, in the wet pulverization method, it is necessary to disperse the material to be pulverized in water. Therefore, in order to increase the dispersion efficiency of the material to be pulverized, a coagulating sedimentation agent and / or a precipitation aid is added to the material to be pulverized. Is common. Examples of the coagulating settling agent and settling aid that can be used in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyiron sulfate, polyferric chloride, iron-silica inorganic high Examples thereof include molecular flocculants, ferric chloride-silica inorganic polymer flocculants, slaked lime (Ca (OH) ₂ ), caustic soda (NaOH), and soda ash (Na ₂ CO ₃ ). These coagulating sedimentation agents and sedimentation aids are alkaline or acidic in pH. The mica used in the present invention is preferably one that does not use a coagulating sedimentation agent and / or a sedimentation aid when wet milling. The use of mica not treated with a coagulating sedimentation agent and / or a sedimentation aid makes it difficult for the polymer in the composite resin composition to decompose, resulting in a large amount of gas generation and a decrease in the molecular weight of the polymer. It is easy to better maintain the performance of molded parts such as electronic parts, electronic parts including low-profile narrow-pitch connectors, and coaxial connectors.

The mica that can be used in the present invention preferably has an average particle diameter of 10 to 100 μm as measured by a microtrack laser diffraction method, and particularly preferably has an average particle diameter of 20 to 80 μm. It is preferable that the average particle diameter of mica is 10 μm or more because the effect of improving the rigidity of the molded product is likely to be sufficient. It is preferable that the average particle diameter of mica is 100 μm or less because the rigidity of the molded product is likely to be sufficiently improved and the weld strength is likely to be sufficient. Furthermore, when the average particle size of mica is 100 μm or less, it is easy to ensure sufficient fluidity for molding electronic components including the asymmetric electronic component, low profile narrow pitch connector, and coaxial connector of the present invention.

The thickness of the mica that can be 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 mica thickness is 0.01 μm or more, the mica is difficult to break during the melt processing of the composite resin composition, and therefore, the rigidity of the molded product may be easily improved. It is preferable that the mica thickness is 1 μm or less because the effect of improving the rigidity of the molded product tends to be sufficient.

The mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like and / or granulated with a binder.

(Other ingredients)
In the composite resin composition of the present invention, in addition to the above-mentioned components, pigments such as nucleating agent, carbon black, inorganic calcined pigment, antioxidant, stabilizer, plasticizer, lubricant, mold release agent, flame retardant, and You may mix | blend 1 or more types in a well-known inorganic filler.

The method for producing the composite resin composition in the present invention is not particularly limited as long as the components in the composite resin composition can be uniformly mixed, and can be appropriately selected from conventionally known methods for producing resin compositions. For example, each component is melt-kneaded and extruded using a melt-kneader such as a single-screw or twin-screw extruder, and then the resulting composite resin composition is processed into a desired form such as powder, flakes, pellets, etc. A method is mentioned.

The composite resin composition according to the present invention is excellent in fluidity, so that the minimum filling pressure at the time of molding is not excessively excessive, and the component having a complicated shape such as an asymmetric electronic component having a latch structure or a notch, a low profile A small and complex part such as a pitch connector, a coaxial connector, or the like can be preferably formed. The minimum filling pressure is specified as the minimum injection filling pressure at which a good molded product can be obtained at 365 ° C. when molding the composite resin composition.

[Electronic parts]
The electronic component of the present invention can be obtained by molding the composite resin composition of the present invention. Although it does not specifically limit as an electronic component, Asymmetrical electronic components, a low profile narrow pitch connector, a coaxial connector, etc. are mentioned.

(Asymmetric electronic components)
By molding the composite resin composition of the present invention, the asymmetric electronic component of the present invention can be obtained. The asymmetric electronic component of the present invention refers to a component that has no symmetry with respect to any of the XY axis plane, the YZ axis plane, and the XZ axis plane of the molded product.

In the case of ordinary connectors (electronic parts) that exist in the market, the XY axis plane, the YZ axis plane, and the XZ axis plane have symmetry, so that the symmetry should be maintained during molding. By using a proper gate position and design, it is possible to control the dimensional accuracy and warpage of the product. On the other hand, the asymmetric electronic component of the present invention has a complicated shape, and it is difficult to suppress warpage deformation by a molding method. In the asymmetric electronic component of the present invention, warpage deformation is suppressed by using a specific composite resin composition.

