JP5826404B2 - Composite resin composition and planar connector molded from the composite resin composition - Google Patents

Description

  The present invention relates to a composite resin composition and a planar connector molded from the composite resin composition.

  The liquid crystalline polymer is a thermoplastic resin excellent in dimensional accuracy, fluidity, and the like. Due to these characteristics, liquid crystalline polymers have been conventionally employed as materials for various electronic components.

  In particular, with the recent improvement in performance of electronic equipment, there is a need for electronic parts (such as connectors) having high heat resistance. For example, Patent Document 1 discloses a planar connector molded from a liquid crystalline polymer composition reinforced with glass fibers. Patent Document 2 discloses a planar connector molded from a liquid crystalline polymer composition reinforced with glass fiber and talc. Such a connector is employed as a planar connector (such as a CPU socket) having a lattice structure inside the outer frame, which requires high heat resistance and the like.

  In recent years, with the increase in the integration rate of planar connectors, the shape required for planar connectors has changed. For example, as the shape of the planar connector, an increase in the number of connector pins, a shape in which the width of the lattice portion is thinner, and the like are required.

JP 2005-276758 A JP 2010-3661 A

  However, when a planar connector that meets the above-mentioned needs is molded from a composition containing a conventional liquid crystalline polymer, the fluidity of the composition is not sufficient and the processability is inferior. Cracks (also referred to as “cracks”) may occur in the part. Accordingly, it has been difficult to obtain a planar connector having high crack resistance. It is also difficult to obtain a planar connector having sufficient flatness and reduced warpage deformation.

  The present invention has been made in view of such circumstances, a composite resin composition capable of obtaining a planar connector having excellent flatness and fluidity, suppressing warpage deformation, and excellent crack resistance, And it aims at providing the planar connector shape | molded from the said composite resin composition.

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

(1) A composite resin composition comprising (A) a liquid crystalline polymer, (B) glass fiber, and (C) one or more inorganic fillers selected from the group consisting of talc and milled fiber,
The (A) liquid crystalline polymer has the following constituent units as essential constituents: (I) 4-hydroxybenzoic acid, (II) 2-hydroxy-6-naphthoic acid, (III) terephthalic acid, (IV) Including isophthalic acid and (V) 4,4′-dihydroxybiphenyl,
The structural unit of (I) is 35 to 75 mol% with respect to all the structural units,
The structural unit of (II) is 2 to 8 mol% with respect to all the structural units,
The structural unit of (III) is 4.5 to 30.5 mol% with respect to all structural units,
The structural unit of (IV) is 2 to 8 mol% with respect to all the structural units,
The structural unit of (V) is 12.5 to 32.5 mol% with respect to all the structural units,
The total amount of the structural units (II) and (IV) is 4 to 10 mol% with respect to all the structural units,
The (A) liquid crystalline polymer is 45 to 60% by mass with respect to the entire composite resin composition,
Said (B) glass fiber is 35-50 mass% with respect to the whole composite resin composition,
The (C) one or more inorganic fillers selected from the group consisting of talc and milled fiber is a composite resin composition that is 0 to 15% by mass with respect to the entire composite resin composition.

  (2) The composite resin composition according to (1), wherein an average glass fiber length of the fiber length of the (B) glass fiber and the fiber length of the (C) milled fiber is 200 to 500 μm.

(3) Molded from the composite resin composition according to (1) or (2),
It has a lattice structure inside the outer frame portion, has an opening inside the lattice structure,
The pitch interval of the lattice portions in the lattice structure is 1.5 mm or less,
The thickness ratio of the outer frame portion and the lattice portion is 1.0 or less,
A planar connector with a pin insertion hole that has an irregular shape.

  (4) The planar connector according to (3), wherein the flexural modulus measured according to ISO 178 is 17 GPa or more.

  According to the present invention, the flatness and fluidity are good, warpage deformation is suppressed, and a planar connector having excellent crack resistance is obtained, and the composite resin composition is molded from the composite resin composition. A flat connector is provided.

It is a figure which shows the planar connector shape | molded in the Example, (a) is a top view, (b) is a right view. In addition, the unit of the numerical value in a figure is mm. It is a figure which shows the gate position of the planar connector shape | molded in the Example, (a) is a top view, (b) is a right view. In addition, the unit of the numerical value in a figure is mm. It is a figure which shows the measuring point in the measurement of the connector flatness performed in the Example. In addition, the unit of the numerical value in a figure is mm. It is a figure which shows the injection molded product for evaluation used in the crack-resistant evaluation performed in the Example. In addition, the unit of the numerical value in a figure is mm. It is a figure which shows the example of the shape of the pin insertion hole which is a deformed hole in the grating | lattice part of the planar connector of this invention.

