WO2021085240A1

WO2021085240A1 - Resin composition and connector

Info

Publication number: WO2021085240A1
Application number: PCT/JP2020/039381
Authority: WO
Inventors: 博樹深津; 昭宏長永
Original assignee: ポリプラスチックス株式会社
Priority date: 2019-10-31
Filing date: 2020-10-20
Publication date: 2021-05-06
Also published as: JPWO2021085240A1; TW202124513A; CN114630865A; MY195150A; KR20220098130A; CN114630865B; JP6944615B1

Abstract

[Problem] To provide: a resin composition which has excellent flowability and rarely undergoes the contamination with foreign matters, and from which a molded article having reduced warpage and/or deformation can be produced; and a connector molded from the resin composition. [Solution] A resin composition comprising (A) a wholly aromatic polyester, (B) a fibrous filler and (C) a sheet-like filler, wherein the component (A) contains constituent units (I) to (IV) as essential constituents, the contents of the constituent units (I), (II), (III) and (IV) respectively fall within specified mol% ranges relative to the total amount of all of the constituent units, the difference between the content of the constituent unit (III) and the content of the constituent unit (IV) is 0.150 mol% or less, the content of the wholly aromatic polyester (A) is 57.5 to 80% by mass, the content of the component (B) is 1.5 to 15% by mass relative to the whole mass of the resin composition, the content of the component (C) is 12.5 to 35% by mass relative to the whole mass of the resin composition, and the total amount of the components (B) and (C) is 20.0 to 42.5% by mass relative to the whole mass of the resin composition, and the weight average fiber length of the component (B) is shorter than 200 μm.

Description

Resin composition and connector

The present invention relates to a resin composition and a connector.

Liquid crystal polymers such as all-aromatic polyester are thermoplastic resins with excellent dimensional accuracy and fluidity. Due to these characteristics, liquid crystal polymers have been adopted as materials for various electronic components.

In particular, with the recent miniaturization and thinning of electronic devices, there is a need for lowering the height and narrowing of the pitch of electronic components (connectors, etc.) that make up the electronic devices. For example, Patent Document 1 discloses a connector molded from a liquid crystal polymer composition reinforced with mica and glass fiber. Such a connector is for connecting a board-to-board connector or a flexible printed circuit board (FPC) and a flexible flat cable (FFC), which are required to have heat resistance, suppression of warpage deformation, fluidity, dimensional stability, and the like. It is used as a connector for flexible printed circuit boards used in

Japanese Unexamined Patent Publication No. 2006-37061

Sublimated products may be generated in the total aromatic polyester during the polymerization reaction. Such sublimated products may be precipitated and deposited on the inner wall of the polymerization vessel or the like, where polycondensation, deterioration, or carbonization may be mixed in the polymer as foreign matter. If foreign matter is mixed in the polymer, it may cause gate clogging during injection molding. Further, when the foreign matter is a carbide, it may cause poor continuity of the electronic component molded from the resin composition. In particular, in electronic components that have been made smaller and / or thinner, there is a higher possibility that conduction failure will occur.
In addition, in the production of miniaturized and thinned electronic components, a resin composition having excellent fluidity and less warpage and deformation of the obtained molded product is required.

The present invention provides a resin composition capable of producing a molded product having excellent fluidity, less contamination of foreign substances, and less warpage and / or deformation, and a connector molded from the resin composition. Make it an issue.

The present invention has the following aspects.
[1] Contains (A) total aromatic polyester, (B) fibrous filler, and (C) plate-like filler, and (A) total aromatic polyester is the following constituent unit as an essential component. It contains (I) to (IV), the content of the structural unit (I) is 40 to 75 mol%, and the content of the structural unit (II) is 0.5 to 7. It is 5 mol%, the content of the constituent unit (III) is 8.5 to 30 mol%, and the content of the constituent unit (IV) is 8.5 to 30 mol%, and the constituent unit ( The difference between the content of III) and the content of the structural unit (IV) is 0.150 mol% or less, the content of (A) total aromatic polyester is 57.5 to 80% by mass, and (B). ) The content of the fibrous filler is 1.5 to 15% by mass with respect to the entire resin composition, and (C) the content of the plate-like filler is 12.5 to 35% by mass with respect to the entire resin composition. %, The total amount of (B) fibrous filler and (C) plate-like filler is 20.0 to 42.5% by mass with respect to the entire resin composition, and (B) the weight of the fibrous filler. A resin composition having an average fiber length of less than 200 μm.

[2] The total content of the structural units (I), (II), (III) and (IV) is 100 mol% with respect to all the structural units of (A) all aromatic polyesters, [1]. The resin composition according to.
[3] The resin composition according to [1] or [2], wherein the (B) fibrous filler contains milled glass fiber.
[4] The resin composition according to any one of [1] to [3], wherein the (C) plate-like filler contains one or more selected from the group consisting of talc and mica.
[5] The resin composition according to any one of [1] to [4], which is used for manufacturing a connector.
[6] Use of the resin composition according to any one of [1] to [4] for manufacturing a connector.
[7] A molded product containing the resin composition according to any one of [1] to [4].
[8] A connector comprising the resin composition according to any one of [1] to [4], having a product total length of less than 30 mm and a product height of less than 5 mm.
[9] The connector according to [8], which is a low profile narrow pitch connector.
[10] The distance between pitches is 0.5 mm or less, the total length of the product is 3.5 mm or more, the product height is 4.0 mm or less, and the low profile is a board-to-board connector or a connector for a flexible printed circuit board. The connector according to [8] or [9], which is a pitch connector.

According to the present invention, there is provided a resin composition capable of producing a molded product having excellent fluidity, less contamination of foreign substances, and less warpage and / or deformation, and a connector molded from the resin composition. be able to.

It is a figure which shows the FPC connector molded in an Example. (A) is a front view, (b) is a plan view, (c) is a side view, (d) is a back view, and (e) is a sectional view taken along the line AA in (b). Yes, (f) is a detailed view of part B in (b). The unit of the numerical value in the figure is mm. It is a figure which shows the measurement point (black circle) in the measurement of the warp of the FPC connector performed in an Example. The unit of the numerical value in the figure is mm. It is explanatory drawing which shows the shape of the mold used for evaluating the molding stability in an Example, (a) is a plan view of the whole, (b) is a plan view which shows the dimension of a mold. (C) is a side view showing the dimensions of the mold, and (d) is a side view showing the configuration of the mold. The unit of the numerical value in the figure is mm. "PL" represents a parting line. “Tunnel gate” represents a tunnel type gate of a mold.

Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired.

[Resin composition]
The resin composition contains (A) a total aromatic polyester, (B) a fibrous filler, and (C) a plate-like filler.

