KR20190026037A - A composite resin composition, and an electronic component molded from the composite resin composition - Google Patents

Abstract

A composite resin composition capable of obtaining an electronic part having excellent heat resistance, suppressing warpage and blister formation, and an electronic component molded from the composite resin composition.
The composite resin composition according to the present invention comprises (A) a liquid crystalline polymer, (B) a fibrous filler, and (C) a plate filler, wherein the liquid crystalline polymer (A) Is a wholly aromatic polyester amide having optical anisotropy at the time of melting which comprises the following constituent units (I) to (VI), and the weight average fiber length of the fibrous filler (B) is 250 탆 or more.

Description

A composite resin composition, and an electronic component molded from the composite resin composition

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 having excellent dimensional accuracy and fluidity. Because of these characteristics, liquid crystalline polymers have heretofore been employed as materials for various electronic parts.

In particular, in recent years there has been a demand for an era of high internal resistance (productivity improvement by mounting technology), high density (deepening), and miniaturization of connectors due to high performance of electronic devices in recent years. The liquid crystalline polymer composition is employed as a connector material.

In recent years, however, in the connector, lightweight thinning (thinning) has further proceeded, so that deflection due to lack of rigidity due to insufficient thickness of the molded product and internal stress due to the insert of the metal terminal has occurred during molding and reflow heating , There arises a problem that soldering failure with the substrate occurs. That is, in the case of reinforcement made of only conventional glass fiber, if the amount of the glass fiber is increased to increase the rigidity, the resin can not be filled in the thin thickness portion, or the insert terminal is deformed by the pressure at molding .

In order to solve the problem of the warpage deformation, a molding method has been studied, and in the material aspect, the mixing of a specific plate filler has been proposed. That is, in the case of a conventional connector (electronic part) which exists in many places on the market, it is possible to control the dimensional accuracy and warp of the product by designing a gate position capable of maintaining symmetry at the time of molding, By using a material with low warpage, a product with less warpage is obtained.

However, with the recent complication of the shape of electronic parts, it is required to provide asymmetric electronic parts which have no symmetry with respect to any of the X, Y and Z axes of the molded product. As such an asymmetric electronic component, a connector for a memory module having a latch structure such as a DDR-DIMM connector (with latches at both ends) is a typical example. Particularly, the connector for a memory module for a notebook computer has a latch structure for installation and has a notch for alignment, resulting in a very complicated shape.

In the case of such an asymmetric electronic component, unlike a conventional connector (symmetrical electronic component) which has symmetry with respect to any one of the XY axis plane, YZ axis plane, and XZ axis plane of the molded product, There is a limit to the improvement of the warpage deformation in the warp yarns. In the case of an asymmetric electronic component having a complicated shape, the orientation of the resin and the filler in the molded product becomes complicated, higher fluidity is required, and the suppression of the flexural deformation becomes more difficult.

As a technique for solving such a problem, for example, Patent Document 1 discloses a technique of forming a liquid crystalline polymer composition in which a specific amount of a fibrous filler and a specific plate filler are blended in a specific amount, and the XY axis plane, the YZ axis plane, Asymmetrical electronic parts having no symmetry with respect to any of the axial surfaces of the non-symmetric electronic parts.

[Patent Document 1] International Publication No. 2008/023839

However, recently, due to factors such as an increase in the integration ratio in asymmetric electronic parts and a change in shape, in particular, a decrease in the pitch distance or product height, and an increase in the number of poles, the liquid crystalline polymer It has been found that conventional liquid crystalline polymer compositions such as compositions can not cope with such problems. That is, the conventional liquid crystalline polymer composition is insufficient in heat resistance and fluidity, and it has been difficult to obtain an asymmetric electronic component whose flexural deformation is suppressed from such a liquid crystalline polymer composition.

Further, the liquid crystalline polymer composition may have a problem of occurrence of blisters. That is, since the liquid crystalline polyester amide which is a liquid crystalline polymer is excellent in high-temperature thermal stability, it is often used for a material requiring heat treatment at a high temperature. However, when a molded article is left in a high-temperature air or in a liquid for a long time, a fine swelling problem called a blister is generated on the surface. In such a phenomenon, a decomposition gas or the like generated when the liquid crystalline polyester amide is in a molten state permeates into the inside of the molded product, and then, when the high temperature heat treatment is performed, the gas expands and pushes the surface of the molded product softened by heating The raised and raised part appears as a blister. The occurrence of blisters may be reduced by sufficiently de-molding from the gas outlet at the time of melt extrusion of the material or by not staying in the molding machine for a long time when molding. However, the range of conditions is so narrow that it is not sufficient to obtain a molded article suppressing the occurrence of blisters, that is, a molded article having blister resistance. In order to solve the problem of blister generation, it is necessary to improve the quality of the liquid crystalline polyester amide itself, but it is insufficient to solve the problem of blister generation by the known liquid crystalline polyester amide or the method using it.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a composite resin composition which is excellent in heat resistance and in which an electronic component with suppressed flexural deformation and blister generation can be obtained and an electronic component molded from the composite resin composition The purpose.

The inventors of the present invention have solved the above problems by combining a liquid crystalline polymer containing a predetermined constituent unit with a fibrous filler and a plate filler so that the weight average fiber length of the fibrous filler is 250 탆 or more . 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 filler,

The liquid crystalline polymer (A) is composed of the following constituent units (I) to (VI) as essential constituents,

The content of the constituent unit (I) relative to the total constituent units is 50 to 70 mol%

The content of the constituent unit (II) relative to the total constituent units is 0.5 mol% or more and less than 4.5 mol%

The content of the constituent unit (III) relative to the total constituent units is 10.25 to 22.25 mol%

The content of the constituent unit (IV) relative to the total constituent units is 0.5 mol% or more and less than 4.5 mol%

The content of the constituent unit (V) relative to the total constituent units is 5.75 to 23.75 mol%

The content of the constituent unit (VI) relative to the total constituent units is 1 to 7 mol%

The total content of the constituent unit (II) and the constituent unit (IV) relative to the total constituent units is from 1 mol% to less than 5 mol%

The total content of the constituent units (I) to (VI) relative to the total constituent units was 100 mol%

(All-aromatic) polyester amide exhibiting optical anisotropy upon melting, wherein the molar ratio of the constituent unit (VI) to the total of the constituent unit (V) and the constituent unit (VI) is 0.04 to 0.37,

 The fibrous filler (B) has a weight-average fiber length of 250 탆 or more,

 The liquid crystalline polymer (A) is contained in an amount of 37.5 to 82.5 mass% with respect to the total of the composite resin composition,

 The fibrous filler (B) is used in an amount of 2.5 to 17.5% by weight based on the total weight of the composite resin composition,

 The (C) plate filler is contained in an amount of 15 to 45% by mass with respect to the total amount of the composite resin composition,

 Wherein the total amount of the fibrous filler (B) and the plate filler (C) is from 17.5 to 62.5 mass% with respect to the total of the composite resin composition.

