JP6345376B1 - Composite resin composition and electronic component molded from the composite resin composition - Google Patents

Abstract

Provided are a composite resin composition that is excellent in heat resistance and capable of obtaining an electronic component in which warpage deformation and blister generation are suppressed, and an electronic component molded from the composite resin composition.
The composite resin composition according to the present invention includes (A) a liquid crystalline polymer, (B) a fibrous filler, and (C) a plate-like filler, and the (A) liquid crystalline polymer is an essential component. It is a wholly aromatic polyester amide having optical anisotropy at the time of melting, comprising a predetermined amount of the following structural units (I) to (VI) as a constituent component, and the weight average fiber length of the (B) fibrous filler Is 250 μm or more.

Description

  The present invention relates to a composite resin composition and an electronic component molded from the composite resin composition.

  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 particular, due to the recent high performance of electronic equipment, there are also demands of the times of higher heat resistance of connectors (improvement of productivity by mounting technology), higher density (multi-core), and miniaturization. Taking advantage of these characteristics, a liquid crystalline polymer composition reinforced with glass fibers is used as a connector material.

  However, in recent years, the connector has become lighter, thinner, and shorter, and due to insufficient rigidity due to insufficient thickness of the molded product 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 warping deformation, the molding technique has been devised, and from the viewpoint of material, a specific plate-like filler has been proposed. In other words, in the case of ordinary connectors (electronic parts) that exist in the market, 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 less 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.

International Publication No. 2008/023839

  However, the liquid crystalline polymer composition disclosed in the above-mentioned Patent Document 1 due to factors such as a shape change accompanying an increase in the integration rate in recent asymmetric electronic components, particularly a decrease in pitch distance, a product height, and an increase in the number of poles. It has been found that conventional liquid crystalline polymer compositions such as products cannot be dealt with in some cases. That is, the conventional liquid crystalline polymer composition has insufficient heat resistance and 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 addition, the liquid crystal polymer composition may have a problem of blistering. That is, liquid crystalline polyesteramide, which is a liquid crystalline polymer, is often used as a material that requires heat treatment at a high temperature because it has good high-temperature thermal stability. However, when the molded product is left in high temperature air and liquid for a long time, there arises a problem that fine blisters called blisters are generated on the surface. This phenomenon is caused by the fact that the decomposition gas generated when the liquid crystalline polyesteramide is in a molten state is brought into the molded product, and then the gas expands when the high-temperature heat treatment is performed. This is because the pushed up part appears as a blister. The generation of blisters can be reduced by sufficiently degassing the vent hole during melt extrusion of the material, or by not allowing the material to stay in the molding machine for a long time during molding. However, the range of conditions is very narrow, and it is not sufficient to obtain a molded product in which generation of blisters is suppressed, that is, a molded product having blister resistance. The fundamental solution to blister generation requires improvement of the quality of the liquid crystalline polyester amide itself, and the known liquid crystalline polyester amide and methods using it are insufficient to solve the problem of blister generation. .

  The present invention has been made in view of such circumstances, and is a composite resin composition that provides an electronic component that is excellent in heat resistance and in which warpage deformation and blister generation are suppressed, and an electronic molded from the composite resin composition. The purpose is to provide parts.

  The inventors of the present invention combine a liquid crystalline polymer containing a predetermined amount of a specific structural unit, a fibrous filler, and a plate-like filler so that the weight average fiber length of the fibrous filler is 250 μm or more. It has been found that the above problems can be solved. Specifically, the present invention provides the following.

(1) A composite resin composition comprising (A) a liquid crystalline polymer, (B) a fibrous filler, and (C) a plate-like filler,
The (A) liquid crystalline polymer is composed of the following structural units (I) to (VI) as essential components:
Content of structural unit (I) is 50-70 mol% with respect to all the structural units,
The content of the structural unit (II) is 0.5 mol% or more and less than 4.5 mol% with respect to all the structural units,
Content of structural unit (III) is 10.25-22.25 mol% with respect to all the structural units,
The content of the structural unit (IV) is 0.5 mol% or more and less than 4.5 mol% with respect to all the structural units,
Content of a structural unit (V) is 5.75-23.75 mol% with respect to all the structural units,
Content of structural unit (VI) is 1-7 mol% with respect to all the structural units,
The total content of the structural unit (II) and the structural unit (IV) with respect to all the structural units is 1 mol% or more and less than 5 mol%,
The total content of the structural units (I) to (VI) with respect to all the structural units is 100 mol%,
A wholly aromatic polyester amide exhibiting optical anisotropy when melted, wherein the molar ratio of the structural unit (VI) to the total of the structural unit (V) and the structural unit (VI) is 0.04 to 0.37. ,
The weight average fiber length of the (B) fibrous filler is 250 μm or more,
Said (A) liquid crystalline polymer is 37.5-82.5 mass% with respect to the whole composite resin composition,
Said (B) fibrous filler is 2.5-17.5 mass% with respect to the whole composite resin composition,
The (C) plate-like filler is 15 to 45% by mass with respect to the entire composite resin composition,
The total amount of said (B) fibrous filler and said (C) plate-like filler is a composite resin composition which is 17.5-62.5 mass% with respect to the whole composite resin composition.

  (2) The total number of moles of the structural unit (III) and the structural unit (IV) is 1 to 1.1 times the total number of moles of the structural unit (V) and the structural unit (VI), or The total number of moles of the structural unit (V) and the structural unit (VI) is 1 to 1.1 times the total number of moles of the structural unit (III) and the structural unit (IV). Composite resin composition.

  (3) The composite resin composition according to (1) or (2), wherein the (B) fibrous filler is a glass fiber.