((A) All aromatic polyester)
The total aromatic polyester contains the following structural units (I) to (IV) as essential constituents. Since the following constituent units (I) to (IV) are contained as essential constituents, it is necessary to provide a molded product having excellent heat resistance and mechanical strength (particularly mechanical strength in a high temperature environment) required for electronic parts. In addition, since the melting point can be lowered to a melting point that can be processed by a general-purpose melting processing device, excellent moldability can be realized even when molding a miniaturized and / or thinned electronic component.

The structural unit (I) is derived from 6-hydroxy-2-naphthoic acid (hereinafter, also referred to as "HNA"). The total aromatic polyester contains 40 to 75 mol% of the structural unit (I) with respect to all the structural units. If the content of the structural unit (I) is less than 40 mol%, the melting point is excessively lowered and the heat resistance is insufficient. If the content of the structural unit (I) exceeds 75 mol%, solidification occurs during polymerization and a polymer cannot be obtained. From the viewpoint of heat resistance and polymerizable property, the content of the structural unit (I) is preferably 40 to 70 mol%, more preferably 40 to 65 mol%, and further preferably 40 to 63 mol%. , Even more preferably 40 to 62 mol%, and particularly preferably 40 to 60 mol%.

The structural unit (II) is derived from 4-hydroxybenzoic acid (hereinafter, also referred to as "HBA"). The total aromatic polyester contains 0.5 to 7.5 mol% of the structural unit (II) with respect to all the structural units. If the content of the structural unit (II) is less than 0.5 mol%, solidification occurs during polymerization and the polymer cannot be discharged. If the content of the structural unit (II) exceeds 7.5 mol%, the melting point is excessively lowered and the heat resistance is insufficient. From the viewpoint of heat resistance and polymerizable property, the content of the structural unit (II) is preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 mol%, and further preferably 1.0 to 7.0 mol%. Is 1.2 to 7.0 mol%, more preferably 1.5 to 6.5 mol%, and particularly preferably 2.0 to 6.0 mol%.

The structural unit (III) is derived from 1,4-phenylenedicarboxylic acid (hereinafter, also referred to as "TA"). The total aromatic polyester contains 8.5 to 30 mol% of the structural unit (III) with respect to all the structural units. When the content of the structural unit (III) is less than 8.5 mol% or more than 30 mol%, at least one of lowering the melting point for lowering the melting point to a temperature that can be processed by a general-purpose melting processing machine and heat resistance It tends to be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (III) is preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 14 to 28. It is in mol%, more preferably 15 to 28 mol%, and particularly preferably 17 to 27 mol%.

The structural unit (IV) is derived from 4,4'-dihydroxybiphenyl (hereinafter, also referred to as "BP"). The total aromatic polyester contains 8.5 to 30 mol% of structural units (IV) with respect to all structural units. If the content of the structural unit (IV) is less than 8.5 mol% or more than 30 mol%, 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 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 14 to 28 mol%. It is in mol%, more preferably 15 to 28 mol%, and particularly preferably 17 to 27 mol%.

The total content of the constituent units (I), (II), (III) and (IV) of the total aromatic polyester is preferably 95 mol% or more based on the total constituent units of the total aromatic polyester. .. By setting the total content of the structural units (I), (II), (III) and (IV) to 95 mol% or more, excellent heat resistance, mechanical strength and moldability can be easily maintained. Can be done. The total content of the structural units (I), (II), (III) and (IV) is more preferably 100 mol% with respect to all the structural units of the total aromatic polyester.

The difference between the content of the constituent unit (III) and the content of the constituent unit (IV) of the total aromatic polyester is 0.150 mol% or less. By setting the difference between the content of the structural unit (III) and the content of the structural unit (IV) to 0.150 mol% or less, the generation of sublimated substances during the polymerization reaction can be suppressed, whereby the resin can be suppressed. It is possible to reduce the mixing of foreign substances into the composition. In the total aromatic polyester, the difference between the content of the structural unit (III) and the content of the structural unit (IV) is preferably 0.145 mol% or less, and more preferably 0.140 mol% or less. It is more preferably 0.135 mol% or less, further preferably 0.130 mol% or less, and particularly preferably 0.125 mol% or less.

As a method for reducing the difference between the content of the structural unit (III) and the content of the structural unit (IV) to 0.150 mol% or less, in addition to adjusting the content according to the amount of the monomer, for example, during the polymerization reaction. It can also be performed by gradually increasing the temperature (for example, changing the heating rate stepwise).

For example, in one embodiment, the temperature during the polymerization reaction is set to 140 ° C. to 360 ° C. in order to reduce the difference between the content of the structural unit (III) and the content of the structural unit (IV) to 0.150 mol% or less. The temperature can be raised in stages.
In one embodiment, the temperature is raised by changing the heating rate (for example, increasing the heating rate stepwise) by dividing the temperature from 140 ° C to 200 ° C, from 200 ° C to 270 ° C, and from 270 ° C to 360 ° C. Can be done.
In one embodiment, the rate of temperature rise from 140 ° C. to 200 ° C. can be 0.4 ° C./min or more and less than 0.8 ° C./min. The rate of temperature rise from 200 ° C. to 270 ° C. can be set to 0.8 ° C./min or more and 1.2 ° C./min or less. The rate of temperature rise from 270 ° C. to 360 ° C. can be set to 0.4 ° C./min or more and 1.2 ° C./min or less.

Next, the properties of all aromatic polyesters will be described. All aromatic polyesters exhibit optical anisotropy when melted. Exhibiting optical anisotropy when melted means that the total aromatic polyester is a liquid crystal polymer.

In the present embodiment, the fact that the total aromatic polyester is a liquid crystal polymer is an indispensable element for the total aromatic polyester to have both thermal stability and easy workability. The total aromatic polyester composed of the constituent units (I) to (IV) may not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the polymer, but it is used in the present embodiment. Polymers are limited to all-aromatic polyesters that exhibit optical anisotropy when melted.

The nature of melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the confirmation of melt anisotropy can be carried out by melting a sample placed on a hot stage manufactured by Rinkamu using a polarizing microscope manufactured by Olympus and observing it at a magnification of 150 times in a nitrogen atmosphere. Liquid crystalline polymers are optically anisotropic and transmit light when inserted between orthogonal polarizers. If the sample is optically anisotropic, polarized light is transmitted even in a molten static liquid state, for example.

Since a nematic liquid crystal polymer causes a significant decrease in viscosity above the melting point, generally, showing liquid crystallinity at a temperature above the melting point is an index of processability. The melting point is preferably as high as possible from the viewpoint of heat resistance, but it is preferably 380 ° C. or lower in consideration of thermal deterioration during melt processing of the polymer and the heating capacity of the molding machine. It is more preferably 260 to 370 ° C, even more preferably 270 to 370 ° C, and particularly preferably 280 to 360 ° C.

