JP6944616B1 - Resin composition and planar connector - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of obtaining a flat connector having less foreign matter mixed in and excellent in flatness, weld strength and crack resistance, and a flat connector using the resin composition. A total aromatic polyester, (B) a fibrous filler, and (C) a plate-like filler are included, and (A) contains constituent units (I) to (IV) as essential constituents. The content of the constituent units (I), (II), (III) and (IV) is in a predetermined mass% range with respect to all the constituent units, and the content of the constituent unit (III) and the constituent units The difference from the content of (IV) is 0.150 mol% or less, the content of (A) total aromatic polyester is 50 to 62.5% by mass, and the content of (B) is the resin composition. The content of (C) is 10 to 25% by mass with respect to the whole, the content of (C) is 25 to 40% by mass with respect to the whole resin composition, and the total amount of (B) and (C) is with respect to the whole resin composition. 37.5 to 50% by mass, and the weight average fiber length of (B) is 200 to 500 μm. [Selection diagram] Fig. 1

Description

The present invention relates to resin compositions and planar connectors.

A liquid crystal polymer such as a totally aromatic polyester is a thermoplastic resin having excellent dimensional accuracy, fluidity, and the like. Due to these characteristics, liquid crystal polymers have been adopted as materials for various electronic components.

In particular, with the recent improvement in the performance of electronic devices, there is a need for electronic components (connectors, etc.) having a fine structure or the like. In order to meet such needs, for example, Patent Document 1 states that it is molded from a resin composition containing a predetermined liquid crystal polymer, glass fiber and plate-like filler, and has excellent flatness, weld strength and crack resistance. A resin composition for obtaining a planar connector is disclosed.

Japanese Unexamined Patent Publication No. 2014-237740

Sublimated products may be generated in the total aromatic polyester during the polymerization reaction. Such a sublimated product may be precipitated and deposited on the inner wall of the polymerization vessel or the like, and polycondensed, deteriorated, or carbonized there may be mixed in the polymer as a foreign substance. 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. Further, in an electronic component having a fine structure such as a planar connector having a lattice structure inside an outer frame represented by a CPU socket, foreign matter may be a starting point and cracks may occur.

An object of the present invention is to provide a resin composition capable of obtaining a flat connector having less foreign matter mixed in and excellent in flatness, weld strength and crack resistance, and a flat connector using the resin composition. And.

［２］構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）の合計の含有量が、（Ａ）全芳香族ポリエステルの全構成単位に対して１００モル％である、［１］に記載の樹脂組成物。
［３］前記（Ｂ）繊維状充填剤がガラス繊維を含む、［１］又は［２］に記載の樹脂組成物。
［４］前記（Ｃ）板状充填剤が、タルク及びマイカからなる群より選ばれる１以上を含む、［１］から［３］のいずれかに記載の樹脂組成物。
［５］前記（Ｃ）板状充填剤が、タルクを含む、［１］から［４］のいずれかに記載の樹脂組成物。
［６］コネクター製造用である、［１］から［５］のいずれかに記載の樹脂組成物。
［７］コネクターを製造するための、［１］から［５］のいずれかに記載の樹脂組成物の使用。
［８］［１］から［５］のいずれかに記載の樹脂組成物を含む、成形品。
［９］［１］から［５］のいずれかに記載の樹脂組成物を含み、外枠部と外枠部の内側に形成された格子構造を有し、前記格子構造における格子部のピッチが１．５ｍｍ以下である、平面状コネクター。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 has the following constituent units as essential constituents. It contains (I) to (IV), the content of the constituent unit (I) is 40 to 75 mol%, and the content of the constituent 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 constituent unit (IV) is 0.150 mol% or less.
The content of (A) total aromatic polyester is 50 to 62.5% by mass with respect to the entire resin composition, and the content of (B) fibrous filler is 10 to 25% by mass with respect to the entire resin composition. %, The content of (C) plate-like filler is 25 to 40% by mass with respect to the entire resin composition, and the total amount of (B) fibrous filler and (C) plate-like filler is the resin composition. A resin composition having a weight average fiber length of 37.5 to 50% by mass and (B) a fibrous filler having a weight average fiber length of 200 to 500 μm with respect to the entire product.