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

[Composite resin composition]
The composite resin composition of the present invention contains a predetermined amount of a specific liquid crystalline polymer, glass fiber, and inorganic filler. Hereinafter, the components constituting the composite resin composition of the present invention will be described.

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

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

  When the constituent unit of (I) is less than 35 mol% or more than 75 mol% with respect to all the constituent units, the melting point of the liquid crystalline polymer becomes remarkably high, and liquid crystallinity is produced in the production of molded products such as planar connectors. This is not preferable because the polymer may solidify in the reactor and a liquid crystalline polymer having a desired molecular weight may not be produced.

  When the amount of the structural unit (II) is less than 2 mol% with respect to all the structural units, there is a possibility that cracks may occur in the lattice portion or the like when a molded product such as a planar connector is produced. Moreover, when the structural unit of (II) exceeds 8 mol% with respect to all the structural units, since the heat resistance of a liquid crystalline polymer will become low, it is unpreferable.

  When the constituent unit of (III) is less than 4.5 mol% or more than 30.5 mol% with respect to all the constituent units, the melting point of the liquid crystalline polymer becomes remarkably high, and a molded product such as a planar connector is produced. At this time, the liquid crystalline polymer is solidified in the reactor, and it may not be possible to produce a liquid crystalline polymer having a desired molecular weight.

  If the structural unit (IV) is less than 2 mol% with respect to all the structural units, cracks may occur in the lattice portion or the like when a molded product such as a planar connector is produced, which is not preferable. Moreover, when the structural unit of (IV) exceeds 8 mol% with respect to all the structural units, since the heat resistance of a liquid crystalline polymer will become low, it is unpreferable.

  When the constituent unit of (V) is less than 12.5 mol% or more than 32.5 mol% with respect to all the constituent units, the melting point of the liquid crystalline polymer becomes remarkably high, and a molded product such as a planar connector is produced. At this time, the liquid crystalline polymer is solidified in the reactor, which makes it impossible to produce a liquid crystalline polymer having a desired molecular weight.

  When the total amount of the structural units (II) and (IV) is less than 4 mol% with respect to all the structural units, the crystallization heat amount of the liquid crystalline polymer can be 2.5 J / g or more. In this case, when a molded product such as a planar connector is manufactured, cracks may occur in the lattice portion and the like, which is not preferable. A preferable value for the heat of crystallization of the liquid crystalline polymer is 2.3 J / g or less, and more preferably 2.0 J / g or less. The crystallization heat quantity indicates the crystallization state of the liquid crystalline polymer, and is a value obtained by differential calorimetry. Specifically, after observing the endothermic peak temperature (Tm1) observed when the liquid crystalline polymer is measured from room temperature at a temperature rising condition of 20 ° C./min, the liquid crystal polymer is held at a temperature of Tm1 + 40 ° C. for 2 minutes, and then 20 ° C. It refers to the calorific value of the exothermic peak obtained from the peak of the exothermic peak temperature observed when measured under the temperature lowering condition per minute.

  Moreover, it is not preferable that the total amount of the structural units (II) and (IV) exceeds 10 mol% with respect to all the structural units because the heat resistance of the liquid crystalline polymer is lowered.

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

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

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

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

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

  The polymerization reaction may be a method (one-step system) in which all the raw material monomers, the acylating agent and the catalyst are charged in the same reaction vessel and the reaction is started, and the hydroxyl groups of the raw material monomers (I), (II) and (V) are acylated. A method of reacting with the carboxyl groups of (III) and (IV) (two-stage system) after acylation with an agent may be used.

  Some liquid crystalline polymers obtained from the structural units (I) to (V) do not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the liquid crystalline polymer. In terms of having easy processability, the liquid crystalline polymer in the present invention is preferably one that forms an anisotropic molten phase, that is, a liquid crystalline polymer that exhibits optical anisotropy when melted.

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

Furthermore, the melt viscosity of the liquid crystalline polymer at a shear rate of 1000 / second at a temperature 10 to 40 ° C. higher than the melting point is 1 × 10 ⁵ Pa · s or less (more preferably ⁵ Pa · s or more and 1 × 10 ² Pa · s. s or less) is preferable in that the fluidity of the composite resin composition is ensured and the filling pressure does not become excessive at the time of forming the lattice portion of the planar connector.