The melt viscosity of the total aromatic polyester at a temperature 10 to 40 ° C. higher than the melting point of the total aromatic polyester and at a shear rate of 1000 / sec is preferably 1000 Pa · s or less. When the melt viscosity is 1000 Pa · s or less, the total aromatic polyester itself or the composition containing the total aromatic polyester tends to secure fluidity at the time of molding, and the filling pressure is unlikely to become excessive. .. The melt viscosity of the total aromatic polyester is more preferably 4 to 500 Pa · s, even more preferably 4 to 250 Pa · s, and particularly preferably 5 to 100 Pa · s. In addition, in this specification, the melt viscosity means the melt viscosity measured in accordance with ISO11443.

Since the above-mentioned all-aromatic polyester produces less sublimated matter during melt polymerization, it is possible to reduce the amount of foreign matter mixed in the resin composition. The amount of sublimated material during melt polymerization can be measured from the mass change of the reflux column and the upper part of the reactor used in melt polymerization. The total aromatic polyester preferably has a sublimated amount of 2.3% or less at the time of melt polymerization. When the amount of sublimated material at the time of melt polymerization is 2.3% or less, the amount of foreign matter mixed in the polymer can be further reduced. The amount of sublimated material during melt polymerization is more preferably 2.0% or less, still more preferably 1.9% or less.

Next, a method for producing an all-aromatic polyester will be described. The total aromatic polyester used in the present embodiment is polymerized by 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 is used, and a melt polymerization method or a combination of the melt polymerization method and the solid phase polymerization method is used. Is preferably used.

The conditions for the polymerization reaction are not particularly limited as long as the polymerization of the above-mentioned structural units proceeds, and for example, the reaction temperature is 200 to 380 ° C. and the final ultimate pressure is 0.1 to 760 Torr (that is, 13 to 101,080 Pa). ) May be.
In one embodiment, the temperature at the time of the polymerization reaction can be raised stepwise from 140 ° C. to 360 ° C. (divided into two or more steps or three or more steps). By gradually raising the temperature at the time of the polymerization reaction from 140 ° C. to 360 ° C., the content of the structural unit (III) and the content of the structural unit (IV) in the obtained total aromatic polyester The difference can easily be 0.150 mol% or less.
In one embodiment, the temperature can be raised by changing the heating rate by dividing the temperature from 140 ° C. to 200 ° C., from 200 ° C. to 270 ° C., and from 270 ° C. to 360 ° C.
In one embodiment, the rate of temperature rise from 140 ° C. to 200 ° C. can be 0.4 ° C./min or more and less than 0.8 ° C./min. The rate of temperature rise from 200 ° C. to 270 ° C. can be set to 0.8 ° C./min or more and 1.2 ° C./min or less. The rate of temperature rise from 270 ° C. to 360 ° C. can be set to 0.4 ° C./min or more and 1.2 ° C./min or less.

In the method for producing a total aromatic polyester of the present embodiment, the amount of 1,4-phenylenedicarboxylic acid used (mol%) and the amount of 4,4'-dihydroxybiphenyl used (mol%) are determined from the viewpoint of increasing the molecular weight. It is preferable that they are equal. It should be noted that the generation of sublimated products during the production of the total aromatic polyester of the present embodiment causes a difference in their contents.

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

Various catalysts can be used for these polymerizations, and typical ones are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris (2). , 4-Pentandionato) Examples include metal salt-based catalysts such as cobalt (III) and organic compound-based catalysts such as 1-methylimidazole and 4-dimethylaminopyridine.

In the reaction, all raw material monomers (6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl), an acylating agent, and a catalyst were used in the same reaction vessel. (One-step method), 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl were acylated with an acylating agent. Later, it can also be reacted with the carboxyl group of 1,4-phenylenedicarboxylic acid (two-stage method).

After the inside of the reaction system reaches a predetermined temperature, melt polymerization is carried out by starting depressurization to a predetermined decompression degree. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the pressure is changed from a reduced pressure state to a normal pressure state to a predetermined pressure state, and the total aromatic polyester is discharged from the reaction system.

The total aromatic polyester produced by the above polymerization method can be further increased in molecular weight by solid-phase polymerization of normal pressure, reduced pressure, or heating in an inert gas.

The content of the total aromatic polyester is 57.5 to 80.0% by mass in the total resin composition. By setting the content of the total aromatic polyester in the range of 57.5 to 80.0% by mass, the liquid crystal resin has excellent fluidity, rigidity, mechanical strength, heat resistance, chemical resistance, and electrical properties. Etc. can be sufficiently expressed. The content of the total aromatic polyester in the resin composition is preferably 57.5 to 77.5% by mass, more preferably 59.7 to 77. From the viewpoint of heat resistance, high rigidity and high fluidity. 2% by mass.

((B) Fibrous filler)
The resin composition contains a fibrous filler. Since it contains a fibrous filler, it is possible to provide a molded product having excellent high-temperature rigidity and suppressed warpage deformation. The fibrous filler is not particularly limited, and is not particularly limited, and is glass fiber, milled glass fiber, carbon fiber, asbestos fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate. Examples include whisker and calcium silicate whisker (wollastonite). The fibrous filler preferably contains one or more selected from milled glass fiber and calcium silicate whisker (wollastonite) in that the high-temperature rigidity of the molded product obtained from the resin composition can be easily improved. More preferably, it contains milled glass fiber.

The weight average fiber length of the fibrous filler is less than 200 μm. Since the weight average fiber length of the fibrous filler is less than 200 μm, it is possible to achieve both high fluidity of the resin composition and suppression of warpage deformation of the molded product. If the weight average fiber length of the fibrous filler is 200 μm or more, the fluidity may decrease and it may become difficult to manufacture a molded product used as a miniaturized or thinned electronic device, which is not preferable. ..
The weight average fiber length of the fibrous filler is preferably 170 μm or less, more preferably 150 μm or less. The lower limit of the weight average fiber length is not particularly limited, and is preferably 50 μm or more, and more preferably 70 μm or more. When the weight average fiber length is 50 μm or more, the high-temperature rigidity of the molded product molded from the resin composition tends to be sufficient, which is preferable.

In the present specification, the weight average fiber length of the fibrous filler refers to the fibrous filler of the incinerated residue obtained by heating the resin composition at 600 ° C. for 2 hours to incinerate it to obtain an incinerated residue. Stereomicroscopic images of 100 images are taken from a CCD camera into a PC and measured by an image measuring machine by an image processing method. This is repeated 10 times, and refers to the average value of the measured values when the number of fibrous fillers reaches about 1000.