  (4) The composite resin composition according to any one of (1) to (3), wherein the (C) plate-like filler is talc.

  (5) An electronic component molded from the composite resin composition according to any one of (1) to (4), having a total product length of 30 mm or more and a product height of 5 mm or more.

  (6) The electronic component according to (5), 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.

  (7) In the memory module connector (5) or (6), the pitch distance is 0.6 mm or less, the total product length is 60.0 mm or more, the product height is 10.0 mm or less, and the number of poles is 200 or more. The electronic component described.

  ADVANTAGE OF THE INVENTION According to this invention, the composite resin composition which is excellent in heat resistance, and can obtain the electronic component by which curvature deformation and blister generation were suppressed, and the electronic component shape | molded from the said composite resin composition are provided.

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 measurement location in the measurement of the curvature of the DDR-DIMM connector performed in the Example.

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

[Composite resin composition]
The composite resin composition in the present invention includes a predetermined amount of a specific liquid crystalline polymer, a fibrous filler, and a plate-like filler, and the fibrous filler has a weight average fiber length of 250 μm or more. Hereinafter, the components constituting the composite resin composition in the present invention will be described.

(Liquid crystal polymer)
The composite resin composition in the present invention includes a liquid crystalline polymer that is the above-mentioned wholly aromatic polyester amide. Since the wholly aromatic polyester amide has a low melting point, the processing temperature can be lowered and the generation of decomposition gas during melting is suppressed. As a result, in the molded product obtained by molding the composite resin composition containing the wholly aromatic polyester amide, blister generation is suppressed and blister resistance is improved. A liquid crystalline polymer can be used individually by 1 type or in combination of 2 or more types.

  The wholly aromatic polyester amide in the present invention comprises the following structural unit (I), the following structural unit (II), the following structural unit (III), the following structural unit (IV), the following structural unit (V), and the following structural unit ( VI).

  The structural unit (I) is derived from 4-hydroxybenzoic acid (hereinafter also referred to as “HBA”). The wholly aromatic polyester amide in the present invention contains 50 to 70 mol% of the structural unit (I) with respect to all the structural units. If the content of the structural unit (I) is less than 50 mol% or exceeds 70 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (I) is preferably 54 to 67 mol%, more preferably 58 to 64 mol%.

  The structural unit (II) is derived from 6-hydroxy-2-naphthoic acid (hereinafter also referred to as “HNA”). The wholly aromatic polyester amide in the present invention contains 0.5 to 4.5 mol% of the structural unit (II) with respect to all the structural units. When the content of the structural unit (II) is less than 0.5 mol% or 4.5 mol% or more, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (II) is preferably 0.75 to 3.75 mol%, more preferably 1 to 3 mol%.

  The structural unit (III) is derived from 1,4-phenylenedicarboxylic acid (hereinafter also referred to as “TA”). The wholly aromatic polyester amide in the present invention contains 10.25 to 22.25 mol% of the structural unit (III) with respect to all the structural units. When the content of the structural unit (III) is less than 10.25 mol% or exceeds 22.25 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (III) is preferably 12.963 to 20.75 mol%, more preferably 15.675 to 19.25 mol%.

  The structural unit (IV) is derived from 1,3-phenylenedicarboxylic acid (hereinafter also referred to as “IA”). The wholly aromatic polyester amide in the present invention contains 0.5 mol% or more and less than 4.5 mol% of the structural unit (IV) with respect to all the structural units. When the content of the structural unit (IV) is less than 0.5 mol% or 4.5 mol% or more, at least one of low melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (IV) is preferably 0.5 to 3.75 mol%, more preferably 0.5 to 3 mol%.

  The structural unit (V) is derived from 4,4′-dihydroxybiphenyl (hereinafter also referred to as “BP”). The wholly aromatic polyester amide in the present invention contains 5.75 to 23.75 mol% of the structural unit (V) with respect to all the structural units. When the content of the structural unit (V) is less than 5.75 mol% or exceeds 23.75 mol%, at least one of the low melting point and the heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (V) is preferably 8.5 to 20.375 mol%, more preferably 11.25 to 17 mol% (for example, 11. 675 to 17 mol%).

  The structural unit (VI) is derived from N-acetyl-p-aminophenol (hereinafter also referred to as “APAP”). The wholly aromatic polyester amide in the present invention contains 1 to 7 mol% of the structural unit (VI) with respect to the total structural units. When the content of the structural unit (VI) is less than 1 mol% or exceeds 7 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (VI) is preferably 1.5 to 7 mol%, more preferably 2 to 7 mol%.

  The wholly aromatic polyester amide in the present invention contains 1 mol% or more and less than 5 mol% of the total of the structural unit (II) and the structural unit (IV) with respect to all the structural units. In the wholly aromatic polyester amide, the lower melting point can be obtained by coexisting the flexible structural unit (II) having a naphthalene skeleton and the flexible structural unit (IV) having a benzene skeleton in a total amount within the above range. Coexistence with heat resistance tends to be sufficient If the total content is less than 1 mol%, the proportion of the flexural constituent unit is too small, and the lowering of the melting point tends to be insufficient. When the total content is 5 mol% or more, the proportion of the flexible structural unit is excessively increased, and thus the heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the total content is preferably 1.75 to 4.75 mol%, more preferably 2.5 to 4.5 mol%.

  In the wholly aromatic polyester amide in the present invention, the molar ratio of the structural unit (VI) to the total of the structural unit (V) and the structural unit (VI) is 0.04 to 0.37. If the molar ratio is less than 0.04, the proportion of structural units having a biphenyl skeleton increases, so that the crystallinity of the wholly aromatic polyester amide is lowered, and it is insufficient to achieve both low melting point and heat resistance. Cheap. Further, when the molar ratio exceeds 0.37, heterogeneous bonds other than ester bonds increase, so that the crystallinity of the wholly aromatic polyester amide is lowered, and the compatibility between the low melting point and the heat resistance tends to be insufficient. . From the viewpoint of achieving both low melting point and heat resistance, the molar ratio is preferably 0.07 to 0.36, more preferably 0.11 to 0.35.