  The composite resin composition of this invention contains 45-60 mass% of said liquid crystalline polymer with respect to the whole composite resin composition in a composite resin composition. If the content of the liquid crystalline polymer is less than 45% by mass relative to the entire composite resin composition, the fluidity deteriorates, which is not preferable. If the content of the liquid crystalline polymer is more than 60% by mass with respect to the entire composite resin composition, the bending elastic modulus and crack resistance of a molded product such as a planar connector obtained from the composite resin composition are reduced. It is not preferable. It is preferable that the composite resin composition of this invention contains 50-60 mass% of said liquid crystalline polymer with respect to the whole composite resin composition in a composite resin composition.

(Glass fiber)
Since the composite resin composition of the present invention contains the above liquid crystalline polymer and glass fiber, a molded product obtained by molding the composite resin composition has high crack resistance.

  The composite resin composition of this invention contains 35-50 mass% of glass fiber with respect to the whole composite resin composition in a composite resin composition. When the glass fiber content is less than 35% by mass with respect to the entire composite resin composition, the flexural modulus of the molded product obtained from the composite resin composition is low, and the molded product is a planar connector or the like. Is not preferable because cracks may occur in the lattice portion. If the glass fiber content is more than 50% by mass relative to the entire composite resin composition, the fluidity of the composition deteriorates, which is not preferable. It is preferable that the glass fiber in this invention is contained in 40-50 mass% with respect to the whole composite resin composition in a composite resin composition.

(Inorganic filler)
The composite resin composition of the present invention further includes one or more inorganic fillers selected from the group consisting of talc and milled fiber. By including these components in the composite resin composition together with the glass fibers, it is possible to obtain a molded body in which warpage deformation is suppressed without deteriorating the fluidity of the composite resin composition. The total amount of these components is 0 to 15% by mass with respect to the entire composite resin composition.

  In the composite resin composition of the present invention, the average glass fiber length calculated from the fiber length of the glass fiber and the fiber length of the milled fiber among the inorganic fillers is preferably 200 to 500 μm. An average fiber length of less than 200 μm is not preferable because cracks may occur in a lattice portion of a molded product such as a planar connector obtained from the composite resin composition. If the average fiber length is more than 500 μm, the fluidity is deteriorated and it may be difficult to mold the composite resin composition.

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

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

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

  Since the composite resin composition of the present invention is excellent in fluidity, the minimum filling pressure at the time of molding is hardly excessive, and a portion having a complicated shape such as a lattice portion of a planar connector can be preferably molded. The minimum filling pressure is specified as the minimum injection filling pressure at which a good molded product can be obtained at 365 ° C. when molding the composite resin composition.

(Flat connector)
By molding the composite resin composition of the present invention, the planar connector of the present invention can be obtained. The shape of the planar connector is not particularly limited, but has a lattice structure inside the outer frame portion, an opening inside the lattice structure, and a pitch interval of the lattice portion in the lattice structure is 1.5 mm. It may be the following, and the planar connector whose thickness ratio of the said outer frame part and the said grating | lattice part is 1.0 or less may be sufficient. Further, the planar connector may be a very thin planar connector in which the width of the resin portion of the lattice portion holding the terminals in the planar connector is 0.5 mm or less and the total height of the product is 5.0 mm or less.

  Examples of the shape of the planar connector of the present invention include those shown in FIG. This flat connector has an overall size of 43.88 mm × 43.88 mm × 3 mmt, an outer frame portion having a thickness of 3 mm or less, a lattice portion having a thickness of 1.5 mm or less, and 13.88 mm in the center portion. X 13.88 mm opening. Further, the pin insertion hole of the planar connector may be partially narrowed in order to prevent the pin inserted into the planar connector from coming off.

  The shape of the pin insertion hole in the lattice portion of the planar connector of the present invention is not particularly limited, and may be square, round, or the like. Examples of the shape of the pin insertion hole that is preferable in the present invention include shapes other than square and round (referred to as “variant” in the present invention), such as the shape shown in FIG. 5 and the shape of a star. It is done. A pin insertion hole having such a shape (referred to as “an irregularly shaped hole” in the present invention) is not only very difficult to mold, but also easily cracks, and the crack resistance of the molded product tends to decrease. However, the planar connector of the present invention has excellent crack resistance even if the pin insertion hole is an irregular hole. Further, the planar connector of the present invention includes not only one having an opening in the lattice part but also one having no opening in the lattice part.