The fiber diameter of the fibrous filler is not particularly limited, and generally about 5 to 15 μm is used. The fibrous filler can be used alone or in combination of two or more. The fiber diameter is the average value of the measured fiber diameters of 100 fibrous fillers obtained by observing the fibrous filler with a scanning electron microscope.

The content of the fibrous filler is 1.5 to 15% by mass with respect to the entire resin composition. When the content of the fibrous filler is less than 1.5% by mass with respect to the entire resin composition, the deflection temperature under load of the molded product such as a connector obtained from the resin composition is low, and the high temperature rigidity is not sufficient. Therefore, it is not preferable. If the content of the fibrous filler is more than 15% by mass with respect to the entire resin composition, the fluidity of the composition may deteriorate and the warpage deformation of the molded product may increase, which is not preferable.
The content of the fibrous filler is preferably 2 to 15% by mass, more preferably 2.5 to 15% by mass, and further preferably 3 to 15% by mass with respect to the entire resin composition.

((C) Plate-shaped filler)
The resin composition contains a plate-like filler. Since it contains a plate-shaped filler, it is possible to obtain a molded product in which warpage deformation is suppressed. Examples of the plate-like filler include talc, mica, glass flakes, and various metal foils. It is preferable to include one or more selected from talc and mica in terms of suppressing warpage deformation of the molded product obtained from the resin composition without deteriorating the fluidity of the resin composition, and it is preferable to include talc. More preferred.

The average particle size of the plate-shaped filler is not particularly limited, and a smaller one is desirable in consideration of the fluidity in the thin-walled portion. On the other hand, in order to reduce the warp deformation of a molded product such as a connector obtained from the resin composition, it is necessary to maintain a certain size. Specifically, 1 to 100 μm is preferable, and 5 to 50 μm is more preferable. The average particle size means a volume-based cumulative average particle size (D50) measured by a laser diffraction method.
The plate-shaped filler can be used alone or in combination of two or more.

(talc)
_{As for talc, the total content of Fe 2} O ₃ , Al ₂ O ₃ and Ca O is 2.5% by mass or less with respect to the total solid content of the talc, _{and the total of Fe 2} O ₃ and Al ₂ O ₃ It is preferable that the content is more than 1.0% by mass and 2.0% by mass or less, and the CaO content is less than 0.5% by mass. _{That is, talc contains at least one of Fe 2} O ₃ , Al ₂ O ₃ and Ca O in addition to _{SiO 2} and MgO, which are the main components thereof, and each component is contained in the above content range. There may be.

_{When the total content of Fe 2} O ₃ , Al ₂ O ₃ and CaO in the above talc is 2.5% by mass or less, the molding processability of the resin composition and the molding of a connector or the like molded from the resin composition are formed. The heat resistance of the product does not deteriorate easily. 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 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 easily available. Further, in the above 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 resin composition and the molding of a connector or the like molded from the resin composition are formed. The heat resistance of the product does not deteriorate easily. The total content of Fe ₂ O ₃ and Al ₂ O ₃ is preferably more than 1.0% by mass and 1.7% by mass or less.

In the above talc, when the CaO content is less than 0.5% by mass, the molding processability of the resin composition and the heat resistance of the molded product such as a connector molded from the resin composition are unlikely to deteriorate. The CaO content is preferably 0.01% by mass or more and 0.4% by mass or less.

The volume-based cumulative average particle size (D50) of talc measured by laser diffraction is 4.0 to 20.0 μm from the viewpoint of preventing warpage deformation of the molded product and maintaining the fluidity of the resin composition. It is preferably 10 to 18 μm, and more preferably 10 to 18 μm.

(Mica)
Mica is a pulverized product of silicate minerals containing aluminum, potassium, magnesium, sodium, iron and the like. Examples of mica include muscovite, phlogopite, biotite, and artificial mica. Of these, muscovite is preferable because it has a good hue and is inexpensive.

In the production of mica, a wet crushing method and a dry crushing method are known as methods for crushing minerals. The wet pulverization method is a method in which rough mica is roughly pulverized by a dry pulverizer, water is added, and the main pulverization is performed by wet pulverization in a slurry state, and then dehydration and drying are performed. Although the dry pulverization method is a low-cost and general method as compared with the wet pulverization method, it is easier to pulverize the mineral thinly and finely by using the wet pulverization method. It is preferable to use a thin and fine pulverized product because mica having a preferable average particle size and thickness described later can be obtained. Therefore, it is preferable to use mica produced by the wet pulverization method.

Since the wet pulverization method requires a step of dispersing the object to be crushed in water, it is common to add a coagulation sedimentation agent and / or a sedimentation aid to the object to be pulverized in order to improve the dispersion efficiency of the object to be pulverized. Is the target. Examples of coagulation sedimentation agents and sedimentation aids include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyiron sulfate, polyferric chloride, iron-silica inorganic polymer flocculant, and chloride. Examples include ferric-silica inorganic polymer flocculant, slaked lime (Ca (OH) ₂ ), caustic soda (NaOH), soda ash (Na ₂ CO ₃ ) and the like. These coagulation sedimentation agents and sedimentation aids have an alkaline or acidic pH.
Mica preferably does not use a coagulation sedimentation agent and / or a sedimentation aid during wet pulverization. When mica that has not been treated with a coagulation sedimentation agent and / or a sedimentation aid is used, decomposition of the polymer in the resin composition is unlikely to occur, and a large amount of gas is less likely to be generated or the molecular weight of the polymer is less likely to decrease. It is easy to maintain the performance of the molded product better.

Mica preferably has an average particle size of 10 to 100 μm measured by a microtrack laser diffraction method, and particularly preferably has an average particle size of 20 to 80 μm. When the average particle size of mica is 10 μm or more, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable. When the average particle size of mica is 100 μm or less, the rigidity of the molded product is likely to be sufficiently improved, and the weld strength is also likely to be sufficient, which is preferable. Further, when the average particle size of mica is 100 μm or less, it is easy to secure sufficient fluidity for molding a connector or the like.

As for the thickness of mica, the average thickness actually measured for 100 pieces by observation with an electron microscope is preferably 0.01 to 1 μm, and particularly preferably 0.03 to 0.3 μm. When the average thickness of mica is 0.01 μm or more, the mica is less likely to crack during the melt processing of the resin composition, and the rigidity of the molded product may be easily improved, which is preferable. When the thickness of mica is 1 μm or less, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable.

Mica may be surface-treated with a silane coupling agent or the like, and / or may be granulated with a binder to form granules.