  From the viewpoint of achieving both low melting point and heat resistance, the total number of moles of the structural unit (III) and the structural unit (IV) (hereinafter also referred to as “number of moles 1A”) is the same as that of the structural unit (V). 1 to 1.1 times the total number of moles of the structural unit (VI) (hereinafter also referred to as “number of moles 2A”), or the total number of the structural unit (V) and the structural unit (VI). The number of moles is preferably 1 to 1.1 times the total number of moles of the structural unit (III) and the structural unit (IV). The number of moles 1A is 1.02 to 1.06 times the number of moles 2A, or the number of moles 2A is more preferably 1.02 to 1.06 times the number of moles 1A. More preferably, the mole number 1A is 1.024 to 1.056 times the mole number 2A, or the mole number 2A is 1.024 to 1.056 times the mole number 1A.

  As described above, the wholly aromatic polyester amide according to the present invention includes the specific structural units (I) to (VI) and the total of the structural unit (II) and the structural unit (IV) as total structural units. In contrast, it has a specific amount, and the molar ratio of the structural unit (VI) to the total of the structural unit (V) and the structural unit (VI) is in a specific range. Is enough. In addition, the wholly aromatic polyester amide of the present invention contains 100 mol% of the structural units (I) to (VI) in total with respect to all the structural units.

  As an index indicating the heat resistance, there is a deflection temperature under load (hereinafter also referred to as “DTUL”). When DTUL is 260 ° C. or higher, the heat resistance tends to be high, which is preferable. DTUL is obtained by melt-kneading 60% by mass of the wholly aromatic polyester amide and 40% by mass of milled fiber having an average fiber diameter of 11 μm and an average fiber length of 75 μm at the melting point of the wholly aromatic polyester amide + 20 ° C. It is a value measured in the state of the polyesteramide resin composition, and can be measured according to ISO75-1,2. From the viewpoint of achieving both low melting point and heat resistance, DTUL is preferably 265 ° C. or higher and 310 ° C. or lower, more preferably 267 to 300 ° C.

  Subsequently, the manufacturing method of the wholly aromatic polyester amide in this invention is demonstrated. The wholly aromatic polyester amide in the present invention is polymerized using a direct polymerization method, a transesterification method or the like. In the polymerization, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, etc., or a combination of two or more of these are used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is used. Is preferably used.

  In the present invention, at the time of polymerization, an acylating agent for the polymerization monomer or a monomer having terminal activated as an acid chloride derivative can be used. Examples of the acylating agent include fatty acid anhydrides such as acetic anhydride.

In the polymerization, various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, fatty acid metal salts, BF ₃ Lewis acid salts such as are mentioned, and fatty acid metal salts are preferred. The amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.003 to 0.2% by weight, based on the total weight of the monomers.

  Moreover, when performing solution polymerization or slurry polymerization, as a solvent, liquid paraffin, a high heat resistant synthetic oil, an inert mineral oil, etc. are used.

  The reaction conditions are, for example, a reaction temperature of 200 to 380 ° C. and a final ultimate pressure of 0.1 to 760 Torr (that is, 13 to 101,080 Pa). Particularly in the melt reaction, for example, the reaction temperature is 260 to 380 ° C., preferably 300 to 360 ° C., the final ultimate pressure is 1 to 100 Torr (that is, 133 to 13,300 Pa), preferably 1 to 50 Torr (that is, 133 to 6,670 Pa). ).

  In the reaction, all the raw material monomers (HBA, HNA, TA, IA, BP, and APAP), the acylating agent, and the catalyst can be charged into the same reaction vessel to start the reaction (one-stage system), or the raw material monomer HBA. , HNA, BP, and APAP hydroxyl groups can be acylated with an acylating agent and then reacted with TA and IA carboxyl groups (two-stage system).

  The melt polymerization is performed after the inside of the reaction system has reached a predetermined temperature, and the pressure reduction is started to a predetermined pressure reduction degree. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the total aromatic polyester amide is discharged from the reaction system through a normal pressure from a reduced pressure state to a predetermined pressure state.

  The wholly aromatic polyester amide produced by the above polymerization method can be further increased in molecular weight by solid-phase polymerization that is heated in an inert gas at normal pressure or reduced pressure. The preferable conditions for the solid state polymerization reaction are a reaction temperature of 230 to 350 ° C., preferably 260 to 330 ° C., and a final ultimate pressure of 10 to 760 Torr (ie 1,330 to 101,080 Pa).