(2) the total molar number 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) ) Is 1 to 1.1 times the total number of moles of the structural unit (III) and the structural unit (IV).

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

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

(5) An electronic component molded from the composite resin composition according to any one of (1) to (4), wherein the total length of the product is not less than 30 mm and the product height is not less than 5 mm.

(6) The electronic component according to (5), wherein the asymmetric electronic component has no symmetry with respect to any of the axes of the XY axis plane, the YZ axis plane, and the XZ axis plane of the molded product.

(7) The electronic component according to (5) or (6), wherein the pitch distance is 0.6 mm or less, the total length of the product is 60.0 mm or more, the product height is 10.0 mm or less, and the number of poles is 200 or more.

According to the present invention, there is provided a composite resin composition which is excellent in heat resistance and capable of obtaining an electronic component in which flexural deformation and blister generation are suppressed, and an electronic component molded from the composite resin composition.

1 shows a DDR-DIMM connector molded in an embodiment. A represents the gate position.
Fig. 2 is a diagram showing measurement points in the bending measurement of the DDR-DIMM connector implemented in the embodiment. Fig.

Hereinafter, embodiments of the present invention will be described in detail.

[Composite resin composition]

The composite resin composition of the present invention contains a predetermined amount of a liquid crystalline polymer, a fibrous filler, and a plate filler in a predetermined amount, and the fibrous filler has a weight average fiber length of 250 탆 or more. Hereinafter, the components constituting the composite resin composition in the present invention will be described.

(Liquid crystalline polymer)

The composite resin composition of the present invention includes the liquid crystalline polymer which is the wholly aromatic polyester amide. Since the wholly aromatic polyester amide has a low melting point, the processing temperature can be lowered, and generation of decomposed gas during melting can be suppressed. As a result, in the molded article obtained by molding the composite resin composition containing the wholly aromatic polyester amide, generation of blisters is suppressed, and blister resistance is improved. The liquid crystalline polymers may be used singly or in combination of two or more.

The wholly aromatic polyester amide in the present invention is a wholly aromatic polyester amide having the following constitutional unit (I), the following constitutional unit (II), the following constitutional unit (III), the following constitutional unit (IV) (VI).

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

The constituent 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 the constituent unit (II) in an amount of not less than 0.5 mol% and not more than 4.5 mol% with respect to all the constituent units. If the content of the constituent unit (II) is less than 0.5 mol% or 4.5 mol% or more, at least one of the low melting point and the heat resistance tends to become insufficient. The content of the constituent unit (II) is preferably from 0.75 to 3.75 mol%, more preferably from 1 to 3 mol%, from the viewpoint of achieving both a low melting point and heat resistance.

The constituent unit (III) is derived from 1,4-phenylene dicarboxylic acid (hereinafter also referred to as "TA"). The wholly aromatic polyester amide in the present invention contains the structural unit (III) in an amount of 10.25 to 22.25 mol% based on the total structural units. If the content of the constituent unit (III) is less than 10.25 mol% or exceeds 22.25 mol%, at least one of the low melting point and the heat resistance tends to become insufficient. The content of the constituent unit (III) is preferably from 12.963 to 20.75 mol%, and more preferably from 15.675 to 19.25 mol% from the viewpoint of achieving both of the low melting point and heat resistance.

The constituent unit (IV) is derived from 1,3-phenylene dicarboxylic acid (hereinafter also referred to as " IA "). The wholly aromatic polyester amide in the present invention contains the constituent unit (IV) in an amount of not less than 0.5 mol% and not more than 4.5 mol% with respect to the total constituent units. If the content of the constituent unit (IV) is less than 0.5 mol% or 4.5 mol% or more, at least one of the low melting point and the heat resistance tends to become insufficient. The content of the constituent unit (IV) is preferably from 0.5 to 3.75 mol%, more preferably from 0.5 to 3 mol%, from the viewpoint of both melting point reduction and heat resistance.

The constituent unit (V) is derived from 4,4'-dihydroxybiphenyl (hereinafter also referred to as " BP "). The wholly aromatic polyester amide in the present invention contains the constituent unit (V) in an amount of 5.75 to 23.75 mol% based on the total constituent units. If the content of the constituent unit (V) is less than 5.75 mol% or more than 23.75 mol%, at least one of the low melting point and the heat resistance tends to become insufficient. The content of the constituent unit (V) is preferably from 8.5 to 20.375 mol%, and more preferably from 11.25 to 17 mol% (for example, from 11.675 to 17 mol%) from the viewpoint of achieving both low melting point and heat resistance.

The constituent 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 the constituent unit (VI) in an amount of 1 to 7 mol% based on the total constituent units. If the content of the constituent unit (VI) is less than 1 mol% or exceeds 7 mol%, at least one of low melting point and heat resistance tends to become insufficient. The content of the constituent unit (VI) is preferably from 1.5 to 7 mol%, more preferably from 2 to 7 mol%, from the viewpoint of achieving both of the low melting point and the heat resistance.

The wholly aromatic polyester amide in the present invention contains 1 mol% or more and less than 5 mol% of the total of the constituent unit (II) and the constituent unit (IV) with respect to the total constituent units. In the wholly aromatic polyester amide, the combination of the bending structural unit (II) having a naphthalene skeleton and the bending structural unit (IV) having a benzene skeleton in the total amount within the above range makes it possible to achieve both a low melting point and a high heat resistance easy. If the total content is less than 1 mol%, the proportion of the bending structural units becomes too small, so that the lowering of the melting point tends to become insufficient. When the total content is 5 mol% or more, the proportion of the bending structural units becomes too large, so that the heat resistance tends to become insufficient. The total content is preferably 1.75 to 4.75 mol%, and more preferably 2.5 to 4.5 mol%, from the viewpoint of achieving both a low melting point and heat resistance.

In the wholly aromatic polyester amide of the present invention, the molar ratio of the constituent unit (VI) to the total of the constituent unit (V) and the constituent unit (VI) is 0.04 to 0.37. If the molar ratio is less than 0.04, the proportion of the constituent unit having a biphenyl skeleton increases, so that the crystallinity of the wholly aromatic polyester amide is lowered, and both the lowering of the melting point and the heat resistance tend to become insufficient. When the molar ratio exceeds 0.37, the wholly aromatic polyester amide crystallinity is lowered because of the increase of heterogeneous bonds other than the ester bond, so that the compatibility between the low melting point and the heat resistance tends to become insufficient. The molar ratio is preferably 0.07 to 0.36, and more preferably 0.11 to 0.35 from the viewpoint of achieving both of the low melting point and heat resistance.