[2] 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, [1]. The resin composition according to.
[3] The resin composition according to [1] or [2], wherein the (B) fibrous filler contains glass fibers.
[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], wherein the (C) plate-like filler contains talc.
[6] The resin composition according to any one of [1] to [5], which is used for manufacturing a connector.
[7] Use of the resin composition according to any one of [1] to [5] for manufacturing a connector.
[8] A molded product containing the resin composition according to any one of [1] to [5].
[9] The resin composition according to any one of [1] to [5] is contained, and the outer frame portion and the lattice portion formed inside the outer frame portion have a lattice structure, and the pitch of the lattice portions in the lattice structure is A cubic connector that is 1.5 mm or less.

According to the present invention, there is provided a resin composition capable of obtaining a flat connector having less foreign matter mixed in and excellent in flatness, weld strength and crack resistance, and a flat connector using the resin composition. be able to.

It is a figure which shows the planar connector molded in an Example. (A) is a plan view of a planar connector. (B) is the details of part A in (a). 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 an electronic component having a fine structure.

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 building block (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 constituent unit (II) with respect to all the constituent units. If the content of the structural unit (II) is less than 0.5 mol%, solidification occurs during polymerization of a molded product such as a planar connector, 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 device and heat resistance is provided. 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 mol%. 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 the structural unit (IV) with respect to the total structural unit. If the content of the structural unit (IV) is less than 8.5 mol% or more than 30 mol%, at least one of lower 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.

In the total aromatic polyester, the difference between the content of the structural unit (III) and the content of the structural unit (IV) is 0.150 mol% or less. By making the difference between the content of the constituent unit (III) and the content of the constituent unit (IV) 0.150 mol% or less, it is possible to suppress the generation of sublimated products during the polymerization reaction, thereby injecting. Gate clogging during molding can be reduced. In addition, it is possible to reduce the mixing of foreign substances into the resin composition, and it is possible to prevent the obtained molded product such as a flat connector from causing poor continuity.
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 compounding amount of the monomer, for example, at the time of 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. For example, the temperature at the time of the polymerization reaction can be raised from 140 ° C. to 360 ° C. in two or more steps or three or more steps.
In one embodiment, the temperature is raised by changing the temperature rising rate (for example, increasing the temperature rising 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 the total aromatic polyester 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, it is generally an index of processability to exhibit liquid crystallinity at a temperature above the melting point. 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 substance 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 substance 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 a total 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, an acylating agent for the polymerized monomer or a monomer having an activated terminal can be used as an acid chloride derivative during the polymerization. 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) Metal salt-based catalysts such as cobalt (III) and organic compound-based catalysts such as 1-methylimidazole and 4-dimethylaminopyridine can be mentioned.

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 50 to 62.5% by mass in the total resin composition. By setting the content of the total aromatic polyester in the range of 50 to 62.5% by mass, the excellent fluidity, rigidity, mechanical strength, heat resistance, chemical resistance, electrical properties, etc. of the liquid crystal resin can be improved. It can be fully expressed. The content of the total aromatic polyester in the resin composition is preferably 50 to 60% by mass, more preferably 52.5 to 60% by mass, from the viewpoint of heat resistance, high rigidity and high fluidity. Particularly preferably, it is 54.3 to 59.7% by mass.

((B) Fibrous filler)
The resin composition comprises a fibrous filler. By including the fibrous filler, the weld strength of the molded product can be improved and the number of cracks can be reduced. The fibrous filler is not particularly limited, and examples thereof include glass fiber, carbon fiber, asbestos fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber and the like. Be done. The fibrous filler is preferably glass fiber because the heat resistance, weld strength and crack resistance of a molded product such as a flat connector obtained from the resin composition can be easily improved.