In the present invention, the process for producing a wholly aromatic polyester amide comprises 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p- in the presence of a fatty acid metal salt. Preferably, the method comprises acylating aminophenol with a fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid and 1,3-phenylenedicarboxylic acid,
Consists of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol For all monomers,
The amount of 4-hydroxybenzoic acid used is 50 to 70 mol%, preferably 54 to 67 mol%, more preferably 58 to 64 mol%, from the viewpoint of achieving both low melting point and heat resistance.
The amount of 6-hydroxy-2-naphthoic acid used is 0.5 mol% or more and less than 4.5 mol%, preferably from 0.75 to 3.75 mol% from the viewpoint of achieving both low melting point and heat resistance. More preferably, 1 to 3 mol%,
The amount of 1,4-phenylenedicarboxylic acid used is 10.25 to 22.25 mol%, and from the viewpoint of achieving both low melting point and heat resistance, it is preferably 12.963 to 20.75 mol%, more preferably 15 675 to 19.25 mol%,
The amount of 1,3-phenylenedicarboxylic acid used is 0.5 mol% or more and less than 4.5 mol%, and preferably 0.5 to 3.75 mol% from the viewpoint of achieving both low melting point and heat resistance. Preferably 0.5-3 mol%,
The amount of 4,4′-dihydroxybiphenyl used is 5.75 to 23.75 mol%, and from the viewpoint of achieving both low melting point and heat resistance, preferably 8.5 to 20.375 mol%, more preferably 11 25-17 mol% (eg, 11.675-17 mol%),
The amount of N-acetyl-p-aminophenol used is 1 to 7 mol%, preferably from 1.5 to 7 mol%, more preferably 2 to 7 mol%, from the viewpoint of achieving both low melting point and heat resistance.
The total amount of 6-hydroxy-2-naphthoic acid and 1,3-phenylenedicarboxylic acid is 1 mol% or more and less than 5 mol%, and preferably 1.75 from the viewpoint of achieving both low melting point and heat resistance. ˜4.75 mol%, more preferably 2.5 to 4.5 mol%,
Sum of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol Is 100 mol%
It is preferable that
The molar ratio of the used amount of N-acetyl-p-aminophenol to the total used amount of 4,4′-dihydroxybiphenyl and N-acetyl-p-aminophenol is 0.04 to 0.37, and the melting point is lowered. From the viewpoint of coexistence with heat resistance, it is preferably 0.07 to 0.36, more preferably 0.11 to 0.35,
The amount of the fatty acid anhydride used is 1.02 of the total hydroxyl equivalent of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol. It is preferably ˜1.04 times. More preferably, the fatty acid metal salt is an acetic acid metal salt and the fatty acid anhydride is acetic anhydride. The total number of moles of 1,4-phenylene dicarboxylic acid and 1,3-phenylene dicarboxylic acid (hereinafter also referred to as “number of moles 1B”) is 4,4′-dihydroxybiphenyl and N-acetyl-p. 1 to 1.1 times the total number of moles with aminophenol (hereinafter also referred to as “number of moles 2B”), or 4,4′-dihydroxybiphenyl and N-acetyl-p-aminophenol The total number of moles is more preferably 1 to 1.1 times the total number of moles of 1,4-phenylenedicarboxylic acid and 1,3-phenylenedicarboxylic acid. The number of moles 1B is 1.02 to 1.06 times the number of moles 2B, or the number of moles 2 is still more preferably 1.02 to 1.06 times the number of moles 1B. The number of moles 1B is 1.024 to 1.056 times the number of moles 2B, or the number of moles 2B is particularly preferably 1.024 to 1.056 times the number of moles 1B.

  Next, the properties of wholly aromatic polyester amide will be described. The wholly aromatic polyester amide in the present invention exhibits optical anisotropy when melted. An optical anisotropy when melted means that the wholly aromatic polyester amide in the present invention is a liquid crystalline polymer.

  In the present invention, the fact that the wholly aromatic polyester amide is a liquid crystalline polymer is an indispensable element for the wholly aromatic polyester amide to have both heat stability and easy processability. The wholly aromatic polyester amide composed of the structural units (I) to (VI) may not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the polymer. Is limited to wholly aromatic polyester amides exhibiting optical anisotropy when melted.

  The property of melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the melting anisotropy can be confirmed by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus and observing it at a magnification of 150 times in a nitrogen atmosphere. The liquid crystalline polymer is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, for example, polarized light is transmitted even in a molten stationary liquid state.

  Since a nematic liquid crystalline polymer causes a significant decrease in viscosity at the melting point or higher, generally exhibiting liquid crystallinity at the melting point or higher is an index of workability. The melting point is preferably as high as possible from the viewpoint of heat resistance, but is preferably 360 ° C. or lower in consideration of heat deterioration during the melt processing of the polymer, the heating ability of the molding machine, and the like. In addition, More preferably, it is 300-360 degreeC, More preferably, it is 340-358 degreeC.

  The melt viscosity of the wholly aromatic polyester amide at a temperature 10 to 30 ° C. higher than the melting point of the wholly aromatic polyester amide in the present invention and a shear rate of 1000 / sec is preferably 500 Pa · s or less, more preferably 0. 0.5 to 300 Pa · s, and even more preferably 1 to 100 Pa · s. When the melt viscosity is within the above range, the wholly aromatic polyester amide itself or the composition containing the wholly aromatic polyester amide is easy to ensure fluidity at the time of molding, and the filling pressure is excessive. It is hard to become. In addition, in this specification, melt viscosity means the melt viscosity measured based on ISO11443.

  As an index representing the above heat resistance, the difference between the melting point and DTUL can also be mentioned. If this difference is 90 ° C. or less, the heat resistance tends to increase, which is preferable. From the viewpoint of achieving both low melting point and heat resistance, the difference is preferably more than 0 ° C and not more than 85 ° C (for example, not less than 50 ° C and not more than 85 ° C), more preferably 55 to 79 ° C.

  The composite resin composition in this invention contains 37.5-82.5 mass% of said liquid crystalline polymer with respect to the whole composite resin composition in a composite resin composition. When the content of the liquid crystalline polymer is less than 37.5% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition is likely to deteriorate, and electronic components obtained from the composite resin composition, etc. This is not preferable because warpage deformation of the molded product may increase. When the content of the liquid crystalline polymer is more than 82.5% by mass with respect to the entire composite resin composition, the bending elastic modulus and crack resistance of a molded article such as an electronic component obtained from the composite resin composition are lowered. Therefore, it is not preferable. In the composite resin composition of the present invention, the liquid crystalline polymer is preferably contained in the composite resin composition in an amount of 44 to 75% by mass, more preferably 60 to 65% by mass, based on the entire composite resin composition. preferable.