The content of the plate-shaped filler is 12.5 to 35% by mass with respect to the entire resin composition. If the content of the plate-shaped filler is less than 12.5% by mass with respect to the entire resin composition, it is not preferable because the suppression of warpage deformation of the molded product obtained from the resin composition is not sufficient. If the content of the plate-shaped filler is more than 35% by mass with respect to the entire resin composition, the fluidity of the resin composition may deteriorate and molding of the resin composition may become difficult, which is not preferable. ..
The content of the plate-shaped filler is preferably 15 to 35% by mass, more preferably 16 to 33% by mass, and further preferably 17.5 to 32% by mass with respect to the entire resin composition.

(Total amount of fibrous filler and plate-like filler)
In the resin composition, the total amount of the fibrous filler and the plate-shaped filler is 20 to 42.5% by mass with respect to the entire resin composition. When the total amount is less than 20% by mass with respect to the entire resin composition, the molded product such as a connector obtained from the resin composition has a low deflection temperature under load, insufficient high-temperature rigidity, and warpage deformation. It is not preferable because it may become large. If the total amount exceeds 42.5% by mass with respect to the entire resin composition, the fluidity of the resin composition deteriorates, and molding is performed when manufacturing small and thin molded products such as low-profile narrow pitch connectors. It is not preferable because it is inferior in sex. The total amount is preferably 20 to 40% by mass, more preferably 20 to 35.5% by mass, and further preferably 22.5 to 35% by mass with respect to the entire resin composition.

(Release agent)
It is preferable to add a mold release agent to the resin composition. The release agent is not particularly limited as long as it is generally available, and examples thereof include fatty acid esters, fatty acid metal salts, fatty acid amides, low molecular weight polyolefins, and the like. Fatty acid esters (eg, pentaerythritol tetrastearate) are preferred.

The amount of the release agent to be blended is preferably in the range of 0.1 to 3% by mass in the resin composition. When the blending amount of the release agent is 0.1% by mass or more, the releasability at the time of molding is improved, and it is easy to obtain a molded product with less warpage and / or deformation. When the blending amount of the release agent is 3% by mass or less, the mold deposit (that is, the deposit on the mold in molding; hereinafter, also referred to as “MD”) is likely to be reduced. The blending amount of the release agent is more preferably 0.1 to 1% by mass, still more preferably 0.1 to 0.5% by mass.

(Other ingredients)
In addition to the above components, the resin composition includes pigments such as nucleating agents, carbon black, and inorganic calcined pigments, antioxidants, stabilizers, plasticizers, flame retardants, and components other than the above components (B) and (C). One or more of the known inorganic fillers of the above may be blended in an amount of 5% by mass or less.
The resin composition includes liquid crystal resins other than the above-mentioned all aromatic polyesters, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyallyl sulfone resin, thermoplastic polyimide resin, and thermoplastic. Other thermoplastic resins such as urethane resin, polyaminobismaleimide resin, polyamideimide resin, and polyetherimide resin may be blended in an amount of 7% by mass or less or 5% by mass or less based on the entire resin composition.

(Resin composition)
The resin composition according to the present embodiment described above contains less foreign matter derived from the sublimated product during polymer polymerization. To check for the presence or absence of foreign matter mixed in the resin composition, apply a white backlight to a film (0.5 g / sheet, film thickness 100 μm) prepared by hot pressing the resin composition, and check the number of foreign matter using a loupe. It can be evaluated by doing. The resin composition in which foreign matter is suppressed can suppress gate clogging during injection molding, has excellent molding stability, and can suppress foreign matter from being mixed into the obtained molded product. As a result, it is possible to suppress poor continuity of the electronic component formed from the resin composition.

Since the resin composition according to the present embodiment described above has excellent fluidity, the minimum filling pressure during molding is unlikely to be excessive, and the resin composition has a small and complicated shape such as a connector, particularly a low profile narrow pitch connector or the like. 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 at which a good molded product can be obtained when the FPC 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 is evaluated.

The resin composition has a melt viscosity of 1 × 105 Pa · s or less (more preferably) measured in accordance with ISO11443 at a temperature 10 to 30 ° C. higher than the melting point of the total aromatic polyester at a shear rate of 1000 / sec. Is 5 Pa · s or more and 1 × 102 Pa · s or less) in that the fluidity of the resin composition is ensured and the filling pressure does not become excessive during molding of the connector, especially the low-profile narrow pitch connector. preferable.

Since the resin composition according to the above-described embodiment contains a fully aromatic polyester, it has excellent heat resistance. As an index showing the heat resistance of the resin composition, there is a deflection temperature under load (hereinafter, also referred to as “DTUL”). When DTUL is 260 ° C. or higher, heat resistance tends to be high, which is preferable. DTUL can be measured according to ISO75-1 and ISO75-1. From the viewpoint of achieving both a low melting point and heat resistance, the DTUL of the resin composition is preferably 265 ° C. or higher and 310 ° C. or lower, and more preferably 267 ° C. or higher and 300 ° C. or lower.

The resin composition preferably has a bending strength of 160 MPa or more in a bending test based on ASTM D790 of a 0.8 mm thick molded product molded from the resin composition.
The resin composition preferably has a bending fracture strain of 2.4% or more in a bending test based on ASTM D790 of a 0.8 mm thick molded product molded from the resin composition.
The resin composition preferably has a flexural modulus of 12000 MPa or more in a bending test based on ASTM D790 of a 0.8 mm thick molded product molded from the resin composition.

(Manufacturing method of resin composition)
The method for producing the resin composition is not particularly limited as long as the components in the resin composition can be uniformly mixed, and can be appropriately selected from the conventionally known methods for producing the resin composition. For example, a method in which each component is melt-kneaded and extruded using a melt-kneading device such as a single-screw or twin-screw extruder, and then the obtained resin composition is processed into a desired form such as powder, flakes, and pellets. Can be mentioned.

[Use]
The resin composition according to the present embodiment can produce a molded product having excellent fluidity, less contamination with foreign substances, and less warpage and / or deformation. Therefore, a connector, a CPU socket, a relay switch component, a bobbin, and the like can be manufactured. It can be preferably used for manufacturing actuators, noise reduction filter cases, electronic circuit boards, heat fixing rolls for OA equipment, and the like. Since it has excellent fluidity and can suppress the occurrence of conduction failure due to the inclusion of foreign matter, it can be particularly preferably used for manufacturing a connector such as a low profile narrow pitch connector. For example, it can be preferably used for manufacturing a low-profile narrow pitch connector having a product total length of less than 30 mm and a product height of less than 5 mm.