The weight average fiber length of the fibrous filler is 200 to 500 μm. By using a fibrous filler having a weight average fiber length of 200 to 500 μm, it is possible to improve the crack resistance of molded products such as planar connectors obtained from the fat composition while maintaining the fluidity of the resin composition. ..
The weight average fiber length of the fibrous filler is preferably 300 to 500 μm, more preferably 350 to 480 μm, and even more preferably 400 to 480 μm.

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 to obtain an incinerated residue. The stereoscopic microscope images of 100 images are taken from the 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 10 to 25% by mass with respect to the entire resin composition. When the content of the fibrous filler is less than 10% by mass with respect to the entire resin composition, the weld strength of the molded product obtained from the resin composition is low, and the molded product is a flat connector or the like. , Cracks are likely to occur in the lattice part and the like. When the content of the fibrous filler is more than 25% by mass with respect to the entire resin composition, the fluidity of the composition is deteriorated, and the obtained molded product is inferior in flatness and may have distortion.
The content of the fibrous filler is preferably 10 to 23% by mass, more preferably 10 to 22% by mass, and further preferably 10 to 20% by mass with respect to the entire resin composition.

((C) Plate-shaped filler)
The resin composition contains a plate-like filler. By including the plate-like inorganic filler in the resin composition together with the above-mentioned fibrous filler, a molded product having excellent flatness, crack resistance and weld strength can be molded without deteriorating the fluidity of the resin composition. A resin composition that can be obtained is obtained.
Examples of the plate-shaped 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 Talk 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 pulverization method and a dry pulverization method are known as methods for pulverizing 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 flocculants, 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.
The 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.

The 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 tends 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.

The 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 25 to 40% by mass with respect to the entire resin composition. If the content of the plate-shaped filler is less than 25% by mass with respect to the entire resin composition, the flatness of the molded product such as the flat connector obtained from the resin composition is not sufficient, which is not preferable. If the content of the plate-shaped filler is more than 40% 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-like filler is preferably 25 to 38% by mass, more preferably 25 to 37% by mass, and further preferably 25 to 35% by mass with respect to the entire resin composition.

(Total amount of fibrous filler and plate filler)
In the resin composition, the total amount of the fibrous filler and the plate-like filler is 37.5 to 50% by mass with respect to the entire resin composition. When the total amount is less than 37.5% by mass with respect to the entire resin composition, the molded product such as a planar connector obtained from the resin composition has a low deflection temperature under load, insufficient high-temperature rigidity, and is not sufficient. , It is not preferable because the flatness may be insufficient. If the total amount exceeds 50% by mass with respect to the entire resin composition, the fluidity of the resin composition deteriorates, and the moldability when manufacturing small and thin molded products such as flat connectors is inferior. Not preferable. The total amount is preferably 40 to 50% by mass, more preferably 40 to 47.5% by mass, and further preferably 40 to 45% 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. 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 easily reduced and the flat surface is excellent in crack resistance. Easy to get a shape connector. 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 fired 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.
Further, the resin composition includes a liquid crystal resin other than the above-mentioned all aromatic polyester, a polyphenylene sulfide resin, a polysulfone resin, a polyether sulfone resin, a polyether ether ketone resin, a polyallyl sulfone resin, a thermoplastic polyimide resin, and a 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, and can also 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 a connector, particularly a component having a small and fine lattice structure such as a planar connector or the like. Etc. 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 planar 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), which is preferable in that the fluidity of the resin composition is ensured and the filling pressure does not become excessive at the time of molding the connector, particularly the planar connector.

Since the resin composition according to the present embodiment described above contains a totally 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.