(Fibrous filler)
The composite resin composition in the present invention includes the above liquid crystalline polymer and a fibrous filler, and the weight average fiber length of the fibrous filler is 250 μm or more. Therefore, the composite resin composition is molded. The obtained molded product is excellent in high-temperature rigidity, and warpage deformation is suppressed. A fibrous filler can be used individually by 1 type or in combination of 2 or more types. The fibrous filler in the present invention is not particularly limited, and is glass fiber, milled fiber, carbon fiber, asbestos fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, titanium. A potassium acid fiber etc. are mentioned. Since the high temperature rigidity of the molded product obtained from the composite resin composition is likely to be improved, glass fibers are preferred as the fibrous filler in the present invention.

  In the composite resin composition of the present invention, the weight average fiber length of the fibrous filler is 250 μm or more, preferably 350 μm or more, and more preferably 450 μm or more. If the weight average fiber length is less than 250 μm, the molded article obtained from the composite resin composition is not sufficiently high in rigidity at high temperatures, and the warped deformation of the molded article may be increased. The upper limit of the weight average fiber length is not particularly limited, and is preferably 700 μm or less, and more preferably 500 μm or less. When the weight average fiber length is 600 μm or less, the fluidity of the composite resin composition is good, and warpage deformation of the molded product is hardly increased, which is preferable. In this specification, the weight average fiber length of the fibrous filler means that the composite resin composition is heated at 600 ° C. for 2 hours to be ashed to obtain an ashed residue, and this ashed residue is converted to 5% by mass polyethylene glycol. A dispersion is obtained by dispersing in an aqueous solution, and the weight average fiber length measured with an image measuring device is used for this dispersion.

  Moreover, the fiber diameter of the fibrous filler in the present invention is not particularly limited, and generally about 5 to 15 μm is used.

  The composite resin composition in the present invention contains 2.5 to 17.5 mass% of the fibrous filler in the composite resin composition with respect to the entire composite resin composition. When the content of the fibrous filler is less than 2.5% by mass with respect to the entire composite resin composition, a molded article such as an electronic component obtained from the composite resin composition has a low load deflection temperature and high temperature rigidity. Is not preferable because it is not sufficient. If the content of the fibrous filler is more than 17.5% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition is deteriorated, and warpage deformation of the molded product may be increased. It is not preferable. The fibrous filler in the present invention is preferably contained in the composite resin composition in an amount of 4 to 16% by mass, more preferably 5 to 15% by mass with respect to the entire composite resin composition.

(Plate filler)
The composite resin composition in the present invention further contains a plate-like filler. By including a plate-like filler in the composite resin composition in the present invention, a molded product in which warpage deformation is suppressed can be obtained. A plate-shaped filler can be used individually by 1 type or in combination of 2 or more types.

  The plate-like filler is contained in an amount of 15 to 45% by mass with respect to the entire composite resin composition. If the content of the plate-like filler is less than 15% by mass with respect to the entire composite resin composition, it is not preferable because warpage deformation of a molded product such as an electronic component obtained from the composite resin composition may increase. . If the content of the plate-like filler is more than 45% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition may be deteriorated, which is not preferable. The plate-like filler in the present invention is preferably contained in the composite resin composition in an amount of 20 to 40% by mass, more preferably 25 to 35% by mass with respect to the entire composite resin composition.

  Examples of the plate-like filler in the present invention include talc, mica, glass flakes, various metal foils, etc., and warpage of a molded product obtained from the composite resin composition without deteriorating the fluidity of the composite resin composition. Talc is preferable in terms of suppressing deformation. Further, the average particle size of the plate-like filler is not particularly limited, and a smaller one is desirable in consideration of fluidity in the thin portion. On the other hand, it is necessary to maintain a certain size in order to reduce warping deformation of a molded product such as an electronic component obtained from the composite resin composition. Specifically, 1-100 micrometers is preferable and 5-50 micrometers is more preferable.

〔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% by mass or less based on the total solid content of the talc, Fe ₂ O ₃ and Al _It is preferable that the total content of ₂ O ₃ is more than 1.0 mass% and not more than 2.0 mass%, and the content of CaO is less than 0.5 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 is contained in the above content range. It may be contained.

In the above 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 electronic parts molded from the composite resin composition, etc. The heat resistance of the molded product is difficult 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. 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 electronic parts molded from the composite resin composition, etc. The heat resistance of the molded product is difficult 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%.

  Furthermore, in the above talc, when the CaO content is less than 0.5% by mass, the molding processability of the composite resin composition and the heat resistance of molded products such as electronic parts molded from the composite resin composition deteriorate. Hateful. 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 preferable that it is 0.0-20.0 micrometers, and it is more preferable that it is 10-18 micrometers.

[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.

  In addition, in the production of mica, wet pulverization methods and dry pulverization methods 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, since the wet pulverization method requires a step of dispersing the material to be pulverized in water, a coagulating sedimentation agent and / or settling aid is added to the material to be pulverized in order to increase the dispersion efficiency of the material to be pulverized. Is common. Examples of the coagulating sedimentation agent and sedimentation 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. If mica not treated with a coagulating sedimentation agent and / or sedimentation aid is used, it is difficult for the polymer in the composite resin composition to decompose, and a large amount of gas generation and molecular weight reduction of the polymer are unlikely to occur. It is easy to better maintain the performance of a molded product such as a part.