[Molding]
The molded product according to the present embodiment is molded from the resin composition according to the present embodiment and includes the above resin composition. Since it is formed from the resin composition, it is possible to obtain a molded product with less foreign matter mixed in and less warpage and / or deformation.

[connector]
The connector according to the present embodiment is molded from the resin composition according to the present embodiment and includes the above resin composition. Since it is formed from a resin composition, it is possible to obtain a connector with less foreign matter mixed in and less warpage and / or deformation. Since there is little foreign matter mixed in, poor continuity can be prevented.
For example, a connector having a product overall length of less than 30 mm, preferably 20 mm or less, a product width of less than 3 mm, preferably less than 2 mm, and a product height of less than 5 mm, preferably less than 4.5 mm. Can be mentioned. The connector having a product total length of less than 30 mm and a product height of less than 5 mm is not particularly limited, and examples thereof include a low profile narrow pitch connector, a coaxial connector, a micro SIM connector, and a micro SD connector.
Of these, a low profile narrow pitch connector is preferable. The "low profile narrow pitch connector" is a low profile and narrow pitch connector. The low profile narrow pitch connector is not particularly limited, and includes, for example, a board-to-board connector (also known as a "BtoB connector"), a flexible printed circuit board connector (flexible printed circuit board (FPC), and a flexible flat cable (FFC). (Used to connect, also known as "FPC connector") and the like. Among them, the distance between pitches is 0.5 mm or less, the total length of the product is 3.5 mm or more and less than 30 mm, the product height is 4.0 mm or less, and the low profile is a board-to-board connector or a flexible printed circuit board connector. Narrow pitch connectors are preferred.

The molding method for obtaining the connector is not particularly limited, and it is preferable to select molding conditions without residual internal stress in order to prevent deformation of the obtained connector. In order to lower the filling pressure and reduce the residual internal stress of the obtained connector, the cylinder temperature of the molding machine is preferably a temperature equal to or higher than the melting point of the total aromatic polyester.

The mold temperature is preferably 70 to 100 ° C. When the mold temperature is 70 to 100 ° C., it is possible to prevent the resin composition filled in the mold from causing poor flow, and it is also possible to prevent the occurrence of burrs. The injection speed is preferably 150 mm / sec or more. When the injection speed is 150 mm / sec or more, it is possible to prevent the generation of unfilled molded products, prevent the increase in residual internal stress due to the filling pressure becoming too high, and make the connector with good flatness. ..

The connector is prevented from being mixed with foreign matter. The degree of contamination of foreign matter is determined as follows. That is, the degree of mixing can be determined by the number of times the gate is clogged during molding of the connector. Since gate clogging is caused by the generation of foreign matter during molding, it can be evaluated that the mixing of foreign matter is suppressed when the gate clogging does not occur.

The connector is suppressed from warping deformation. The degree of warpage of the connector is determined as follows. That is, with the FPC 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 squares plane is used as a sled. In the connector according to the present embodiment, the change in warpage is suppressed before and after performing IR reflow.

Blister generation is suppressed in the connector. A blister is a fine bulge that occurs on the surface of a molded product when it is left in hot air or liquid for a long time. The degree of blister generation is determined by the blister temperature. That is, the presence or absence of blister generation on the surface of the molded product sandwiched in a hot press at a predetermined temperature for 5 minutes is visually observed, and the maximum temperature at which the number of blister generation becomes zero is defined as the blister temperature. It is evaluated that the higher the blister temperature, the more the blister generation is suppressed.

The connector has excellent heat resistance, for example, heat resistance as evaluated by high temperature rigidity. High temperature rigidity is evaluated by measuring the deflection temperature under load in accordance with ISO75-1 and ISO75-1.

The present invention will be described in more detail with reference to Examples below, but the interpretation of the present invention is not limited by these Examples.

[Synthesis Example 1]
The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 6-Hydroxy-2-naphthoic acid 0.883 mol (48 mol%) (HNA)
(II) 4-Hydroxybenzoic acid 0.037 mol (2 mol%) (HBA)
(III) 1,4-phenylenedicarboxylic acid 0.46 mol (25 mol%) (TA)
(IV) 4,4'-Dihydroxybiphenyl 0.46 mol (25 mol%) (BP)
Potassium acetate catalyst 150ppm
Tris (2,4-pentanedionato) cobalt (III) catalyst 150ppm
1.91 mol of acetic anhydride (1.04 times the total hydroxyl equivalent of HBA and BP)

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C, and the reaction was carried out at 140 ° C for 1 hour. Then, the temperature is further raised under the speed conditions shown in Table 1, and the pressure is reduced to 10 Torr (that is, 1330 Pa) over 20 minutes, and melt polymerization is carried out while distilling acetic acid, excess acetic anhydride, and other low boiling points. went. After the stirring torque reaches a predetermined value, nitrogen is introduced to change the pressure from a reduced pressure state to a pressurized state through normal pressure, and the product is discharged from the lower part of the polymerization vessel and pelletized to obtain a pellet-shaped prepolymer. It was. The obtained prepolymer was heat-treated (solid-phase polymerization) at 300 ° C. for 3 hours under a nitrogen stream to obtain the desired polymer.

[Synthesis Examples 2 to 8]
A polymer was obtained in the same manner as in Example 1 except that the type of raw material monomer, the amount used (mol%), and the rate of temperature rise were as shown in Table 1.
[Synthesis Examples 9 to 14]
A polymer was obtained in the same manner as in Example 1 except that the type of raw material monomer, the amount used (mol%), and the rate of temperature rise were as shown in Table 2.

[Sublimation quantity]
In the melt polymerization in Synthesis Examples 1 to 14, the amount of sublimated material was measured from the mass change of the reflux column and the upper part of the reactor. The evaluation results are shown in Tables 1 and 2.

[Measurement]
The melting point, melt viscosity, and amount of terminal groups of all aromatic polyesters of Synthesis Examples 1 to 14 were measured by the following methods. The results are shown in Tables 1 and 2.

(Melting point)
After measuring the heat absorption peak temperature (Tm1) observed when all aromatic polyester is heated from room temperature to 20 ° C./min with a differential scanning calorimeter (DSC, manufactured by Perkin Elmer), (Tm1 + 40). ) After holding at a temperature of ° C for 2 minutes, once cooled to room temperature under a temperature decreasing condition of 20 ° C / min, and then heating again under a heating condition of 20 ° C / min, the temperature of the heat absorption peak observed is measured. did.

(Melting viscosity)
Using Capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), using an orifice with an inner diameter of 0.5 mm and a length of 30 mm at a temperature of 380 ° C., a shear rate of 1000 / sec, and ISO11443, all aromatic polyester. (The melt viscosity of Synthesis Examples 4 and 8 was measured at a temperature of 350 ° C.).