(Hereinafter also referred to as "the number of moles of 1A") of the constituent unit (III) and the constituent unit (IV) from the viewpoint of achieving both of the low melting point and the heat resistance, Or the total number of moles of the constituent unit (V) and the constituent unit (VI) is 1 to 1.1 times the number of moles (hereinafter also referred to as "the number of moles of 2A") or the total number of moles of the constituent unit 1 < / RTI > It is more preferable that the number of moles of 1A is 1.02 to 1.06 times the number of moles of 2A or the number of moles of 2A is 1.02 to 1.06 times the number of moles of 1A. More preferably, the number of moles of 1A is 1.024 to 1.056 times the number of moles of 2A or the number of moles of 2A is 1.024 to 1.056 times the number of moles of 1A.

As described above, the wholly aromatic polyester amide in the present invention is obtained by subjecting each of the total of the specific constituent units (I) to (VI) and the constituent unit (II) and the constituent unit (IV) On the other hand, since the molar ratio of the constituent unit (VI) to the total of the constituent unit (V) and the constituent unit (VI) is within a specific range, both the lowering of the melting point and the heat resistance are sufficient. The wholly aromatic polyester amide of the present invention contains the constituent units (I) to (VI) in a total amount of 100 mol% with respect to the total constituent units.

As an index showing the above-mentioned heat resistance, a load bending temperature (hereinafter also referred to as " DTUL ") can be mentioned. When the DTUL is 260 占 폚 or higher, heat resistance tends to be high, which is preferable. DTUL was obtained by mixing 60 mass% of the wholly aromatic polyester amide, 40 mass% of a milled fiber having an average fiber diameter of 11 탆 and an average fiber length of 75 탆 at a melting point + 20 캜 of the wholly aromatic polyester amide The value measured in the state of the polyester amide resin composition obtained by kneading can be measured according to ISO 75-1,2. From the viewpoint of both melting point and heat resistance, DTUL is preferably 265 DEG C or more and 310 DEG C or less, and more preferably 267 to 300 DEG C. [

Next, a method for producing the wholly aromatic polyester amide in the present invention will be described. The wholly aromatic polyester amide in the present invention is polymerized by a direct polymerization method, an ester exchange method or the like. In the polymerization, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like or a combination of two or more thereof is used, and a melt polymerization method or a combination of a melt polymerization method and a solid- And is preferably used.

In the present invention, when polymerizing, an acylating agent for a polymerized monomer or a monomer in which a terminal is 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 thereof include dialkyltin oxide, diaryltin oxide, titanium dioxide, alkoxytitanium silicates, titanium alcoholates, fatty acid metal salts and Lewis acid salts such as BF ₃ And a fatty acid metal salt is preferable. The amount of the catalyst to be used is generally about 0.001 to 1% by mass, particularly about 0.003 to 0.2% by mass, based on the total mass of the monomers.

When the solution polymerization or slurry polymerization is carried out, liquid paraffin, high heat-resistant synthetic oil, inert mineral oil and the like are used as the solvent.

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

The reaction can be started by introducing the entire raw material monomers (HBA, HNA, TA, IA, BP, and APAP), the acylating agent, and the catalyst into the same reaction vessel BP, and APAP can be acylated with an acylating agent and then reacted with carboxyl groups of TA and IA (two-step method).

After the reaction system reaches a predetermined temperature, the melt polymerization is started at a predetermined reduced pressure degree. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the entire aromatic polyester amide is discharged from the reaction system from a reduced pressure state to a predetermined pressurized state through a normal pressure.

The wholly aromatic polyester amide produced by the above polymerization method can further increase the molecular weight by solid-state polymerization in which it is heated in an inert gas at atmospheric pressure or reduced pressure. Preferable conditions for the solid phase polymerization reaction are a reaction temperature of 230 to 350 占 폚, preferably 260 to 330 占 폚, and a final pressure of 10 to 760 Torr (i.e., 1,330 to 101,080 Pa).

The process for producing a wholly aromatic polyester amide in the present invention comprises reacting 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl and Acylation of N-acetyl-p-aminophenol with fatty acid anhydride and transesterification with 1,4-phenylene dicarboxylic acid and 1,3-phenylene dicarboxylic acid,

Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylene dicarboxylic acid, 1,3-phenylene dicarboxylic acid, 4,4'-dihydroxybiphenyl, and Acetyl-p-aminophenol,

Hydroxybenzoic acid is used in an amount of 50 to 70 mol%, preferably 54 to 67 mol%, more preferably 58 to 64 mol%, from the viewpoint of both low melting point and heat resistance,

It is preferable that the amount of 6-hydroxy-2-naphthoic acid is 0.5 mol% or more and less than 4.5 mol%, preferably 0.75 to 3.75 mol%, more preferably 1 to 3 mol%, from the viewpoint of both low melting point and heat resistance %,

The amount of 1,4-phenylene dicarboxylic acid used is preferably from 10.25 to 22.25 mol%, more preferably from 12.963 to 20.75 mol%, and still more preferably from 15.675 to 19.25 mol%, from the viewpoint of both low melting point and heat resistance,

The content of 1,3-phenylene dicarboxylic acid is preferably 0.5 to 3.75 mol%, more preferably 0.5 to 3 mol%, from the viewpoint of both the low melting point and the heat resistance,

The amount of 4,4'-dihydroxybiphenyl to be used is from 5.75 to 23.75 mol%, preferably from 8.5 to 20.375 mol%, and more preferably from 11.25 to 17 mol% (from the viewpoint of both low melting point and heat resistance) , For example, 11.675 to 17 mol%),

The amount of N-acetyl-p-aminophenol to be used is preferably from 1 to 7 mol%, more preferably from 1.5 to 7 mol%, more preferably from 2 to 7 mol%, from the viewpoint of both low melting point and heat resistance,

The total amount of 6-hydroxy-2-naphthoic acid and 1,3-phenylene dicarboxylic acid is 1 mol% or more and less than 5 mol%, preferably 1.75 to 4.75 mol %, More preferably 2.5 to 4.5 mol%

Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylene dicarboxylic acid, 1,3-phenylene dicarboxylic acid, 4,4'-dihydroxybiphenyl, and The total amount of N-acetyl-p-aminophenol used is 100 mol%

, ≪ / RTI >

The molar ratio of the amount of N-acetyl-p-aminophenol to the total amount of 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol used is 0.04 to 0.37, , Preferably 0.07 to 0.36, and more preferably 0.11 to 0.35,

The amount of the fatty acid anhydride to be used is preferably such that the total hydroxyl equivalent of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, It is preferably 1.02 to 1.04 times. It is more preferable that the fatty acid metal salt is a nitric acid metal salt and the fatty acid anhydride is anhydrous acetic acid. 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 preferably 4,4'-dihydroxybiphenyl and N- 1 to 1.1 times the total number of moles of acetyl-p-aminophenol (hereinafter also referred to as " moles 2B "), or the total number of moles of 4,4'-dihydroxybiphenyl and N-acetyl- Is preferably 1 to 1.1 times the total number of moles of 1,4-phenylene dicarboxylic acid and 1,3-phenylene dicarboxylic acid. More preferably, the number of moles of 1B is 1.02 to 1.06 times the number of moles of 2B, or the number of moles of 2B is 1.02 to 1.06 times the number of moles of 1B. It is particularly preferable that the number of moles of 1B is 1.024 to 1.056 times the number of moles of 2B or the number of moles of 2B is 1.024 to 1.056 times the number of moles of 1B.