(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)
Since the resin composition according to the present embodiment can produce a molded product having excellent fluidity and heat resistance, a connector, a CPU socket, a relay switch component, a bobbin, an actuator, a noise reduction filter case, and an electronic circuit can be manufactured. It can be preferably used for manufacturing a substrate or a heat fixing roll for OA equipment. In particular, since it is possible to manufacture a molded product having excellent flatness, weld strength and crack resistance, it can be preferably used for manufacturing a connector having a fine structure such as a flat connector.

[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 a resin composition, it can be a molded product having excellent flatness, weld strength and crack resistance.

[Plane connector]
The planar 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 can be a flat connector having excellent flatness, weld strength and crack resistance. Further, since the amount of foreign matter mixed in is small, it is possible to prevent poor continuity and the occurrence of cracks originating from the foreign matter.

The shape of the planar connector is not particularly limited, but may be a planar connector having a lattice structure inside the outer frame portion and having a pitch interval of the lattice portions of 1.5 mm or less in the lattice structure.
In one embodiment, the planar connector has an outer frame portion and a lattice structure formed inside (in the plate surface direction) of the outer frame portion, and the pitch of the lattice portions in the lattice structure is 1.5 mm or less. It is preferably 1.3 mm or less, and more preferably 1.2 mm or less.
In the "lattice structure", a plurality of through holes (pin insertion holes) are formed at predetermined intervals in the vertical direction and the horizontal direction by a plurality of resin portions extending in the vertical direction and the horizontal direction of the plate surface of the planar connector. Means the structure that exists.
"Lattice portion" means a portion including one through hole and a resin portion between the through hole and the adjacent through hole.
The "pitch" is the sum of the width of the resin portion of the lattice portion constituting the lattice structure and the width of the through hole. The width of the through hole is the longest linear distance (interval) between adjacent resin portions.
Further, the width of the resin portion of the lattice portion that holds the terminals in the planar connector is preferably 0.5 mm or less, more preferably 0.3 mm or less, still more preferably 0.2 mm or less, and the height (thickness) of the entire product. It may be a very thin flat connector having a thickness of 5.0 mm or less, more preferably 3.0 mm or less, still more preferably 2.0 mm or less, and particularly preferably 1.0 mm or less.
As a specific shape of the planar connector, for example, the one shown in FIG. 1 can be mentioned.

The planar connector 10 shown in FIG. 1 has a plate shape of 39.82 mm × 39.82 mm × height (thickness) 1.0 mm, 5.0 mm from the upper and lower ends of the outer frame portion 1, and left and right ends, respectively. It has a lattice structure 3 inside (inside) from a position of 2.0 mm from each. The lattice structure 3 includes a lattice portion 2 composed of a resin portion formed of a conductive material and a pin insertion hole, and has a pitch interval of 1.2 mm and 30 columns × 25 rows inside the outer frame portion 1. (A total of 750 pieces) of lattice portions 2 are formed. The number of the lattice portions 2 can be selected as needed, and can be, for example, 500 to 1000.
The shape of the pin insertion hole in the lattice portion of the planar connector is not particularly limited, and may be a square, round, irregular hole, or the like.

The molding method for obtaining a flat connector is not particularly limited, but in order to prevent deformation of the obtained flat connector and obtain a flat connector having good flatness, a molding condition with a small residual internal stress should be selected. Is preferable. In order to lower the filling pressure and reduce the residual internal stress of the obtained planar connector, the cylinder temperature of the molding machine is preferably a temperature equal to or higher than the melting point of the liquid crystal polymer.

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 flat connector suppresses the entry of 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 planar 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.

Blister generation is suppressed in the flat 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 flat connector has excellent flatness with suppressed deformation and warpage. For the flatness of the connector, place the connector on a horizontal desk, measure the height of the flat connector with an image measuring device, measure 0.5 mm from the end face of the connector at 10 mm intervals, and measure the maximum height. Specified as the difference between and the minimum height.