A typical example of such an asymmetric electronic component is a certain type of connector or socket.
Connector for memory module such as DIMM connector, DDR-DIMM connector, DDR2-DIMM connector, DDR-SO-DIMM connector, DDR2-SO-DIMM connector, DDR-Micro-DIMM connector, DDR2-Micro-DIMM connector Is mentioned. Of these, DDR-DIMM connectors and DDR2-DIMM connectors are preferred, especially for thin-walled and complex memory module connectors for laptop computers, with a pitch-to-pitch distance of 0.8 mm or less and a total product length of 60.0 mm. As described above, it is particularly preferable that the product height is 6.0 mm or less and the number of poles is 150 or more. Such a memory module connector is subjected to an IR reflow process for surface mounting at a peak temperature of 230 to 280 ° C, the warp before the IR reflow process is 0.1 mm or less, and the warp before and after the reflow. However, according to the present invention, such a requirement can be satisfied.

Examples of the socket include a memory card socket such as a card bus, CF card, memory stick, PC card, SD card, SDMo, smart card, smart media card, microSD card, miniSD card, xD picture card, TransFlash, etc. A memory card socket having a rail structure and a product height of 3.0 mm or less is suitable.

(Low profile narrow pitch connector)
By molding the composite resin composition in the present invention, the low profile narrow pitch connector of the present invention can be obtained. The shape of the low-profile narrow-pitch connector of the present invention is not particularly limited, but the low-profile narrow-pitch connector has a pitch distance of 0.5 mm or less, a total product length of 4.0 mm or more, and a product height of 4.0 mm or less. It may be. Further, the type of the low-profile narrow-pitch connector of the present invention is not particularly limited, but a board-to-board connector (also known as “BtoB connector”), a flexible printed circuit board (FPC), and a flexible flat cable (FFC) are connected. It may be a flexible printed circuit board connector (also known as an “FPC connector”) or the like.

(Coaxial connector)
The coaxial connector of the present invention can be obtained by molding the composite resin composition of the present invention. In order to produce a coaxial connector by molding a resin composition, it is necessary that the resin composition is excellent in fluidity. However, since the composite resin composition in the present invention is excellent in fluidity, this composite resin composition is The coaxial connector can be manufactured smoothly by using. Although it does not specifically limit as a coaxial connector, For example, the coaxial connector with a thickness of 100 micrometers or less is mentioned.

The molding method for obtaining the electronic component of the present invention, such as the asymmetric electronic component of the present invention, low-profile narrow pitch connector, coaxial connector, etc. is not particularly limited, but in order to prevent deformation of the obtained electronic component, warpage deformation is particularly suppressed. In order to obtain the obtained asymmetric electronic component, or in order to prevent deformation or the like of the obtained low profile narrow pitch connector or coaxial connector, it is preferable to select molding conditions without residual internal stress. In order to lower the filling pressure and reduce the residual internal stress of the obtained electronic parts such as asymmetric electronic parts, low profile narrow pitch connectors, coaxial connectors, etc., the cylinder temperature of the molding machine should be higher than the melting point of the liquid crystalline polymer. preferable.

The mold temperature is preferably 70 to 100 ° C. If the mold temperature is not too low, it is particularly preferable that the mold temperature is 70 ° C. or higher because the composite resin composition filled in the mold hardly causes poor flow. If the mold temperature is not too high, it is particularly preferable that the mold temperature is 100 ° C. or lower because problems such as burrs are unlikely to occur. The injection speed is preferably 150 mm / second or more. If the injection speed is not too low, particularly when the injection speed is 150 mm / sec or more, it is unlikely that only an unfilled molded product will be obtained. A completely filled molded product has a high filling pressure and a residual internal stress. It is difficult to obtain a large molded product, and it is unlikely that only an electronic component having a problem in terms of shape such as an asymmetric electronic component having a large warp deformation and a connector having poor flatness may be obtained.