Next, the properties of the wholly aromatic polyester amide will be described. The wholly aromatic polyester amide in the present invention exhibits optical anisotropy upon melting. The optical anisotropy at the time of melting means that the wholly aromatic polyester amide in the present invention is a liquid crystalline polymer.

In the present invention, the wholly aromatic polyester amide is a liquid crystalline polymer, and the wholly aromatic polyester amide is an indispensable element to combine heat stability and easy processability. The wholly aromatic polyester amide composed of the constituent units (I) to (VI) may be one which does not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the polymer. However, And is defined as a wholly aromatic polyester amide exhibiting anisotropy.

The properties of the melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the confirmation of the melting anisotropy can be carried out by melting a sample placed on a hot stage made by LINCAMAS, using a polarizing microscope manufactured by Olympus, and observing the sample at a magnification of 150 times under a nitrogen atmosphere. The liquid crystalline polymer is optically anisotropic and transmits light when inserted between orthogonal polarizers. If the sample is optically anisotropic, for example, polarized light is transmitted even in the state of the molten stop solution.

Since the nematic liquid crystal polymer causes remarkable decrease in viscosity above the melting point, it is an index of workability that exhibits liquid crystallinity at a melting point or higher. The melting point is preferably as high as possible from the viewpoint of heat resistance, but it is preferable that the melting point is 360 DEG C or less in consideration of heat deterioration at the time of melt processing of the polymer and heating ability of the molding machine. More preferably 300 to 360 ° C, and even more preferably 340 to 358 ° C.

The melt viscosity of the wholly aromatic polyester amide at a temperature 10 to 30 캜 higher than the melting point of the wholly aromatic polyester amide in the present invention and at a shear rate of 1000 / sec is preferably 500 Pa · s or less, Is preferably from 0.5 to 300 Pa · s, and even more preferably from 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 tends to secure fluidity at the time of molding, and the filling pressure is hard to be excessive . In the present specification, the term "melt viscosity" means the melt viscosity measured in accordance with ISO 11443.

As an index showing the above-mentioned heat resistance, a difference between the melting point and DTUL can be mentioned. If the difference is 90 DEG C or less, heat resistance tends to be high, which is preferable. 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), and more preferably 55 to 79 ° C, from the viewpoint of achieving both of low melting point and heat resistance.

In the composite resin composition of the present invention, the above liquid crystalline polymer is contained in the composite resin composition in an amount of 37.5 to 82.5 mass% with respect to the total of the composite resin composition. If the content of the liquid crystalline polymer is less than 37.5 mass% with respect to the total amount of the composite resin composition, the fluidity of the composite resin composition tends to deteriorate and the warpage of the molded article such as an electronic component obtained from the composite resin composition may increase It is not preferable. When the content of the liquid crystalline polymer exceeds 82.5 mass% with respect to the total amount of the composite resin composition, the flexural modulus and crack resistance of a molded product such as an electronic component obtained from the composite resin composition are undesirably lowered. In the composite resin composition of the present invention, the above liquid crystalline polymer is preferably contained in the composite resin composition in an amount of preferably from 44 to 75 mass%, more preferably from 60 to 65 mass%, based on the entire composite resin composition.

(Fibrous filler)

The composite resin composition of the present invention comprises the above liquid crystalline polymer and a fibrous filler, and the fibrous filler has a weight-average fiber length of 250 m or more. Therefore, the molded article obtained by molding the composite resin composition has excellent high- , The warpage is suppressed. The fibrous fillers may be used singly or in combination of two or more kinds. The fibrous filler in the present invention is not particularly limited and examples of the fibrous filler include fibers such as glass fibers, molybdenum fibers, carbon fibers, asbestos fibers, silica fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, And the like. The high-temperature rigidity of the molded article obtained from the composite resin composition tends to be improved. Therefore, glass fiber is preferable 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 preferably 250 占 퐉 or more, more preferably 350 占 퐉 or more, and more preferably 450 占 퐉 or more. If the weight average fiber length is less than 250 탆, the molded article obtained from the composite resin composition is not likely to have a sufficient high-temperature rigidity and the warpage of the molded article may be increased. The upper limit of the weight average fiber length is not particularly limited, and is preferably 700 탆 or less, more preferably 500 탆 or less. When the weight average fiber length is 600 탆 or less, the fluidity of the composite resin composition becomes favorable, and the warpage of the molded article is hardly increased. In the present specification, the weight average fiber length of the fibrous filler means that the composite resin composition is heated at 600 DEG C for 2 hours to obtain a painting residue, and the painted residue is dispersed in a 5 mass% polyethylene glycol aqueous solution to obtain a dispersion , And the weight-average fiber length measured by using an image measuring instrument for the dispersion.

In addition, the fiber diameter of the fibrous filler in the present invention is not particularly limited, and it is generally about 5 to 15 탆.

The composite resin composition of the present invention contains the fibrous filler in the composite resin composition in an amount of 2.5 to 17.5 mass% with respect to the total composite resin composition. If the content of the fibrous filler is less than 2.5% by mass with respect to the total amount of the composite resin composition, a molded article such as an electronic component obtained from the composite resin composition is not preferable because of low load-bending temperature and insufficient high-temperature rigidity. When the content of the fibrous filler exceeds 17.5 mass% with respect to the total amount of the composite resin composition, the fluidity of the composite resin composition deteriorates and the warpage of the molded article tends to increase. The fibrous filler in the present invention is preferably contained in the composite resin composition in an amount of 4 to 16 mass%, more preferably 5 to 15 mass%, based on the entire composite resin composition.

(Plate filler)

The composite resin composition of the present invention further includes a plate filler. By incorporating the plate filler into the composite resin composition of the present invention, a molded article having suppressed flexural deformation can be obtained. The plate fillers may be used singly or in combination of two or more.

The plate filler is contained in an amount of 15 to 45 mass% with respect to the total of the composite resin composition. When the content of the plate filler is less than 15% by mass with respect to the total amount of the composite resin composition, warpage deformation of a molded article such as an electronic component obtained from the composite resin composition may increase. If the content of the plate filler exceeds 45 mass% with respect to the total amount of the composite resin composition, the fluidity of the composite resin composition may be deteriorated. The plate filler in the present invention is preferably contained in the composite resin composition in an amount of 20 to 40 mass%, more preferably 25 to 35 mass%, with respect to the total composite resin composition.