The flat connector has excellent weld strength and crack resistance. Although the weld strength and crack resistance of the molded product correlate with each other, a flat connector having good weld strength and crack resistance can be obtained.

The connector is excellent in 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.

Hereinafter, the present invention will be described in more detail with reference to Examples, 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) 0.883 mol (48 mol%) of 6-hydroxy-2-naphthoic acid (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. After that, the temperature is further raised under the speed conditions shown in Table 1 (that is, the temperature is raised from 140 ° C. to 200 ° C. at a heating rate of 0.6 ° C./min, and then to 270 ° C. at a heating rate of 1 ° C./min. Then, the temperature is raised to 360 ° C. at a heating rate of 0.5 ° C./min), and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 20 minutes to remove acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was carried out while distilling. 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. rice field. 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 2-8]
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 / or 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 / or 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 PerkinElmer), (Tm1 + 40). ) After holding at a temperature of 20 ° C for 2 minutes, once cooled to room temperature under a temperature lowering 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. bottom.

(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, a total aromatic polyester is heated in the presence of tetramethylammonium hydroxide (TMAH) using a pyrolysis device (“PY2020iD” manufactured by Frontier Lab Co., Ltd.), 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 components shown in Table 1 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.
The fillers used in Examples and Comparative Examples are as follows.
Fibrous filler Glass fiber: Nippon Electric Glass Co., Ltd., "ECS03T-786", fiber diameter 10 μm, average fiber length 3 mm (manufacturer's nominal value)
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)
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.
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 2-9, Comparative Examples 1-8]
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.
[Comparative Examples 9 to 18]
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 in which about 100 fibrous fillers of the ashing residue were taken was taken into a PC from a CCD camera 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. The results are shown in Tables 1 and 2 as "weight average fiber length".

(Melting 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 1-3, 5-7, 9-14: 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): 1 piece / g or more.

(Weld strength)
The resin composition was injection-molded on a test piece for measurement (125 mm × 13 mm × 0.4 mm, 2-point film gate) under the following molding conditions. The weld strength of the obtained test piece was measured under the following measurement conditions.
<Molding conditions>
Molding machine; Sumitomo Heavy Industries SE100DU
Cylinder temperature;
370 ° C (Examples 1 to 7, Example 9, Comparative Examples 1 to 7, Comparative Examples 9 to 18)
340 ° C (Example 8, Comparative Example 8)
Mold temperature; 90 ° C
Injection speed; 200 mm / sec
Holding pressure; 70 MPa
<Measurement conditions>
Measuring machine: RTM-100 manufactured by Orientec Tensilon universal tester
Load cell; 100 kg
Distance between chucks; 2.5 mm
Chuck force; 2.0 kgf / cm2
Tensile speed; 0.5 mm / min

Evaluation was made according to the following criteria.
3 (excellent): The weld strength was 8.0 MPa or more.
2 (Good): The weld strength was 6.0 MPa or more and less than 8.0 MPa.
1 (defective): The weld strength was less than 6.0 MPa.

(Crack resistance)
IR reflow was performed on the planar connector shown in FIG. 1 under the following conditions, the grid portion was observed with an optical microscope, and the number of cracks was measured. The smaller the number of cracks, the higher the crack resistance.
<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 min
Temperature conditions;
Preheat zone; 150 ° C
Reflow zone; 240 ° C
Peak temperature; 260 ° C

Evaluation was made according to the following criteria.
3 (excellent): The number of cracks generated in one product is less than 4.
2 (Good): The number of cracks generated in one product is 4 or more and less than 8.
1 (defective): The number of cracks generated in one product is 8 or more.

(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, Example 9, Comparative Examples 1 to 7, Comparative Examples 9 to 18)
340 ° C (Example 8, Comparative Example 8)
Mold temperature: 80 ° C
Injection speed: 33 mm / sec

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 blister 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, Example 9, Comparative Examples 1 to 7, Comparative Examples 9 to 18)
340 ° C (Example 8, Comparative Example 8)
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.