In particular, warpage deformation is suppressed in the asymmetric electronic component of the present invention. The degree of warping of the asymmetric electronic component is determined as follows. That is, the asymmetric electronic component is placed on a horizontal desk, the height of the asymmetric electronic component is measured by an image measuring machine, and the difference between the maximum height and the minimum height from the least squares plane is determined as the sled of the asymmetric electronic component. To do. In the asymmetric electronic component of the present invention, changes in warpage are suppressed before and after performing IR reflow.

Also, the electronic parts of the present invention such as the asymmetric electronic parts of the present invention, low profile narrow pitch connectors, coaxial connectors, etc. are excellent in high temperature rigidity. The high temperature stiffness is evaluated by measuring the deflection temperature under load in accordance with ISO 75-1 and 2 standard.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

(Method for producing liquid crystalline polymer 1)
A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a pressure reduction / outflow line was charged with the following raw material monomers, a metal catalyst, and an acylating agent, and nitrogen substitution was started.
(I) 4-hydroxybenzoic acid: 1041 g (48 mol%) (HBA)
(II) 6-Hydroxy-2-naphthoic acid: 89 g (3 mol%) (HNA)
(III) Terephthalic acid: 565 g (21.7 mol%) (TA)
(IV) Isophthalic acid: 78 g (3 mol%) (IA)
(V) 4,4′-dihydroxybiphenyl: 711 g (24.3 mol%) (BP)
Potassium acetate catalyst: 110 mg
Acetic anhydride: 1645g

After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further increased to 360 ° C. over 5.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 20 minutes, while acetic acid, excess acetic anhydride, and other low boiling points are distilled off. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change from a reduced pressure state to a normal pressure through a normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to pelletize. The obtained pellet had a melting point of 358 ° C., a crystallization temperature of 303 ° C., a crystallization heat amount of 1.6 J / g, and a melt viscosity of 9 Pa · s.

In this example, the melting point, crystallization temperature, crystallization heat quantity, and melt viscosity of the pellet were measured under the following conditions.

[Measurement of melting point]
After observing the endothermic peak temperature (Tm1) observed when the liquid crystalline polymer was measured at room temperature from 20 ° C./min with a DSC manufactured by TA Instruments, 2 at a temperature of (Tm1 + 40) ° C. After being held for a minute, the sample was once cooled to room temperature under a temperature drop condition of 20 ° C./min, and then the temperature of the endothermic peak observed when measured under a temperature rise condition of 20 ° C./min was measured again.

[Measurement of crystallization temperature]
After observing the endothermic peak temperature (Tm1) observed when the liquid crystalline polymer was measured at room temperature from 20 ° C./min with a DSC manufactured by TA Instruments, 2 at a temperature of (Tm1 + 40) ° C. After maintaining for a minute, an exothermic peak temperature observed when measuring under a temperature drop condition of 20 ° C./min was measured.

[Measurement of heat of crystallization]
After observing the endothermic peak temperature (Tm1) observed when the wholly aromatic polyester and the polyester resin composition were measured from room temperature at a temperature rising condition of 20 ° C./min on a DSC manufactured by TA Instruments, (Tm1 + 40 ) After holding at a temperature of 2 ° C. for 2 minutes, the calorific value of the exothermic peak obtained from the peak of the exothermic peak temperature observed when the temperature was measured under a temperature decreasing condition of 20 ° C./min was measured.

[Measurement of melt viscosity]
Using a Capillograph Type 1B manufactured by Toyo Seiki Co., Ltd. with L = 20 mm and d = 1 mm, and a temperature 10 to 20 ° C. higher than the melting point of the liquid crystalline polymer, a shear rate of 1000 / sec, and a liquid crystal conforming to ISO11443 The melt viscosity of the conductive polymer was measured.

(Method for producing liquid crystalline polymer 2)
A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a pressure reduction / outflow line was charged with the following raw material monomers, a metal catalyst, and an acylating agent, and nitrogen substitution was started.
(I) 4-Hydroxybenzoic acid: 188.4 g (60 mol%) (HBA)
(II) 6-hydroxy-2-naphthoic acid: 21.4 g (5 mol%) (HNA)
(III) Terephthalic acid: 66.8 g (17.7 mol%) (TA)
(IV) 4,4′-dihydroxybiphenyl: 52.2 g (12.3 mol%) (BP)
(V) 4-acetoxyaminophenol: 17.2 g (5 mol%) (APAP)
Potassium acetate catalyst: 15mg
Acetic anhydride: 226.2 g

After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further raised to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (ie, 667 Pa) over 15 minutes while acetic acid, excess acetic anhydride, and other low boiling points are distilled off. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change from a reduced pressure state to a normal pressure through a normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to pelletize. The obtained pellet had a melting point of 334 ° C., a crystallization temperature of 290 ° C., a crystallization heat amount of 2.7 J / g, and a melt viscosity of 18 Pa · s.