(Monomer composition (content))
The monomer composition was calculated by the pyrolysis gas chromatography method described in Polymer Degradation and Stability 76 (2002) 85-94. Specifically, using a pyrolysis device (“PY2020iD” manufactured by Frontier Lab Co., Ltd.), all aromatic polyester is heated in the presence of tetramethylammonium hydroxide (TMAH), and gas is pyrolyzed / methylated. Was generated. This gas was analyzed using gas chromatography (“GC-6890N” manufactured by Azilent Technology Co., Ltd.), and the peak area derived from 1,4-phenylenedicarboxylic acid and the peak derived from 4,4′-dihydroxybiphenyl were analyzed. From the ratio to the area, the difference between the content of the constituent unit derived from 1,4-phenylenedicarboxylic acid and the content of the constituent unit derived from 4,4'-dihydroxybiphenyl was calculated.

[Example 1]
The total aromatic polyester obtained in Synthesis Example 1 and the following components were mixed using a twin-screw extruder to obtain a resin composition. The extrusion conditions are as follows. The blending amount of each component is as shown in Table 1.
(B) Fibrous filler Milled glass fiber (milled fiber): "EPH-80M" manufactured by Nippon Electric Glass Co., Ltd., fiber diameter 10.5 μm, average fiber length 80 μm (manufacturer's nominal value)
Calcium silicate whiskers (Wollastonite): "NYGLOS 8" manufactured by IMERYS, average fiber diameter 8 μm, average fiber length 130 μm, aspect ratio 16)
The manufacturer's nominal value is different from the measured value (weight average fiber length) in the composition. The weight average fiber length will be described later.
(C) Plate-shaped filler talc: "Crown talc PP" manufactured by Matsumura Sangyo Co., Ltd., average particle size 10 μm
Mica: "AB-25S" manufactured by Yamaguchi Mica Industry Co., Ltd., average particle size 25 μm
Release agent: Pentaerythritol tetrastearate (manufactured by Emery Oleo Chemicals Japan Co., Ltd.)

(Extrusion conditions)
The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperature of all other cylinders was 360 ° C. All aromatic polyesters were supplied through the main feed port. The filler was supplied from the side feed port.

[Examples 2 to 9, Comparative Examples 1 to 6]
A resin composition was obtained in the same manner as in Example 1 except that the blending amount of each component was as shown in Table 1.
[Examples 10 and 11, Comparative Examples 7 to 16]
A resin composition was obtained in the same manner as in Example 1 except that the blending amount of each component was as shown in Table 2.

[Measurement and evaluation]
The weight average fiber length of the fibrous filler in the resin composition, various physical properties of the resin composition, and the like were measured by the following methods. The results are shown in Tables 1 and 2.

(Weight average fiber length of fibrous filler)
5 g of the resin composition pellet was heated at 600 ° C. for 2 hours to incinerate. After the ashing residue was sufficiently dispersed in a 5 mass% polyethylene glycol aqueous solution, it was transferred to a petri dish with a dropper, and the fibrous filler was observed under 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). That is, a stereomicroscopic image of about 100 fibrous fillers of the ashing residue was taken from the CCD camera into a PC and measured by an image processing method with an image measuring machine. This was repeated 10 times, and the average value of the measured values when the number of fibrous fillers reached about 1000 was taken as the weight average fiber length.

(Melted viscosity of resin composition)
Using Capillograph 1B type 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 all aromatic polyester, at a shear rate of 1000 / sec, ISO11443. The melt viscosity of the resin composition was measured according to the above.
Evaluation was made according to the following criteria.
2 (Good): The melt viscosity was 50 Pa · s or less.
1 (defective): The melt viscosity was more than 50 Pa · s.
The measured temperature is as follows.
Resin composition using all aromatic polyesters of Synthesis Examples 1 to 3, 5 to 7, 9 to 14: 380 ° C.
Resin composition using all aromatic polyesters of Synthesis Examples 4 and 8: 350 ° C.

(Foreign matter)
The resin composition was made into a film (0.5 g / sheet, film thickness 100 μm) using a high temperature hot press machine (“NP-SNH” manufactured by Toyo Seiki Seisakusho Co., Ltd.). A white backlight was applied to the film, and the number of foreign substances of 0.3 mm or more was confirmed using a loupe. The number of foreign substances was confirmed for 5 films (2.5 g), and the number of foreign substances per unit weight was determined.
Evaluation was made according to the following criteria.
2 (good): The number of foreign substances was 0 / g.
1 (defective): The number of foreign substances was 1 piece / g or more.

(Bending test)
The resin composition was injection-molded under the following molding conditions to obtain a molded product having a size of 130 mm × 13 mm × 0.8 mm, and the bending strength, bending breaking strain, and bending elastic modulus were measured according to ASTM D790.
<Molding conditions>
Molding machine: Sumitomo Heavy Industries, SE100DU
Cylinder temperature:
370 ° C (Examples 1 to 7, Examples 9 to 11, Comparative Examples 1 to 5, Comparative Examples 7 to 16)
340 ° C. (Example 8, Comparative Example 6)
Mold temperature: 80 ° C
Injection speed: 33 mm / sec
Holding pressure: 50 MPa

Evaluation was made according to the following criteria.
Bending strength 2 (good): The bending strength was 160 MPa or more.
1 (defective): The bending strength was less than 160 MPa.
Bending fracture strain 2 (good): The bending fracture strain was 2.4% or more.
1 (defective): The bending fracture strain was less than 2.4%.
Bending elastic modulus 2 (good): The bending elastic modulus was 12000 MPa or more.
1 (defective): The flexural modulus was less than 12000 MPa.

(Deflection temperature under load)
Under the following molding conditions, the resin composition was injection-molded to obtain a molded product having a size of 4 mm × 10 mm × 80 mm, and the deflection temperature under load was measured in accordance with ISO75-1 and ISO75-1.
<Molding conditions>
Molding machine: Sumitomo Heavy Industries, SE100DU
Cylinder temperature:
370 ° C (Examples 1 to 7, Examples 9 to 11, Comparative Examples 1 to 5, Comparative Examples 7 to 16)
340 ° C. (Example 8, Comparative Example 6)
Mold temperature: 90 ° C
Injection speed: 33 mm / sec
Holding pressure: 50 MPa

Evaluation was made according to the following criteria.
2 (Good): The deflection temperature under load was 260 ° C. or higher.
1 (defective): The deflection temperature under load was less than 260 ° C.