Examples of the plate filler in the present invention include talc, mica, glass flake, various metal foils, and the like. In view of suppressing the warpage of the molded article obtained from the composite resin composition without deteriorating the fluidity of the composite resin composition, desirable. In addition, the average particle diameter of the plate filler is not particularly limited, and is preferably small considering the fluidity in a thin thickness portion. On the other hand, in order to reduce warpage of a molded article such as an electronic component obtained from the composite resin composition, it is necessary to maintain a constant size. Specifically, the thickness is preferably 1 to 100 mu m, more preferably 5 to 50 mu m.

[Talc]

The talc used in the present invention is characterized in that 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, and the content of Fe ₂ O ₃ and Al ₂ O ₃ It is preferable that the total content is more than 1.0% by mass and not more than 2.0% by mass, and the content of CaO is less than 0.5% by mass. That is, the talc usable in the present invention contains at least one of Fe ₂ O ₃ , Al ₂ O _3, and CaO in addition to its main components SiO ₂ and MgO, have.

When the total content of Fe ₂ O ₃ , Al ₂ O _3, and CaO in the talc is 2.5% by mass or less, the molding processability of the composite resin composition and the heat resistance of molded articles such as electronic parts molded from the composite resin composition are 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.

Further, in the above talc, talc having a total content of Fe ₂ O ₃ and Al ₂ O ₃ of more than 1.0% by mass is easy to obtain. When the total content of Fe ₂ O ₃ and Al ₂ O ₃ in the talc is 2.0 mass% or less, the molding processability of the composite resin composition and the heat resistance of a molded product such as an electronic component molded from the composite resin composition are unlikely to deteriorate. The total content of Fe ₂ O ₃ and Al ₂ O ₃ is preferably 1.0% by mass or more and 1.7% by mass or less.

When the content of CaO in the talc is less than 0.5% by mass, the molding processability of the composite resin composition and the heat resistance of molded articles such as electronic parts molded from the composite resin composition are hardly deteriorated. The content of CaO is preferably 0.01 mass% or more and 0.4 mass% or less.

The cumulative mean particle diameter (D ₅₀ ) of the talc in terms of mass or volume as measured by the laser diffraction method is preferably 4.0 to 20.0 占 퐉 in terms of prevention of warpage deformation of the molded article and maintenance of fluidity of the composite resin composition More preferably 10 to 18 占 퐉.

[Mica]

Mica is a pulverized product of silicate minerals including aluminum, potassium, magnesium, sodium, iron and the like. The mica which can be used in the present invention includes muscovite, gold mica, biotite, artificial mica and the like. Among them, muscovite is preferable in terms of good color and low cost.

In the production of mica, wet pulverization and dry pulverization are known as methods for pulverizing minerals. The wet grinding method is a method in which raw mica is roughly pulverized in a dry pulverizer, pulverized (wet pulverized) in a slurry state by adding water, and then dehydrated and dried. Compared with the wet pulverization method, the dry pulverization method is a general method at a low cost, but it is easier to finely pulverize minerals using a wet pulverization method. It is preferable to use a thin and fine pulverized product in the present invention because it is possible to obtain a mica having a preferable average particle diameter and thickness to be described later. Therefore, in the present invention, it is preferable to use a mica produced by a wet grinding method.

In addition, in the wet pulverization method, a step of dispersing the pulverized material in water is required. Therefore, in order to increase the dispersion efficiency of the pulverized material, it is common to add a flocculant and / or precipitating agent to the pulverized material. Examples of the flocculating agent and sedimentation aid that can be used in the present invention include aluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, chloride chloride, ferric sulfate, ferric chloride, iron-silica inorganic polymer flocculant, ferric chloride- Inorganic polymer flocculant, calcium hydroxide (Ca (OH) ₂ ), caustic soda (NaOH), soda ash (Na ₂ CO ₃ ) and the like. These flocculating agents and precipitating agents are alkaline or acidic in pH. It is preferable that the mica used in the present invention does not use the flocculating agent and / or precipitating agent when wet pulverizing. Use of a mica which is not treated with a flocculant and / or sedimentation aid makes it difficult to cause decomposition of the polymer in the composite resin composition, and it is difficult to generate a large amount of gas or lower the molecular weight of the polymer. It is easy to keep the performance of the molded product better.

The mica which can be used in the present invention preferably has an average particle size of 10 to 100 m measured by Microtrac laser diffraction method, and particularly preferably 20 to 80 m. If the average particle diameter of the mica is 10 탆 or more, the effect of improving the rigidity of the molded article tends to be sufficient, which is preferable. When the average particle diameter of the mica is 100 탆 or less, improvement in the rigidity of the molded product tends to be sufficient, and the weld strength tends to be sufficient, which is preferable. When the average particle diameter of the mica is 100 탆 or less, it is easy to ensure sufficient fluidity for molding the electronic parts and the like of the present invention.

The thickness of the mica used in the present invention is preferably 0.01 to 1 m, more preferably 0.03 to 0.3 m, as measured by electron microscopic observation. When the thickness of the mica is not less than 0.01 탆, the mica is not easily broken at the time of melt processing of the composite resin composition, and therefore, the rigidity of the molded article may be easily improved. When the thickness of the mica is 1 占 퐉 or less, the effect of improving the rigidity of the molded article is easily satisfactory.

The mica which can be used in the present invention may be surface-treated with a silane coupling agent or the like, and may be granulated at the same time 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 filler is from 17.5 to 62.5 mass% with respect to the total of the composite resin composition. If the total amount is less than 17.5% by mass based on the total amount of the composite resin composition, a molded article such as an electronic component obtained from the composite resin composition has a low load-bending temperature and insufficient high-temperature rigidity, Which is undesirable. When the total amount exceeds 62.5 mass% with respect to the total amount of the composite resin composition, the flowability of the composite resin composition deteriorates, and the warpage of the molded article may be increased, which is not preferable. The total amount is preferably 25 to 56 mass%, and more preferably 35 to 40 mass%, with respect to the entire composite resin composition.

(Other components)

In the composite resin composition of the present invention, at least one of a pigment such as a nucleating agent, carbon black, an inorganic calcined pigment, an antioxidant, a stabilizer, a plasticizer, a lubricant, a releasing agent, a flame retardant, can do.

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 탆 or more. And can be appropriately selected from the manufacturing method. For example, there is a method of melt-kneading and extruding the respective components using a melt-kneading apparatus such as a single-screw or twin-screw extruder, and then processing the obtained composite resin composition into a desired form such as powder, flake, have.