(Components other than liquid crystalline polymers)
Each liquid crystalline polymer obtained above and the following components were mixed using a twin screw extruder to obtain a composite resin composition. The amount of each component is as shown in Tables 1 to 3.
(B) Glass fiber and / or milled fiber Glass fiber: ECS03T-786H manufactured by Nippon Electric Glass Co., Ltd., fiber diameter 10 μm, chopped strand having a length of 3 mm Milled fiber: PF70E001 manufactured by Nittobo Co., Ltd., fiber diameter 10 μm, Average fiber length 70μm
(C) Plate-like inorganic filler Talc; Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd., average particle size 10 μm
Mica: AB-25S manufactured by Yamaguchi Mica Industry Co., Ltd., average particle size 25 μm

The extrusion conditions for obtaining the composite resin composition are as follows.
[Extrusion conditions]
[Examples 1 to 11, Comparative Examples 4, 5, 10, 11, Reference Examples 1 to 4]
The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperatures of the other cylinders were all 370 ° C. All liquid crystalline polymers were supplied from the main feed port. The filler was supplied from the side feed port.
[Comparative Examples 1 to 3, 6 to 9]
The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperature of the other cylinders was all 350 ° C. All liquid crystalline polymers were supplied from the main feed port. The filler was supplied from the side feed port.

In addition, the average glass fiber length of the glass fiber and milled fiber in a composite resin composition was measured with the following method.
[Measurement of average glass fiber length]
5 g of the composite resin composition pellets were heated and ashed at 600 ° C. for 2 hours. The incineration residue was sufficiently dispersed in a 5% by mass polyethylene glycol aqueous solution, then transferred to a petri dish with a dropper, and glass fibers or milled fibers were observed with a microscope. At the same time, the weight average fiber length of the glass fiber or milled fiber was measured using an image measuring instrument (LUZEXFS manufactured by Nireco Corporation).

<Production and evaluation of asymmetric electronic components>
Based on the following method, the physical properties of the DDR-DIMM connector molded from the composite resin composition were measured. Each evaluation result is shown in Table 1.

(DDR connector sled)
The composite resin composition was injection-molded under the following molding conditions (gate: tunnel gate, gate size: φ0.75 mm), and the overall size as shown in FIG. 1 was 70.0 mm × 26.0 mm × 4.0 mmt, A DDR-DIMM connector having a pitch distance of 0.6 mm and a pin hole number of 100 × 2 was obtained.
[Molding condition]
Molding machine: Sumitomo Heavy Industries SE30DUZ
Cylinder temperature (indicates temperature from nozzle side):
360 ° C.-365 ° C.-340 ° C.-330 ° C. (Examples 1 to 3, Comparative Examples 4 and 5, Reference Examples 1 and 2)
350 ° C.-350 ° C.-340 ° C.-330 ° C. (Comparative Examples 1 to 3)
Mold temperature: 80 ℃
Injection speed: 300 mm / sec Holding pressure: 50 MPa
Holding time: 2 seconds Cooling time: 10 seconds Screw rotation speed: 120 rpm
Screw back pressure: 1.2MPa

The obtained connector was placed on a horizontal desk, and the height of the connector was measured with Mitutoyo Quick Vision 404 PROCNC image measuring machine. At that time, the height was measured at a plurality of positions indicated by black circles in FIG. 2, and the difference between the maximum height and the minimum height from the least square plane was defined as the DDR connector warp. The warpage was measured before and after IR reflow performed under the following conditions.
[IR reflow conditions]
Measuring machine: RF-300 (using far infrared heater)
Sample feed rate: 140 mm / sec Reflow furnace passage time: 5 minutes Preheat zone temperature condition: 150 ° C.
Reflow zone temperature condition: 190 ° C
Peak temperature: 251 ° C

(DDR connector deformation)
The difference in warpage before and after reflow measured by the above method was determined as the amount of deformation of the DDR connector.