  The molding method for obtaining the planar connector of the present invention is not particularly limited, but there is no residual internal stress in order to prevent deformation of the obtained planar connector and to obtain a planar connector having good flatness (described later). It is preferable to select the molding conditions. In order to lower the filling pressure and reduce the residual internal stress of the planar connector obtained, the cylinder temperature of the molding machine is preferably a temperature equal to or higher than the melting point of the liquid crystalline polymer.

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

  The planar connector of the present invention has a good flexural modulus and is excellent in crack resistance. The bending elastic modulus of the planar connector of the present invention may be 17 GPa or more. A planar connector having an elastic modulus of 17 GPa or more is hardly cracked even if it has a thin lattice portion, and has excellent crack resistance. In addition, a bending elastic modulus is measured based on ISO178.

  Further, deformation of the planar connector of the present invention is suppressed. The degree of deformation of the planar connector is determined using the flatness of the planar connector as an index. Specifically, the flat connector is placed on a horizontal desk, the height of the flat connector is measured with an image measuring device, and the position of 0.5 mm is measured at 10 mm intervals from the connector end surface. The difference between the height and the minimum height is defined as flatness. In the planar connector of the present invention, the change in flatness is suppressed before and after performing IR reflow.

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

(Method for producing liquid crystalline polymer 1)
A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a pressure reduction / outflow line was charged with the following raw material monomers, a metal catalyst, and an acylating agent, and nitrogen substitution was started.
(I) 2-hydroxy-6-naphthoic acid; 166 g (48 mol%) (HNA)
(II) Terephthalic acid; 76 g (25 mol%) (TA)
(III) 4,4′-dihydroxybiphenyl; 86 g (25 mol%) (BP)
(IV) 4-hydroxybenzoic acid; 5 g (2 mol%) (HBA)
Potassium acetate catalyst; 22.5mg
Acetic anhydride; 191 g

  After the raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further increased to 360 ° C. over 5.5 hours, and then reduced to 5 Torr (ie, 667 Pa) over 30 minutes to melt while distilling acetic acid, excess acetic anhydride, and other low-boiling components. Polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change from a reduced pressure state to a normal pressure through a normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to pelletize. The obtained pellets were heat-treated at 300 ° C. for 8 hours under a nitrogen stream. The melting point of the pellet was 349 ° C., the heat of crystallization was 5.6 J / g, and the melt viscosity was 23 Pa · s.

In this example, the melt viscosity was measured under the following conditions.
A Capillograph Type 1B manufactured by Toyo Seiki Co., Ltd. with L = 20 mm and d = 1 mm was used, and the liquid crystal was liquid crystallized in conformity with ISO 11443 at a shear rate of 1000 / sec. The melt viscosity of the conductive polymer was measured.

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

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

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

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

(Components other than liquid crystalline polymers)
Each liquid crystalline polymer obtained above and the following components were mixed using a twin screw extruder to obtain a composite resin composition. The amount of each component is as shown in Tables 1 and 2. Hereinafter, “%” in the table represents mass%.
Glass fiber: ECS03T-786H manufactured by Nippon Electric Glass Co., Ltd., chopped strand talc having a fiber diameter of 10 μm and a length of 3 mm; Crown talc PP manufactured by Matsumura Sangyo Co., Ltd., average particle diameter of 10 μm
Milled fiber: PF70E001 manufactured by Nittobo Co., Ltd., fiber diameter 10 μm, fiber length 70 μm

  Based on the following method, the physical properties of the obtained liquid crystalline polymer or planar connector were measured. Each evaluation result is shown in Tables 1 and 2.

(Average glass fiber length)
5 g of the composite resin composition pellets were heated and ashed at 600 ° C. for 2 hours. The incineration residue was sufficiently dispersed in a 5% aqueous polyethylene glycol solution, then transferred to a petri dish with a dropper, and the glass fiber was observed with a microscope. Simultaneously, the weight average fiber length of the glass fiber was measured using an image measuring device (LUZEXFS manufactured by Nireco Corporation). In addition, about the composition containing a milled fiber, an average glass fiber length points out the average of the fiber length of glass fiber and a milled fiber.