Since the composite resin composition of the present invention has excellent fluidity, the minimum filling pressure at the time of molding is unlikely to be excessively high, and it is possible to provide an electronic part, particularly a component having a complicated shape such as an asymmetric electronic part having a latch structure or a notch 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 at which a good molded article can be obtained when injection molding the DDR-DIMM connector shown in Fig. 1 is specified as the minimum filling pressure. The lower the minimum filling pressure, the better the fluidity is evaluated.

The melt viscosity of the composite resin composition measured according to ISO 11443 is 1 占 10 ⁵ Pa 占 퐏 or less (more preferably ⁵ Pa 占 퐏 or more, more preferably ¹⁰ Pa 占 퐏 or more, at a temperature 10 to 30 占 폚 higher than the melting point of the liquid crystalline polymer, 1 X ¹⁰ < ² > Pa s), it is preferable that the molding of a part having a complicated shape in an electronic part, especially the molding of a part having a complicated shape such as a latch structure or a notch in asymmetric electronic parts, And the filling pressure is not 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 for example, an electronic component having a total product length of 30 mm or more and a product height of 5 mm or more is exemplified. Asymmetric electronic parts among the electronic parts of the present invention are those having no symmetry with respect to any of the axial surfaces of the XY axis plane, the YZ axis plane, and the XZ axis plane of the molded product.

In the case of a conventional connector (electronic part) existing in many markets, it has symmetry on any one of the XY axis plane, the YZ axis plane, and the XZ axis plane. In order to maintain the symmetry, , It is possible to control the dimensional accuracy and warpage of the product. On the other hand, asymmetrical electronic parts are complicated in shape, and it is difficult to suppress flexural deformation by a molding method. In the electronic component of the present invention, particularly the asymmetric electronic component, the flexural 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 connector for a memory module and an interface connector. As the connector for the memory module, for example, a DIMM connector; DDR connectors such as DDR-DIMM connector, DDR2-DIMM connector, DDR-SO-DIMM connector, DDR2-SO-DIMM connector, DDR-Micro-DIMM connector and DDR2-Micro-DIMM connector. Examples of the interface connector include a SATA connector, a SAS connector, and an NGFF connector. Among them, DDR connector, SATA connector, SAS connector, and NGFF connector are popular, especially for memory modules with a thin thickness and a complicated shape for notebook applications. The connector has a pitch distance of 0.6 mm or less, a total length of 60.0 mm or more , The product height is 10.0 mm or less, and the number of poles is 200 or more. Such a connector for a memory module is used for an IR reflow process for surface mounting at a peak temperature of 230 to 280 DEG C and has a warp of not more than 0.1 mm before the IR reflow process and a difference of warp before and after reflow of 0.05 mm or less. According to the present invention, this requirement can be satisfied.

Examples of the socket include memory card sockets such as a card bus, a CF card, a memory stick, a PC card, an SD card, an SDMo, a smart card, and a smart media card.

The molding method for obtaining the electronic component of the present invention is not particularly limited, and in order to obtain an electronic component whose bending deformation is suppressed, it is preferable to select molding conditions without residual internal stress. In order to lower the filling pressure and decrease the residual internal stress of the obtained electronic component, the temperature of the cylinder of the molding machine is preferably not lower than the melting point of the liquid crystalline polymer.

The mold temperature is preferably 70 to 100 占 폚. If the mold temperature is low, it is not preferable because the composite resin composition filled in the mold may cause flow defects. If the mold temperature is high, there is a possibility that problems such as burrs may occur, which is not preferable. The injection speed is preferably 150 mm / sec or more. If the injection speed is low, there is a possibility that only an uncharged molded product can be obtained. Even if a fully charged molded product is obtained, a molded product having a high residual stress due to a high filling pressure, .

In the electronic component of the present invention, warpage is suppressed. The extent of deflection of the electronic component is determined as follows. That is, in the DDR-DIMM connector shown in Fig. 1, the heights are measured at a plurality of positions indicated by the black origin in Fig. 2, and the difference between the maximum height and the minimum height in the least-squared plane is referred to as bending. In the electronic component of the present invention, the change in warpage is suppressed before and after the IR reflow is performed.

In the electronic component of the present invention, generation of blisters is suppressed. The degree of blister generation is judged by the blister temperature. That is, the presence or absence of blistering on the surface of a molded product sandwiched for 5 minutes in a hot press at a predetermined temperature is visually observed, and the maximum temperature at which the number of blisters is zero is defined as the blister temperature. It is estimated that the higher the blister temperature is, the more blistering is suppressed.

Further, the electronic component of the present invention is excellent in heat resistance evaluated by heat resistance, for example, high temperature stiffness. The high temperature stiffness is evaluated by measuring the flexural flexure temperature in accordance with ISO 75-1,2.

[ Example ]

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

≪ Synthesis Example 1 &

The following raw material monomer, fatty acid metal salt catalyst, and acylating agent were added to a polymerization vessel equipped with a stirrer, a refluxing column, a monomer inlet, a nitrogen inlet, and a decompression /

(I) 9.7 mol (58 mol%) of 4-hydroxybenzoic acid (HBA)

(II) 0.17 mol (1 mol%) of 6-hydroxy-2-naphthoic acid (HNA)

(III) terephthalic acid 3.2 mol (19.25 mol%) (TA)

(IV) 0.25 mol (1.5 mol%) of isophthalic acid (IA)

(V) 4,4'-dihydroxybiphenyl 2.5 mol (15.25 mol%) (BP)

(VI) 0.83 mol (5 mol%) of N-acetyl-p-aminophenol (APAP)

Potassium acetate catalyst 110 mg

1734 g of anhydrous acetic acid (1.03 times the total hydroxyl equivalent of HBA, HNA, BP and APAP)

After the raw materials were added, the temperature of the reaction system was raised to 140 캜, and the reaction was allowed to proceed at 140 캜 for 1 hour. Next, the temperature was raised to 360 ° C over a period of 5.5 hours, and the pressure was reduced to 10 Torr (i.e., 1330 Pa) for 20 minutes from this point, and the resulting mixture was stirred for dissolution of acetic acid, excess anhydrous acetic acid and other low boiling components Polymerization was carried out. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the pressure from the reduced pressure state to the normal pressure state, and the polymer was discharged from the lower part of the polymerization vessel.

<Evaluation>

The melting point, melt viscosity, and DTUL of the wholly aromatic polyester amide of Synthesis Example 1 were evaluated in the following manner. The evaluation results are shown in Table 1.

[Melting point]

After observing the endothermic peak temperature (Tm1) observed when the polymer was measured from a room temperature to 20 ° C / min under a temperature elevation condition in a DSC (manufactured by TA Instrument), it was maintained at a temperature of (Tm1 + 40) Deg.] C / min, cooled once to room temperature, and then the endothermic peak temperature observed when the temperature was raised at a rate of 20 [deg.] C / min was measured.