(DDR connector minimum filling pressure)
When the DDR-DIMM connector of FIG. 1 was injection molded, the minimum injection filling pressure at which a good molded product was obtained was measured as the minimum filling pressure.

(Load deflection temperature)
Under the following molding conditions, the composite resin composition was injection molded to obtain a molded product, and the deflection temperature under load was measured in accordance with ISO75-1,2.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, SE100DU
Cylinder temperature (indicates temperature from nozzle side):
360 ° C.-370 ° C.-370 ° C.-360 ° C.-340 ° C.-330 ° C. (Examples 1 to 3, Comparative Examples 4 and 5, Reference Examples 1 and 2)
350 ° C-350 ° C-350 ° C-350 ° C-340 ° C-330 ° C (Comparative Examples 1 to 3)
Mold temperature: 80 ℃
Injection speed: 2 m / min Holding pressure: 50 MPa
Holding time: 2 seconds Cooling time: 10 seconds Screw rotation speed: 120 rpm
Screw back pressure: 1.2MPa

As shown in Table 1, the composite resin composition of the present invention has good fluidity, and the asymmetric electronic component molded from the composite resin composition is suppressed from warping deformation and has high-temperature rigidity. It was excellent.

<Production and evaluation of low-profile narrow-pitch connectors>
Based on the following method, the connector minimum filling pressure and the deflection temperature under load at the time of molding a low profile narrow pitch connector were measured. The results are shown in Tables 2 and 3. In the table, “unfillable” means that the composite resin composition could not be filled in the molding machine.

(Connector minimum filling pressure)
Under the following molding conditions, the composite resin composition as shown in FIG. 3 has an overall size of 17.6 mm × 4.00 mm × 1.16 mm, a pitch distance of 0.5 mm, a pin hole number of 30 × 2 pins, and a minimum thickness. A FPC connector having a thickness of 0.12 mm (gate: tunnel gate (φ0.4 mm)) was injection molded, and the minimum injection filling pressure at which a good molded product was obtained was measured as the minimum filling pressure.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, SE30DUZ
Cylinder temperature (indicates temperature from nozzle side):
365 ° C.-365 ° C.-355 ° C.-345 ° C. (Examples 4 to 11, Comparative Examples 10 and 11, Reference Examples 3 and 4)
350 ° C.-350 ° C.-340 ° C.-330 ° C. (Comparative Examples 6 to 9)
Mold temperature: 80 ℃
Injection speed: 12 m / min Holding pressure: 50 MPa
Holding time: 2 seconds Cooling time: 5 seconds Screw rotation speed: 120-100rpm
Screw back pressure: 1.5-1.0MPa

(Load deflection temperature)
Under the following molding conditions, each composite resin composition was injection-molded to obtain a molded product, and the deflection temperature under load was measured according to ISO75-1 and ISO2.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, SE100DU
Cylinder temperature (indicates temperature from nozzle side):
360 ° C.-370 ° C.-370 ° C.-360 ° C.-340 ° C.-330 ° C. (Examples 4 to 11, Comparative Examples 10 and 11, Reference Examples 3 and 4)
350 ° C-350 ° C-350 ° C-350 ° C-340 ° C-330 ° C (Comparative Examples 6 to 9)
Mold temperature: 80 ℃
Injection speed: 2 m / min Holding pressure: 50 MPa
Holding time: 2 seconds Cooling time: 10 seconds Screw rotation speed: 120 rpm
Screw back pressure: 1.2MPa

As shown in Tables 2 and 3, the composite resin composition of the present invention was excellent in fluidity, and the value of the minimum filling pressure of the low profile narrow pitch connector molded from the composite resin composition was reduced.