(Blister temperature)
Under the following molding conditions, the resin composition is injection-molded to obtain a molded product of 12.5 mm × 120 mm × 0.8 mm, 30 of these molded products are immersed in silicone oil at a predetermined temperature, washed with a detergent, and then naturally. It was dried and visually inspected for blisters on the surface. The blister temperature was set to the minimum temperature at which the number of blisters generated was zero out of 30 molded products.
<Molding conditions>
Molding machine: Sumitomo Heavy Industries, SE100DU
Cylinder temperature:
370 ° C (Examples 1 to 7, Examples 9 to 11, Comparative Examples 1 to 5, Comparative Examples 7 to 16)
340 ° C. (Example 8, Comparative Example 6)
Mold temperature: 90 ° C
Injection speed: 33 mm / sec

Evaluation was made according to the following criteria.
2 (Good): The blister temperature was 260 ° C. or higher.
1 (defective): The blister temperature was less than 260 ° C.

(FPC connector sled)
The resin composition is injection-molded under the following molding conditions (gate: tunnel gate, gate size: φ0.4 mm), and the overall size is 17.6 mm × 4.00 mm × 1.16 mm, pitch as shown in FIG. An FPC connector having a distance of 0.5 mm, a number of pin holes of 30 × 2 pins, and a minimum wall thickness of 0.12 mm was obtained.
<Molding conditions>
Molding machine: Sumitomo Heavy Industries, SE30DUZ
Cylinder temperature:
370 ° C (Examples 1 to 7, Examples 9 to 11, Comparative Examples 1 to 5, Comparative Examples 7 to 16)
340 ° C. (Example 8, Comparative Example 6)
Mold temperature: 80 ° C
Injection speed: 200 mm / sec
Holding pressure: 50 MPa

The obtained connector was allowed to stand on a horizontal desk, and the height of the connector was measured by a Mitutoyo Quick Vision 404PROCNC image measuring machine. At that 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 from the least squares plane was defined as the warp of the FPC connector. The warp was measured before and after the IR reflow performed under the following conditions.
<IR reflow conditions>
Measuring machine: Large desktop reflow soldering device RF-300 (using far-infrared heater) manufactured by Japan Pulse Technology Research Institute
Sample feed rate: 140 mm / sec
Reflow furnace transit time: 5 minutes Preheat zone temperature condition: 150 ° C
Reflow zone temperature conditions: 190 ° C
Peak temperature: 251 ° C

Evaluation was made according to the following criteria.
Before IR reflow 2 (good): The warp was 0.03 mm or less.
1 (defective): The warp was more than 0.03 mm.
After IR reflow 2 (good): The warp was 0.07 mm or less.
1 (defective): The warp was more than 0.07 mm.

(FPC connector deformation amount)
The difference in warpage before and after reflow measured by the above method was determined as the amount of deformation of the FPC connector. Evaluation was made according to the following criteria.
2 (Good): The amount of deformation was 0.04 mm or less.
1 (defective): The amount of deformation was more than 0.04 mm.

(Minimum filling pressure of FPC connector)
When the FPC connector of FIG. 1 was injection-molded, the minimum injection-filling pressure at which a good molded product could be obtained was measured as the minimum filling pressure. Evaluation was made according to the following criteria.
2 (Good): The minimum filling pressure was 110 MPa or less.
1 (defective): The minimum filling pressure was over 110 MPa.

(Molding stability and foreign matter mixed in the molded product: gate clogging)
Using the mold shown in FIG. 3, molding evaluation was performed under the following conditions.
<Molding conditions>
Mold: Tunnel gate mold, gate diameter 0.1 mm, 2 pieces (inject into 2 molds of the same shape at the same time)
Cylinder temperature:
370 ° C (Examples 1 to 7, Examples 9 to 11, Comparative Examples 1 to 5, Comparative Examples 7 to 16)
340 ° C. (Example 8, Comparative Example 6)
Mold temperature: 80 ° C
Injection speed: 33 mm / sec
Holding pressure: 50 MPa
Number of shots: 360 shots Molding stability and the presence or absence of foreign matter mixed in the molded product were evaluated according to the following criteria.
2 (excellent molding stability and few foreign substances): Gate clogging did not occur.
1 (poor molding stability and a large amount of foreign matter): Gate clogging occurred once or more.

As shown in Tables 1 and 2, the resin composition obtained in the examples has excellent fluidity. In addition, since all aromatic polyesters in which the generation of sublimated substances during the polymerization reaction are suppressed are used, foreign substances are less likely to be mixed. The connector molded from this resin composition had excellent heat resistance, less warpage and / or deformation, and blister generation was suppressed.

Claims

It contains (A) a total aromatic polyester, (B) a fibrous filler, and (C) a plate-like filler.
(A) The total aromatic polyester contains the following structural units (I) to (IV) as essential constituents, and the content of the structural unit (I) is 40 to 75 mol% with respect to all the structural units. Yes, the content of the constituent unit (II) is 0.5 to 7.5 mol%, the content of the constituent unit (III) is 8.5 to 30 mol%, and the content of the constituent unit (IV). The amount is 8.5 to 30 mol%, and the difference between the content of the constituent unit (III) and the content of the constituent unit (IV) is 0.150 mol% or less.
(A) The total aromatic polyester content is 57.5 to 80% by mass.
(B) The content of the fibrous filler is 1.5 to 15% by mass with respect to the entire resin composition.
(C) The content of the plate-shaped filler is 12.5 to 35% by mass with respect to the entire resin composition.
The total amount of the (B) fibrous filler and the (C) plate-like filler is 20.0 to 42.5% by mass with respect to the entire resin composition.
(B) A resin composition in which the weight average fiber length of the fibrous filler is less than 200 μm.
The first aspect of the present invention, wherein the total content of the constituent units (I), (II), (III) and (IV) is 100 mol% with respect to all the constituent units of (A) all aromatic polyesters. Resin composition.
The resin composition according to claim 1 or 2, wherein the (B) fibrous filler contains milled glass fiber.
The resin composition according to any one of claims 1 to 3, wherein the (C) plate-like filler contains one or more selected from the group consisting of talc and mica.
The resin composition according to any one of claims 1 to 4, which is used for manufacturing a connector.
Use of the resin composition according to any one of claims 1 to 4 for manufacturing a connector.
A molded product containing the resin composition according to any one of claims 1 to 4.
A connector containing the resin composition according to any one of claims 1 to 4, having a product total length of less than 30 mm and a product height of less than 5 mm.
The connector according to claim 8, which is a low profile narrow pitch connector.
The distance between pitches is 0.5 mm or less,
The total length of the product is 3.5 mm or more,
The product height is 4.0 mm or less,
The connector according to claim 8 or 9, which is a low-profile narrow-pitch connector that is a board-to-board connector or a connector for a flexible printed circuit board.