(Connector flatness)
The resin composition has the shape shown in FIG. 1, the overall size is 39.82 mm × 39.82 mm × 1 mmt, and the grid portion pitch interval is 1.2 mm. ) Was injection-molded under the following molding conditions. As the gate, a film gate from the long side of the lattice portion was used, and the gate thickness was set to 0.3 mm.
<Molding conditions>
Molding machine; Sumitomo Heavy Industries SE100DUZ
Cylinder temperature;
370 ° C (Examples 1 to 7, Example 9, Comparative Examples 1 to 7, Comparative Examples 9 to 18)
340 ° C (Example 8, Comparative Example 8)
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 device. At that time, the position of 0.5 mm from the end face of the connector was measured at intervals of 10 mm, and the difference between the maximum height and the minimum height was specified as the flatness. The lower the flatness value, the flatter the connector.
The flatness was measured before and after IR reflow performed under the following conditions, and evaluated according to the following criteria.
<IR reflow conditions>
Measuring machine: Large desktop reflow soldering device RF-300 (using far-infrared heater) manufactured by Japan Pulse Technology Laboratory
Sample feed rate: 140 mm / sec
Reflow furnace transit time: 5 min
Preheat zone temperature conditions: 150 ° C
Reflow zone temperature conditions: 240 ° C
Peak temperature: 260 ° C

(Connector flatness before reflow)
2 (Good): The difference between the maximum height and the minimum height was 0.12 mm or less.
1 (defective): The difference between the maximum height and the minimum height was more than 0.12 mm.

(Difference in connector flatness before and after reflow)
2 (Good): The difference in flatness before and after reflow was 0.06 mm or less.
1 (defective): The difference in flatness before and after reflow was more than 0.06 mm.

(Minimum filling pressure for planar connector)
When the planar connector of FIG. 1 was injection-molded at 365 ° C., the minimum injection filling pressure for obtaining a good molded product 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 molded products: gate clogging)
Using the mold shown in FIG. 2, 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, Example 9, Comparative Examples 1 to 7, Comparative Examples 9 to 18)
340 ° C (Example 8, Comparative Example 8)
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 compositions obtained in the examples can produce a planar connector having excellent fluidity, less contamination with foreign substances, and less warpage and / or deformation. The connector formed from this resin composition was excellent in flatness, weld strength and crack resistance, and blister generation was suppressed.

10 Flat connector 1 Outer frame part 2 Lattice part 3 Lattice structure

Claims (9)

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 constituent units (I) to (IV) as essential constituents, and the content of the constituent units (I) is 40 to 75 mol% with respect to all the constituent 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 content of the total aromatic polyester is 50 to 62.5% by mass with respect to the entire resin composition.
(B) The content of the fibrous filler is 10 to 25% by mass with respect to the entire resin composition.
(C) The content of the plate-shaped filler is 25 to 40% by mass with respect to the entire resin composition.
The total amount of the (B) fibrous filler and (C) plate-like filler is 37.5 to 50% by mass with respect to the entire resin composition.
(B) A resin composition having a weight average fiber length of the fibrous filler of 200 to 500 μm.

1. Resin composition. The resin composition according to claim 1 or 2, wherein the fibrous filler (B) contains glass fiber. The resin composition according to any one of claims 1 to 3, wherein the plate-shaped filler (C) 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, wherein the plate-shaped filler (C) contains talc. The resin composition according to any one of claims 1 to 5, which is used for manufacturing a connector. Use of the resin composition according to any one of claims 1 to 5 for manufacturing a connector. A molded product containing the resin composition according to any one of claims 1 to 5. It contains the resin composition according to any one of claims 1 to 5, and has an outer frame portion and a lattice structure formed inside the outer frame portion.
A planar connector in which the pitch of the lattice portion in the lattice structure is 1.5 mm or less.

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