(Flexural modulus)
The composite resin composition was injection molded under the following molding conditions, and the flexural modulus was measured according to ISO178.
[Molding condition]
Molding machine: Sumitomo Heavy Industries SE100DU
Cylinder temperature (indicates temperature from nozzle side);
360 ° C.-370 ° C.-370 ° C.-360 ° C.-340 ° C.-330 ° C. (Examples 1-6, Comparative Examples 3-7)
370 ° C.-370 ° C.-370 ° C.-370 ° C.-370 ° C.-380 ° C. (Comparative Example 1)
350 ° C-350 ° C-350 ° C-350 ° C-340 ° C-330 ° C (Comparative Example 2)
Mold temperature: 80 ℃
Injection speed: 2m / min
Holding pressure: 50 MPa
Holding time: 2 sec
Cooling time: 10 sec
Screw rotation speed: 120rpm
Screw back pressure: 1.2 MPa

(Connector flatness)
As shown in FIG. 1, the composite resin composition has an overall size of 43.88 mm × 43.88 mm × 3 mmt, an opening of 13.88 mm × 13.88 mm in the center, and a lattice pitch of 1.0 mm. The flat connector (number of pin holes: 1248) was injection molded. As the gate, a special gate (overflow) shown in FIG. 2 was used.

  The obtained connector was placed on a horizontal desk, and the height of the connector was measured by Mitutoyo Quick Vision 404 PROCNC image measuring device. At that time, as shown in FIG. 3, 0.5 mm positions were measured at 10 mm intervals from the connector end face, and the difference between the maximum height and the minimum height from the least square plane was defined as flatness.

(Connector deformation amount)
IR reflow was performed under the following conditions, the flatness was measured by the method described above, and the difference in flatness of the flat connector before and after reflow was determined as the amount of connector deformation.
[IR reflow conditions]
Measuring instrument: Nippon-Pulse R & D Laboratories large-size desktop reflow soldering device RF-300 (far infrared heater used)
Sample feed rate: 140 mm / sec Reflow furnace passage time: 5 minutes Preheating zone temperature condition: 150 ° C.
Reflow zone temperature condition; 225 ° C
Peak temperature: 287 ° C
[Molding condition]
Molding machine; Sumitomo Heavy Industries SE30DUZ
Cylinder temperature (indicates temperature from nozzle side);
360 ° C.-365 ° C.-340 ° C.-330 ° C. (Examples 1-6, Comparative Examples 3-7)
370 ° C.-370 ° C.-370 ° C.-380 ° C. (Comparative Example 1)
350 ° C.-350 ° C.-340 ° C.-330 ° C. (Comparative Example 2)
Mold temperature: 80 ℃
Injection speed: 300mm / sec
Holding pressure: 50 MPa
Holding time: 2 sec
Cooling time: 10 sec
Screw rotation speed: 120rpm
Screw back pressure: 1.2 MPa

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

(Crack resistance)
The evaluation injection-molded product shown in FIG. 4 has an outer diameter of 23.6 mm, 31 holes of φ3.2 mm inside, and a minimum wall thickness of 0.16 mm. A three-point gate indicated by an arrow in FIG. Use a stereomicroscope to observe the cracking of the molded product at a magnification of 5 times, and observe the occurrence of cracks around the hole. If there was a crack in the molded product, “X”; if not, “○” It was judged.
[Molding condition]
Molding machine; Sumitomo Heavy Industries SE30DUZ
Cylinder temperature (indicates temperature from nozzle side);
370 ° C.-375 ° C.-360 ° C.-350 ° C. (Examples 1-6, Comparative Examples 3-7)
360 ° C.-360 ° C.-360 ° C.-370 ° C. (Comparative Example 1)
350 ° C.-350 ° C.-340 ° C.-330 ° C. (Comparative Example 2)
Mold temperature: 140 ° C
Injection speed: 150mm / sec
Holding pressure: 100 MPa
Holding time: 2 sec
Cooling time: 10 sec
Screw rotation speed: 120rpm
Screw back pressure: 1.2 MPa

  As shown in Tables 1 and 2, the planar connector of the present invention was excellent in flatness, warp deformation, fluidity and crack resistance, and had a flexural modulus of 17 GPa or more. Further, when a similar test was performed on a planar connector obtained from the composite resin composition of the present invention, in which the pin insertion hole is a deformed hole (a deformed hole having the shape of FIG. 5), the same preferable results were obtained. Obtained.