  The mica that can be used in the present invention preferably has an average particle diameter measured by a microtrack laser diffraction method of 10 to 100 μm, 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 diameter of mica is 100 μm or less, it is easy to ensure sufficient fluidity for molding the electronic component of the present invention.

  The thickness of 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.

  In the composite resin composition of the present invention, the total amount of the fibrous filler and the plate-like filler is 17.5 to 62.5% by mass with respect to the entire composite resin composition. When the total amount is less than 17.5% by mass with respect to the entire composite resin composition, a molded article such as an electronic component obtained from the composite resin composition has a low load deflection temperature and high temperature rigidity is not sufficient, Moreover, since there exists a possibility that curvature deformation may become large, it is unpreferable. When the total amount is more than 62.5% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition is deteriorated and the warpage deformation of the molded product may be increased. The total amount is preferably 25 to 56% by mass and more preferably 35 to 40% by mass with respect to the entire composite resin composition.

(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 the weight average fiber length of the fibrous filler can be 250 μm or more, and is conventionally known. It can select suitably from the manufacturing method of a resin composition. 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.

  Since the composite resin composition in the present invention is excellent in fluidity, the minimum filling pressure at the time of molding is hardly excessive, and has a complicated shape such as an electronic component, in particular, an asymmetric electronic component having a latch structure or a notch. Parts and the like can be preferably molded. The degree of fluidity is determined by the minimum filling pressure of the connector. That is, the minimum injection filling pressure that can obtain a good molded product when the DDR-DIMM connector shown in FIG. 1 is injection-molded is specified as the minimum filling pressure. The lower the minimum filling pressure, the better the fluidity.

The melt viscosity of the composite resin composition measured in accordance with ISO 11443 at a temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline polymer at a shear rate of 1000 / sec (more preferably ⁵ Pa・ When molding a part having a complicated shape in an electronic component that is s or more and 1 × 10 ² Pa · s or less), in particular, a part having a complicated shape such as a latch structure or a notch in an asymmetric electronic component Is preferable in that the fluidity of the composite resin composition is ensured and the filling pressure does not become excessive.

(Electronic parts)
The electronic component of the present invention can be obtained by molding the composite resin composition of the present invention. The electronic component of the present invention is not particularly limited, and examples thereof include an electronic component having a total product length of 30 mm or more and a product height of 5 mm or more. Among the electronic components of the present invention, an asymmetric electronic component 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 shape of an asymmetric electronic component is complicated, and it is difficult to suppress warpage deformation by a molding method. In the electronic component of the present invention, in particular, the asymmetric electronic component, warpage deformation is suppressed by using the composite resin composition of the present invention.

Typical examples of such electronic components include connectors and sockets.
Examples of the connector include a memory module connector and an interface connector. Memory module connectors include, for example, DIMM connectors; DDR-DIMM connectors, DDR2-DIMM connectors, DDR-SO-DIMM connectors, DDR2-SO-DIMM connectors, DDR-Micro-DIMM connectors, DDR2-Micro-DIMM connectors, etc. DDR connectors and the like. Examples of the interface connector include a SATA connector, a SAS connector, and an NGFF connector. Of these, DDR connectors, SATA connectors, SAS connectors, and NGFF connectors are suitable, especially for thin-walled and complex memory module connectors for laptop computers, with a pitch distance of 0.6 mm or less and a total product length. Particularly preferred are those of 60.0 mm or more, product height of 10.0 mm or less, and the number of poles of 200 or more. Such a connector for a memory module is subjected to an IR reflow process for surface mounting at a peak temperature of 230 to 280 ° C., and 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 memory card sockets such as a card bus, CF card, memory stick, PC card, SD card, SDMo, smart card, and smart media card.

  The molding method for obtaining the electronic component of the present invention is not particularly limited, and it is preferable to select molding conditions having no residual internal stress in order to obtain an electronic component in which warpage deformation is suppressed. In order to lower the filling pressure and reduce the residual internal stress of the obtained electronic component, the cylinder temperature of the molding machine is preferably a temperature equal to or higher than the melting point of the liquid crystalline polymer.

  The mold temperature is preferably 70 to 100 ° C. If the mold temperature is low, the composite resin composition filled in the mold may cause flow failure, which is not preferable. If the mold temperature is high, problems such as the occurrence of burrs may occur, which is not preferable. The injection speed is preferably 150 mm / second or more. If the injection speed is low, there is a possibility that only an unfilled molded product can be obtained. Even if a completely filled molded product is obtained, it becomes a molded product with a high filling pressure and a large residual internal stress. Only parts may be obtained.

  In the electronic component of the present invention, warpage is suppressed. The degree of warpage of the electronic component is determined as follows. That is, with the DDR-DIMM connector shown in FIG. 1, the height is 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 is taken as a warp. In the electronic component of the present invention, changes in warpage are suppressed before and after performing IR reflow.

  Moreover, in the electronic component of the present invention, the generation of blisters is suppressed. The degree of blistering is determined by the blister temperature. That is, the presence or absence of blisters on the surface of a molded product sandwiched between hot presses at a predetermined temperature for 5 minutes is visually observed, and the highest temperature at which the number of blisters generated becomes zero is defined as the blister temperature. It is evaluated that the higher the blister temperature, the more blister generation is suppressed.