[DTUL]

40% by mass of a polymer (60% by mass) and glass fiber (EFH75-01 manufactured by Central Glass Co., Ltd., a milled fiber, an average fiber diameter of 11 占 퐉 and an average fiber length of 75 占 퐉) was fed to a twin screw extruder (TEX30? At a cylinder temperature of the polymer + 20 占 폚 to obtain a polyester amide resin composition pellet.

The polyester amide resin composition pellets were molded under the following molding conditions using a molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) to obtain a test piece for measurement (4 mm × 10 mm × 80 mm). Using these test specimens, the flexural flexure temperature was measured in accordance with ISO 75-1,2. The bending stress was 1.8 MPa. The results are shown in Table 1.

〔Molding conditions〕

Cylinder temperature: Polymer melting point + 15 ° C

Mold temperature: 80 ℃

Back pressure: 2 MPa

Injection speed: 33mm / sec

[Melt viscosity]

Using a capillograph made by TOYO SEIKI KOGYO CO., LTD., An orifice having an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30 캜 higher than the melting point of the liquid crystalline polymer was used, and a shear rate of 1000 / The melt viscosity of the liquid crystalline polymer was measured. The measurement temperature is as shown in Table 1.

&Lt; Synthesis Examples 2 to 18, Comparative Synthesis Examples 1 to 11 >

A polymer was obtained in the same manner as in Synthesis Example 1 except that the kind of raw material monomer and the loading ratio (mol%) were as shown in Tables 1 to 3. The same evaluation as in Synthesis Example 1 was carried out. The evaluation results are shown in Tables 1 to 3.

&Lt; Examples 1 to 12, Comparative Examples 1 to 5 >

In the following Examples and Comparative Examples, the liquid crystalline polymer 1 is the liquid crystalline polymer obtained in Synthesis Example 15. The liquid crystalline polymers 2 and 3 were prepared as follows.

In this example, the melting point and the melt viscosity of the pellets were measured under the following conditions, respectively.

[Measurement of melting point]

After observing the endothermic peak temperature (Tm1) observed when the liquid crystalline polymer was measured from the room temperature at a temperature elevation rate of 20 deg. C / min in a DSC manufactured by TA Instrument, it was maintained at a temperature of (Tm1 + 40) The temperature of the endothermic peak observed when the sample was once cooled to room temperature under the temperature lowering condition of &lt; RTI ID = 0.0 &gt; 20 C / min &lt; / RTI &gt;

[Measurement of melt viscosity]

Using an orifice having 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 by using a capillograph 1B type manufactured by Toyo Seiki Seisakusho Co., The melt viscosity of the liquid crystalline polymer was measured. The measurement temperature was 360 캜 for liquid crystalline polymer 1, 350 캜 for liquid crystalline polymer 2, and 380 캜 for liquid crystalline polymer 3.

(Production method of liquid crystalline polymer 2)

The following raw material monomer, metal catalyst, and acylating agent were added to a polymerization vessel equipped with a stirrer, a refluxing column, a monomer inlet, a nitrogen inlet, and a pressure /

(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: 1659 g

After the raw materials were put into the polymerization vessel, the temperature of the reaction system was raised to 140 占 폚 and the reaction was carried out at 140 占 폚 for 1 hour. Next, the temperature was further raised to 340 캜 for 4.5 hours, and the pressure was reduced to 10 Torr (i.e., 1330 Pa) over 15 minutes from here. Molten polymerization was carried out while distilling acetic acid, excess acetic anhydride and other low- Respectively. After the stirring torque reached a predetermined value, nitrogen was introduced, the pressure was changed from the reduced pressure state to the atmospheric pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized by pelletizing. The obtained pellets had a melting point of 336 캜 and a melt viscosity of 19 Pa · s.

(Production method of liquid crystalline polymer 3)

The following raw material monomer, metal catalyst, and acylating agent were added to a polymerization vessel equipped with a stirrer, a refluxing column, a monomer inlet, a nitrogen inlet, and a pressure /

(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 put into the polymerization vessel, the temperature of the reaction system was raised to 140 占 폚 and the reaction was carried out at 140 占 폚 for 1 hour. Next, the temperature was further raised to 360 DEG C over 5.5 hours, and thereafter the pressure was reduced to 5 Torr (i.e., 667 Pa) over 20 minutes from this point, and molten polymerization was carried out while acetic acid, excess acetic anhydride and other low- . After the stirring torque reached a predetermined value, nitrogen was introduced, the pressure was changed from the reduced pressure state to the atmospheric pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized by pelletizing. The obtained pellets had a melting point of 355 DEG C and a melt viscosity of 10 Pa · s.

(Component other than the liquid crystalline polymer)

Each of the liquid crystalline polymers obtained above and the following components were mixed using a twin-screw extruder to obtain a composite resin composition. The blending amounts of the respective components are as shown in Tables 4 and 5. In the following tables, &quot;% &quot;

(B) fibrous filler

Glass fiber 1: ECS03T-786H manufactured by Denki Kagaru Co., Ltd., fiber strand 10 mu m, length 3 mm

Glass fiber 2: ECS03T-790DE manufactured by Denki Kagaru Co., Ltd., fiber strand 6 mu m, length 3 mm

Melt fiber: PF70E001 manufactured by Nitto Co., Ltd., fiber diameter: 10 mu m, average fiber length: 70 mu m (nominal value of the manufacturer)

The maker nominal value is different from 100 占 퐉 in Table 4 which is an actually measured value in the composition.

(C)

Talc; Crown talc PP, manufactured by Matsumura Industry Co., Ltd., average particle diameter 10 占 퐉

The extrusion conditions for obtaining the composite resin composition are as follows.

[Extrusion conditions]

[Examples 1 to 12 and Comparative Examples 1 to 3]

The temperature of the cylinder provided in the main feed port was set to 250 ° C and the temperature of the other cylinder was set to 360 ° C. The liquid crystalline polymer supplied everything to the main feed port. The filler was also fed into the side feed ports.

[Comparative Example 4]

The temperature of the cylinder provided in the main feed port was set to 250 ° C, and the temperature of the other cylinder was set to 350 ° C. The liquid crystalline polymer supplied everything to the main feed port. The filler was also fed into the side feed ports.

[Comparative Example 5]

The temperature of the cylinder provided in the main feed port was set to 250 ° C, and the temperature of the other cylinders was set to 380 ° C. The liquid crystalline polymer supplied everything to the main feed port. The filler was also fed into the side feed ports.

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 was heated at 600 캜 for 2 hours to be painted. The painting residue was sufficiently dispersed in a 5 mass% aqueous polyethylene glycol solution, and then transferred to a chalet with a syringe, 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 analyzer (Nireco LUZEXFS Co., Ltd.).