Claims

A composite resin composition for electronic parts, comprising (A) a liquid crystalline polymer, (B) a milled fiber, and (C) a plate-like inorganic filler,
The (A) liquid crystalline polymer has, as essential constituent components, the following constituent units: (I) constituent units derived from 4-hydroxybenzoic acid, (II) constituent units derived from 2-hydroxy-6-naphthoic acid, ( III) a structural unit derived from terephthalic acid, (IV) a structural unit derived from isophthalic acid, and (V) a structural unit derived from 4,4′-dihydroxybiphenyl,
The content of the structural unit (I) with respect to all the structural units is 35 to 75 mol%,
The content of the structural unit (II) with respect to the total structural unit is 2 to 8 mol%,
The content of the structural unit (III) with respect to all the structural units is 4.5 to 30.5 mol%,
The content of the structural unit (IV) with respect to all the structural units is 2 to 8 mol%,
The content of the structural unit (V) with respect to all the structural units is 12.5 to 32.5 mol%,
The total amount of the structural units (II) and (IV) is 4 to 10 mol% with respect to all the structural units,
The content of the (A) liquid crystalline polymer is 40 to 80% by mass with respect to the entire composite resin composition,
The content of the (B) milled fiber is 10 to 30% by mass with respect to the entire composite resin composition,
The composite resin composition for electronic parts, wherein the content of the (C) plate-like inorganic filler is 10 to 35% by mass with respect to the entire composite resin composition.
The electronic component is an asymmetric electronic component;
The content of the (A) liquid crystalline polymer is 47.5 to 65% by mass with respect to the entire composite resin composition,
The content of the (B) milled fiber is 15 to 30% by mass with respect to the entire composite resin composition,
The composite resin composition for electronic parts according to claim 1, wherein the content of the (C) plate-like inorganic filler is 20 to 35 mass% with respect to the entire composite resin composition.
The composite resin composition for electronic parts according to claim 2, wherein the (C) plate-like inorganic filler is at least one selected from the group consisting of talc and mica.
The electronic component is a low profile narrow pitch connector;
The composite resin composition for electronic parts according to claim 1, wherein the content of the (C) plate-like inorganic filler is 10 to 30% by mass with respect to the entire composite resin composition.
The (A) liquid crystalline polymer has a value of [melting point−crystallization temperature] of 50 to 60 ° C., measured at a shear rate of 1000 / sec at a temperature 10 to 20 ° C. higher than the melting point, according to ISO 11443. The composite resin composition for electronic parts according to claim 4, wherein the melt viscosity is 5 to 15 Pa · s.
The average fiber length of the (B) milled fiber is 50 to 100 μm, and
The composite resin composition for electronic parts according to claim 4 or 5, wherein the (C) plate-like inorganic filler is at least one selected from the group consisting of talc and mica.
An electronic component molded from the composite resin composition for an electronic component according to claim 1.
The content of the (A) liquid crystalline polymer is 47.5 to 65% by mass with respect to the entire composite resin composition,
The content of the (B) milled fiber is 15 to 30% by mass with respect to the entire composite resin composition,
The content of the (C) plate-like inorganic filler is 20 to 35% by mass with respect to the entire composite resin composition,
The electronic component according to claim 7, wherein the electronic component is an asymmetric electronic component having no symmetry with respect to any of the XY axis plane, the YZ axis plane, and the XZ axis plane of the molded product.
The electronic component according to claim 8, wherein the (C) plate-like inorganic filler is at least one selected from the group consisting of talc and mica.
10. The electronic component according to claim 8, which is a memory module connector having a pitch distance of 0.8 mm or less, a total product length of 60.0 mm or more, a product height of 6.0 mm or less, and a pole number of 150 or more.
10. The electronic component according to claim 8, wherein the electronic component is a memory card socket having a rail structure and a product height of 3.0 mm or less.
The content of the (C) plate-like inorganic filler is 10 to 30% by mass with respect to the entire composite resin composition,
The distance between pitches is 0.5 mm or less,
The total product length is 4.0mm or more,
The product height is 4.0 mm or less,
The electronic component according to claim 7, wherein the electronic component is a low-profile narrow-pitch connector that is a board-to-board connector or a flexible printed board connector.
The (A) liquid crystalline polymer has a value of [melting point−crystallization temperature] of 50 to 60 ° C., measured at a shear rate of 1000 / sec at a temperature 10 to 20 ° C. higher than the melting point, according to ISO 11443. The electronic component according to claim 12, wherein the melt viscosity is 5 to 15 Pa · s.
The average fiber length of the (B) milled fiber is 50 to 100 μm, and
The electronic component according to claim 12 or 13, wherein the (C) plate-like inorganic filler is at least one selected from the group consisting of talc and mica.