Claims (7)

A composite resin composition comprising (A) a liquid crystalline polymer, (B) glass fiber, and (C) one or more inorganic fillers selected from the group consisting of talc and milled fiber,
The (A) liquid crystalline polymer has the following constituent units as essential constituents: (I) 4-hydroxybenzoic acid, (II) 2-hydroxy-6-naphthoic acid, (III) terephthalic acid, (IV) Including isophthalic acid and (V) 4,4′-dihydroxybiphenyl,
The structural unit of (I) is 35 to 75 mol% with respect to all the structural units,
The structural unit of (II) is 2 to 8 mol% with respect to all the structural units,
The structural unit of (III) is 4.5 to 30.5 mol% with respect to all structural units,
The structural unit of (IV) is 2 to 8 mol% with respect to all the structural units,
The structural unit of (V) is 12.5 to 32.5 mol% with respect to all the structural units,
The total amount of the structural units (II) and (IV) is 4 to 10 mol% with respect to all the structural units,
Said (A) liquid crystalline polymer is 45-60 mass% with respect to the whole composite resin composition,
Said (B) glass fiber is 35-50 mass% with respect to the whole composite resin composition,
The (C) one or more inorganic fillers selected from the group consisting of talc and milled fiber is a composite resin composition that is greater than 0 % by mass and less than or equal to 15% by mass with respect to the total composite resin composition.   2. The composite resin composition according to claim 1, wherein an average glass fiber length of the fiber length of the (B) glass fiber and the fiber length of the (C) milled fiber is 200 to 500 μm.   A composite resin composition comprising (A) a liquid crystalline polymer, (B) glass fiber, and (C) one or more inorganic fillers selected from the group consisting of talc and milled fiber,
  The (A) liquid crystalline polymer has the following constituent units as essential constituents: (I) 4-hydroxybenzoic acid, (II) 2-hydroxy-6-naphthoic acid, (III) terephthalic acid, (IV) Including isophthalic acid and (V) 4,4′-dihydroxybiphenyl,
  The structural unit of (I) is 35 to 75 mol% with respect to all the structural units,
  The structural unit of (II) is 2 to 8 mol% with respect to all the structural units,
  The structural unit of (III) is 4.5 to 30.5 mol% with respect to all structural units,
  The structural unit of (IV) is 2 to 8 mol% with respect to all the structural units,
  The structural unit of (V) is 12.5 to 32.5 mol% with respect to all the structural units,
  The total amount of the structural units (II) and (IV) is 4 to 10 mol% with respect to all the structural units,
  Said (A) liquid crystalline polymer is 45-60 mass% with respect to the whole composite resin composition,
  Said (B) glass fiber is 35-50 mass% with respect to the whole composite resin composition,
  The (C) one or more inorganic fillers selected from the group consisting of talc and milled fiber is 0 to 15% by mass with respect to the entire composite resin composition,
  (B) The composite resin composition whose fiber length of a glass fiber is 200-500 micrometers.   The composite resin composition according to claim 3, wherein an average glass fiber length of the fiber length of the (C) milled fiber is 200 to 500 µm. A composite resin composition comprising (A) a liquid crystalline polymer, (B) glass fiber, and (C) one or more inorganic fillers selected from the group consisting of talc and milled fiber,
The (A) liquid crystalline polymer has the following constituent units as essential constituents: (I) 4-hydroxybenzoic acid, (II) 2-hydroxy-6-naphthoic acid, (III) terephthalic acid, (IV) Including isophthalic acid and (V) 4,4′-dihydroxybiphenyl,
The structural unit of (I) is 35 to 75 mol% with respect to all the structural units,
The structural unit of (II) is 2 to 8 mol% with respect to all the structural units,
The structural unit of (III) is 4.5 to 30.5 mol% with respect to all structural units,
The structural unit of (IV) is 2 to 8 mol% with respect to all the structural units,
The structural unit of (V) is 12.5 to 32.5 mol% with respect to all the structural units,
The total amount of the structural units (II) and (IV) is 4 to 10 mol% with respect to all the structural units,
Said (A) liquid crystalline polymer is 45-60 mass% with respect to the whole composite resin composition,
Said (B) glass fiber is 35-50 mass% with respect to the whole composite resin composition,
One or more inorganic fillers selected from the group consisting of (C) talc and milled fiber are molded from a composite resin composition that is 0 to 15% by mass with respect to the total composite resin composition,
It has a lattice structure inside the outer frame portion, and has an opening inside the lattice structure,
The pitch interval of the lattice portions in the lattice structure is 1.5 mm or less,
The thickness ratio of the outer frame part and the lattice part is 1.0 or less,
A planar connector with a pin insertion hole that has an irregular shape.   The planar connector according to claim 5, wherein an average glass fiber length of the fiber length of the (B) glass fiber and the fiber length of the (C) milled fiber is 200 to 500 μm. The planar connector according to claim 5 or 6 , wherein the flexural modulus measured in accordance with ISO 178 is 17 GPa or more.

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