  Further, the electronic component of the present invention is excellent in heat resistance, for example, heat resistance as evaluated by high temperature rigidity. The high-temperature rigidity is evaluated by measuring the deflection temperature under load in accordance with ISO75-1,2.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<Synthesis Example 1>
A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a decompression / outflow line was charged with the following raw material monomers, fatty acid metal salt catalyst, and acylating agent, and nitrogen substitution was started.
(I) 9.7 mol (58 mol%) 4-Hydroxybenzoic acid (HBA)
(II) 6-hydroxy-2-naphthoic acid 0.17 mol (1 mol%) (HNA)
(III) Terephthalic acid 3.2 mol (19.25 mol%) (TA)
(IV) 0.25 mol (1.5 mol%) isophthalic acid (IA)
(V) 2.5 mol of 4,4′-dihydroxybiphenyl (15.25 mol%) (BP)
(VI) N-acetyl-p-aminophenol 0.83 mol (5 mol%) (APAP)
Potassium acetate catalyst 110mg
1734 g of acetic anhydride (1.03 times the total hydroxyl equivalent of HBA, HNA, BP and APAP)
After charging the raw materials, 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 (ie, 1330 Pa) over 20 minutes to melt while distilling acetic acid, excess acetic anhydride, and other low-boiling components. Polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced and the pressure was changed from a reduced pressure state to a normal pressure, and the polymer was discharged from the lower part of the polymerization vessel.

<Evaluation>
About the wholly aromatic polyester amide of the synthesis example 1, evaluation of melting | fusing point, melt viscosity, and DTUL was performed with the following method. The evaluation results are shown in Table 1.

[Melting point]
After observing the endothermic peak temperature (Tm1) observed by DSC (manufactured by TA Instruments) at a temperature rising condition of 20 ° C./min from room temperature, the temperature is 2 at (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.

[DTUL]
60% by mass of polymer and 40% by mass of glass fiber (Central Glass Co., Ltd. EFH75-01, milled fiber, average fiber diameter 11 μm, average fiber length 75 μm) twin screw extruder (TEX30α type, manufactured by Nippon Steel) Was melt kneaded at a cylinder temperature of the melting point of the polymer + 20 ° C. to obtain polyesteramide resin composition pellets.
The polyesteramide resin composition pellets were molded under the following molding conditions using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) to obtain test specimens (4 mm × 10 mm × 80 mm). . Using this test piece, the deflection temperature under load was measured by a method based on ISO75-1,2. Note that 1.8 MPa was used as the bending stress. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature: Polymer melting point + 15 ° C
Mold temperature: 80 ℃
Back pressure: 2MPa
Injection speed: 33mm / sec

[Melt viscosity]
Using a Capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd., using an orifice with an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline polymer, and a shear rate of 1000 / sec. The melt viscosity of the liquid crystalline polymer was measured. The measured temperatures were as shown in Table 1.

<Synthesis Examples 2-18, Comparative Synthesis Examples 1-11>
A polymer was obtained in the same manner as in Synthesis Example 1 except that the type of raw material monomer and the charging ratio (mol%) were as shown in Tables 1 to 3. Further, the same evaluation as in Synthesis Example 1 was performed. The evaluation results are shown in Tables 1-3.

<Examples 1-12, Comparative Examples 1-5>
In the following Examples and Comparative Examples, the liquid crystalline polymer 1 is the liquid crystalline polymer obtained in Synthesis Example 15. Liquid crystalline polymers 2 and 3 were produced as follows.

  In this example, the melting point 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 melt viscosity]
Using Capillograph Type 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., using an orifice with an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline polymer, with a shear rate of 1000 / sec, In conformity, the melt viscosity of the liquid crystalline polymer was measured. The measurement temperatures for liquid crystal polymer 1 were 360 ° C., liquid crystal polymer 2 was 350 ° C., and liquid crystal polymer 3 was 380 ° C.

(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: 1380 g (60 mol%) (HBA)
(II) 6-hydroxy-2-naphthoic acid: 157 g (5 mol%) (HNA)
(III) Terephthalic acid: 484 g (17.5 mol%) (TA)
(IV) 4,4′-dihydroxybiphenyl: 388 g (12.5 mol%) (BP)
(V) 4-acetoxyaminophenol: 126 g (5 mol%) (APAP)
Potassium acetate catalyst: 110 mg
Acetic anhydride: 1659g

  After the raw materials were charged 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, 1330 Pa) over 15 minutes, while acetic acid, excess acetic anhydride, and other low-boiling components 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 336 ° C. and a melt viscosity of 19 Pa · s.

(Method for producing liquid crystalline polymer 3)
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: 1040 g (48 mol%) (HBA)
(II) 6-hydroxy-2-naphthoic acid: 89 g (3 mol%) (HNA)
(III) Terephthalic acid: 547 g (21 mol%) (TA)
(IV) Isophthalic acid: 91 g (3.5 mol%) (IA)
(V) 4,4′-dihydroxybiphenyl: 716 g (24.5 mol%) (BP)
Potassium acetate catalyst: 110 mg
Acetic anhydride: 1644 g

  After the raw materials were charged 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 5 Torr (ie, 667 Pa) over 20 minutes while distilling acetic acid, excess acetic anhydride, and other low-boiling components. 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 355 ° C. and a melt viscosity of 10 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 4 and 5. Hereinafter, “%” in the table represents mass%.
(B) Fibrous filler Glass fiber 1: ECS03T-786H manufactured by Nippon Electric Glass Co., Ltd., fiber diameter 10 μm, chopped strand having a length of 3 mm Glass fiber 2: ECS03T-790DE manufactured by Nippon Electric Glass Co., Ltd., fiber diameter 6 μm , 3 mm long chopped strand Milled fiber: PF70E001 manufactured by Nittobo Co., Ltd., fiber diameter 10 μm, average fiber length 70 μm (manufacturer nominal value)
In addition, said manufacturer's nominal value differs from 100 micrometers in Table 4 which is an actual measurement value in a composition.
(C) Plate-shaped filler talc; Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd., average particle size 10 μm

The extrusion conditions for obtaining the composite resin composition are as follows.
[Extrusion conditions]
[Examples 1 to 12, Comparative Examples 1 to 3]
The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperatures of the other cylinders were all 360 ° C. All liquid crystalline polymers were supplied from the main feed port. The filler was supplied from the side feed port.
[Comparative Example 4]
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.
[Comparative Example 5]
The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperatures of the other cylinders were all 380 ° C. All liquid crystalline polymers were supplied from the main feed port. The filler was supplied from the side feed port.