(Measurement of melt viscosity of composite resin composition)

Using a capillograph 1B type manufactured by TOYO SEIKI KOGYO CO., LTD., An orifice having an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30 캜 higher than the melting point of the liquid crystalline polymer, The melt viscosity of the composite resin composition was measured. The measurement temperature was 360 占 폚 for the composite resin composition using the liquid crystalline polymer 1, 350 占 폚 for the composite resin composition using the liquid crystalline polymer 2, and 380 占 폚 for the composite resin composition using the liquid crystalline polymer 3. 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. The evaluation results are shown in Tables 4 and 5.

(Bending test)

The composite resin composition was injection-molded under the following molding conditions to obtain a molded article having a thickness of 0.8 mm, and the bending strength, the breaking deformation, and the bending elastic modulus were measured in accordance with ASTM D790.

[Molding conditions]

Molding machine: Sumitomo Heavy Industries, SE100DU

Cylinder temperature:

     360 占 폚 (Examples 1 to 12, Comparative Examples 1 to 3)

     350 占 폚 (Comparative Example 4)

     370 占 폚 (Comparative Example 5)

Mold temperature: 80 ℃

Injection speed: 33mm / sec

(Load bending temperature)

The composite resin composition was injection-molded under the following molding conditions to obtain a molded article, and the load bending temperature was measured according to ISO 75-1,2.

[Molding conditions]

Molding machine: Sumitomo Heavy Industries, SE100DU

Cylinder temperature:

     360 占 폚 (Examples 1 to 12, Comparative Examples 1 to 3)

     350 占 폚 (Comparative Example 4)

     370 占 폚 (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 molded article having a welded portion of 12.5 mm X 120 mm X 0.8 mm. One piece of this molded article obtained by dividing the molded part into two pieces in the welded part was sandwiched in a hot press at a predetermined temperature for 5 minutes. Next, whether or not a blister was generated on the surface of the specimen was visually inspected. The blister temperature was set at a maximum temperature at which the number of blisters was zero. The predetermined temperature was set at an interval of 10 ° C in the range of 250 to 300 ° C.

[Molding conditions]

Molding machine: Sumitomo Heavy Industries, SE100DU

Cylinder temperature:

     360 占 폚 (Examples 1 to 12, Comparative Examples 1 to 3)

     350 占 폚 (Comparative Example 4)

     370 占 폚 (Comparative Example 5)

Mold temperature: 90 ℃

Injection speed: 33mm / sec

(DDR connector flexure)

The composite resin composition was injection molded (gate: tunnel gate, gate size: 0.75 mm) under the following molding conditions to obtain a total size of 70.0 mm Х26.0 mm Х4.0 mm, a pitch distance of 0.6 mm, a fin spacing of 100 Х2 Of DDR-DIMM connector.

[Molding conditions]

Molding machine: Sumitomo Heavy Industries Machinery SE30DUZ

Cylinder temperature:

     360 占 폚 (Examples 1 to 12, Comparative Examples 1 to 3)

     350 占 폚 (Comparative Example 4)

     370 占 폚 (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 a Quickvision 404 PROCNC image measuring instrument manufactured by Mitsutoyo. At this time, the heights were measured at a plurality of positions indicated by black circles in Fig. 2, and the difference between the maximum height and the minimum height in the least square plane was defined as the bending of the DDR connector. The warpage was measured before and after the IR reflow performed under the following conditions.

[IR reflow condition]

Measuring instrument: Large desk reflow soldering machine RF-300 made by Nippon Pulse Technology Research Institute (using far infrared heater)

Sample feed rate: 140mm / sec

Reflow time: 5 minutes

Temperature conditions in the pre-heat zone: 150 ° C

Temperature condition of reflow zone: 190 ℃

Peak temperature: 251 ° C

(DDR connector strain)

The difference in warp before and after reflow as measured by the above-described method was obtained as a DDR connector deformation amount.

(DDR connector minimum charging pressure)

When the DDR-DIMM connector of Fig. 1 was injection molded, the minimum injection filling pressure at which a good molded article could be obtained was measured as the minimum filling pressure.

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

Claims (7)

A composite resin composition comprising (A) a liquid crystalline polymer, (B) a fibrous filler, and (C) a plate filler,
The liquid crystalline polymer (A) is composed of the following constituent units (I) to (VI) as essential constituents,
The content of the constituent unit (I) relative to the total constituent units is 50 to 70 mol%
The content of the constituent unit (II) relative to the total constituent units is 0.5 mol% or more and less than 4.5 mol%
The content of the constituent unit (III) relative to the total constituent units is 10.25 to 22.25 mol%
The content of the constituent unit (IV) relative to the total constituent units is 0.5 mol% or more and less than 4.5 mol%
The content of the constituent unit (V) relative to the total constituent units is 5.75 to 23.75 mol%
The content of the constituent unit (VI) relative to the total constituent units is 1 to 7 mol%
The total content of the constituent unit (II) and the constituent unit (IV) relative to the total constituent units is from 1 mol% to less than 5 mol%
The total content of the constituent units (I) to (VI) relative to the total constituent units was 100 mol%
A wholly aromatic polyester amide exhibiting optical anisotropy upon melting, wherein the molar ratio of the constituent unit (VI) to the total of the constituent unit (V) and the constituent unit (VI) is 0.04 to 0.37,
The fibrous filler (B) has a weight-average fiber length of 250 탆 or more,
The liquid crystalline polymer (A) is contained in an amount of 37.5 to 82.5 mass% with respect to the total of the composite resin composition,
The fibrous filler (B) is used in an amount of 2.5 to 17.5% by weight based on the total weight of the composite resin composition,
The (C) plate filler is contained in an amount of 15 to 45% by mass with respect to the total amount of the composite resin composition,
Wherein the total amount of the fibrous filler (B) and the plate filler (C) is from 17.5 to 62.5 mass% with respect to the total of the composite resin composition.
[Chemical Formula 1]

The method according to claim 1,
The total number of moles of the constituent unit (III) and the constituent unit (IV) is 1 to 1.1 times the total number of moles of the constituent unit (V) and the constituent unit (VI) Wherein the number of moles is 1 to 1.1 times the total number of moles of the structural unit (III) and the structural unit (IV). 3. The method according to claim 1 or 2,
The fibrous filler (B) is a glass fiber. 4. The method according to any one of claims 1 to 3,
The (C) plate filler is a talc-containing composite resin composition. An electronic part which is molded from the composite resin composition according to any one of claims 1 to 4 and has a total length of 30 mm or more and a product height of 5 mm or more. 6. The method of claim 5,
An asymmetric electronic part having no symmetry about any of the axial surfaces of the XY-axis surface, the YZ-axis surface, and the XZ-axis surface of the molded product. The method according to claim 5 or 6,
An electronic component that is a connector for a memory module with a pitch distance of 0.6 mm or less, a product length of 60.0 mm or more, a product height of 10.0 mm or less, and a number of poles of 200 or more.

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