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

(Measurement of melt viscosity of composite resin composition)
Using Capillograph Type 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., using an orifice with an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline polymer, with a shear rate of 1000 / sec, In conformity, the melt viscosity of the composite resin composition was measured. The measurement temperature is 360 ° C. for the composite resin composition using the liquid crystalline polymer 1, 350 ° C. for the composite resin composition using the liquid crystalline polymer 2, and the composite resin composition using the liquid crystalline polymer 3. Was 380 ° C. The results are shown in Tables 4 and 5.

  Based on the following method, the physical properties of the connector molded from the composite resin composition were measured. Each evaluation result is shown in Table 4 and Table 5.

(Bending test)
Under the following molding conditions, the composite resin composition was injection molded to obtain a molded product having a thickness of 0.8 mm, and bending strength, breaking strain, and bending elastic modulus were measured in accordance with ASTM D790.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, SE100DU
Cylinder temperature:
360 ° C. (Examples 1 to 12, Comparative Examples 1 to 3)
350 ° C. (Comparative Example 4)
370 ° C. (Comparative Example 5)
Mold temperature: 80 ℃
Injection speed: 33mm / sec

(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:
360 ° C. (Examples 1 to 12, Comparative Examples 1 to 3)
350 ° C. (Comparative Example 4)
370 ° C. (Comparative Example 5)
Mold temperature: 80 ℃
Injection speed: 33mm / sec

(Blister temperature)
The composite resin composition was injection molded under the following molding conditions to obtain a 12.5 mm × 120 mm × 0.8 mm molded product having a weld portion. A fragment obtained by dividing the molded product into two parts at the weld part was used as one specimen, and was sandwiched in a hot press at a predetermined temperature for 5 minutes. Thereafter, it was visually examined whether blisters were generated on the surface of the specimen. The blister temperature was the maximum temperature at which the number of blisters generated was zero. The predetermined temperature was set in increments of 10 ° C. in the range of 250 to 300 ° C.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, SE100DU
Cylinder temperature:
360 ° C. (Examples 1 to 12, Comparative Examples 1 to 3)
350 ° C. (Comparative Example 4)
370 ° C. (Comparative Example 5)
Mold temperature: 90 ℃
Injection speed: 33mm / sec

(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:
360 ° C. (Examples 1 to 12, Comparative Examples 1 to 3)
350 ° C. (Comparative Example 4)
370 ° C. (Comparative Example 5)
Mold temperature: 80 ℃
Injection speed: 200mm / sec

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 Preheating 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.

  As shown in Tables 4 and 5, the electronic parts molded from the composite resin composition in the present invention were excellent in heat resistance, and warpage deformation and blister generation were suppressed.

Claims (7)

A composite resin composition comprising (A) a liquid crystalline polymer, (B) a fibrous filler, and (C) a plate-like filler,
The (A) liquid crystalline polymer consists of only the following structural units (I) to (VI) as essential structural components,
Content of structural unit (I) is 50-70 mol% with respect to all the structural units,
The content of the structural unit (II) is 0.5 mol% or more and less than 4.5 mol% with respect to all the structural units,
Content of structural unit (III) is 10.25-22.25 mol% with respect to all the structural units,
The content of the structural unit (IV) is 0.5 mol% or more and less than 4.5 mol% with respect to all the structural units,
Content of a structural unit (V) is 5.75-23.75 mol% with respect to all the structural units,
Content of structural unit (VI) is 1-7 mol% with respect to all the structural units,
The total content of the structural unit (II) and the structural unit (IV) with respect to all the structural units is 1 mol% or more and less than 5 mol%,
The total content of the structural units (I) to (VI) with respect to all the structural units is 100 mol%,
A wholly aromatic polyester amide exhibiting optical anisotropy when melted, wherein the molar ratio of the structural unit (VI) to the total of the structural unit (V) and the structural unit (VI) is 0.04 to 0.37. ,
The weight average fiber length of the (B) fibrous filler is 250 μm or more,
Said (A) liquid crystalline polymer is 37.5-82.5 mass% with respect to the whole composite resin composition,
Said (B) fibrous filler is 2.5-17.5 mass% with respect to the whole composite resin composition,
The (C) plate-like filler is 15 to 45% by mass with respect to the entire composite resin composition,
The total amount of said (B) fibrous filler and said (C) plate-like filler is a composite resin composition which is 17.5-62.5 mass% with respect to the whole composite resin composition.

  The total number of moles of the structural unit (III) and the structural unit (IV) is 1 to 1.1 times the total number of moles of the structural unit (V) and the structural unit (VI), or the structural unit ( The composite resin composition according to claim 1, wherein the total number of moles of V) and the structural unit (VI) is 1 to 1.1 times the total number of moles of the structural unit (III) and the structural unit (IV). object.   The composite resin composition according to claim 1 or 2, wherein the (B) fibrous filler is a glass fiber.   The composite resin composition according to claim 1, wherein the (C) plate-like filler is talc.   An electronic component molded from the composite resin composition according to any one of claims 1 to 4, having a total product length of 30 mm or more and a product height of 5 mm or more.   6. The electronic component according to claim 5, 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 5 or 6, which is a memory module connector having a pitch distance of 0.6 mm or less, a total product length of 60.0 mm or more, a product height of 10.0 mm or less, and a pole number of 200 or more.

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